JPH0452640A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To lessen the change in color tone and to enhance chromaticity by specifying the sensitivity of a green sensitive layer and the sensitivity of a red sensitive layer to the prescribed monochromatic light and incorporating a specific coupler into the green sensitive layer. CONSTITUTION:The sensitivity (SG<580>) of the green sensitive emulsion layer and the sensitivity (SR<580>) of the red sensitive emulsion layer of the photographic sensitive material, the ISO sensitivity of which is S, to 580nm monochromatic light measured after this material is uniformly exposed with 2/Slux.sec white light is specified to -0.3<=SG<580>-SR<580=0.3 and the coupler of formula I is provided into this green sensitive layer. In the formula, R1 denotes hydrogen or substituent; Z denotes the nonmetal atom group necessary for forming a 5-membered azole ring contg. 2 to 3 pieces of nitrogen; X denotes hydrogen or elimination group. The compd. of formula II, etc., are usable as the coupler of the formula.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a color photographic material, and in particular to a color photographic material that has excellent color reproducibility even when photographed under daylight but also when photographed using fluorescent lighting. Regarding photographic materials.

(Prior Art) Many efforts have been made to improve the color reproducibility of color photographic light-sensitive materials. For example, in the case of color negative film, color film is used to remove unnecessary absorption of the coloring dye of the coupler. Invention of coupler. JP-A-50-2537
By adding a coupler that reacts with the oxidation product of a developing agent to release a development inhibitor in a para-phenylenediamine color developer disclosed in 2003, the interlayer inhibitory effect has been enhanced and color saturation has been improved. etc. However, the color reproducibility of current color photographic materials also has serious drawbacks and dissatisfaction. One of them is that when photographed under fluorescent lights, the image appears green.

As a known technique for improving the color reproducibility of color photographic materials, US Pat. No. 3,672,898 discloses a method for reducing changes in color reproducibility when photographing under various light sources with different color temperatures. With the spectral sensitivity specified in this patent, the spectral sensitivity of the red-sensitive emulsion layer becomes too short-wave, and green color reproduction tends to deteriorate significantly.

It is also known that pyrazoloazole couplers have little side absorption and are useful for improving color reproduction.

These couplers are described, for example, in U.S. Pat.
No. 7, JP-A-59-171956, JP-A No. 61-5364
No. 4, No. 61-65243, No. 62-186262, No. 63-307453, etc. However, these patents do not specify spectral sensitivity, and this alone makes it impossible to improve color reproducibility under fluorescent light.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color photographic material with high color saturation and little change in color even when used in daylight or under fluorescent light. It is in.

(Means for Solving the Problems) The above object of the present invention is to have one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support. In a silver halide color photographic light-sensitive material having an ISO sensitivity of S, a green-sensitive silver halide emulsion layer with respect to monochromatic light of 580 nm was measured after uniformly exposing the light-sensitive material to white light of 2/51 ux-3 ec. The sensitivity (SG"0) of the red-sensitive silver halide emulsion layer (SR"0) is -〇, 3≦5o510 3
．． S@.

≦0.3, and is achieved by a silver halide photographic light-sensitive material characterized in that the green-sensitive silver halide emulsion layer contains a coupler represented by the following general formula [I].

General formula [■] 8. −Z Here, R1 represents a hydrogen atom or a substituent.

Z represents a nonmetallic atomic group necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a fused ring). X represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent.

The present invention will be explained in detail below.

First, how to obtain S, sho, and 5R610 mentioned here will be explained and defined below. The method for measuring the ISO sensitivity of color photographic materials is 15O5800-1979 (E
). ISO sensitivity is S
By using a light source with the same relative spectral energy distribution as that used to determine the ISO sensitivity of a color photographic light-sensitive material,
Using the same exposure time as when calculating the ISO sensitivity, 2XI/
A uniform exposure is given to the light-sensitive material to be tested with an exposure amount of 5 Jux·sec. At this time, the test was carried out at a temperature of 20±5℃ and a relative humidity of 6.
The test is carried out indoors at a temperature of 0±10%, and the photosensitive material to be tested is left in this state for one hour or more before use. Within one hour after the uniform exposure, exposure using monochromatic light of 560 nm is applied with varying illuminance. As with the measurement of ISO sensitivity, the exposure device is of the non-intermittent exposure/illuminance still type, and changes in illuminance are achieved by a light modulator such as an optical wedge. The exposure time is 1/10 second. Monochromatic light of 580 nm here means that the peak wavelength of relative spectral energy is 580±2
nm and has a half width of 20 nm or less.

To obtain this monochromatic light, a common exposure light source such as a tungsten lamp may be combined with a commercially available interference filter.

After exposure to monochromatic light, the photosensitive material to be tested must be maintained at a temperature of 20±5°C and a relative humidity of 6o±10% until development processing, and development processing must be completed within 30 minutes or more and within 6 hours after exposure. The processing method shall be as recommended by the film manufacturer. Concentration measurements are performed using blue, green, and red filters having the spectral characteristics shown in FIG. 1. The detailed conditions of the measurement method conform to the ISO method.

Photographic sensitivity S. iso, 3. sio is the minimum concentration (
The exposure amount at a point with a density of +0.6 (after giving uniform exposure) is HG530 1 ux @ sec % HR”0
1 ux-see, calculated according to the following formula.

■ The present inventors applied the technology of JP-A-62-160448 in order to obtain design guidelines for a color photographic material that exhibits little change in color tone when photographed under fluorescent light or under daylight. Although we considered this, we were unable to achieve this objective while maintaining color saturation.

The inventors of the present invention focused on the spectral sensitivity distribution of the green-sensitive layer and the red-sensitive layer, since the finish becomes greenish under fluorescent light, and conducted various studies.
. sso 3. It has been found that it is important to keep iio within a certain range. However, when this spectral sensitivity is adopted, the chromaticity, for example, the saturation of green color, decreases.

When a coupler represented by the general formula [I] of the present invention is used as a magenta coupler, the coloring dye thereof has less cyan components on the long wavelength side than the coloring dye of the 5-pyrazolone coupler, so the saturation of green color decreases. It became clear that it would not be possible.

Therefore, as in the present invention, a coupler represented by the general formula [I] is used as a magenta coupler, and the spectral sensitivity distribution of the green-sensitive layer and the red-sensitive layer is set to 0.3≦Sc 530 SR""-0.3. By doing so, we were able to improve the color change under fluorescent light without reducing the color saturation.

In the present invention, the spectral sensitivity distribution of the green-sensitive layer and the red-sensitive layer can be obtained, for example, by using a suitable combination of spectral sensitizing dyes having the structural formulas shown below.

The green-sensitive silver halide emulsion layer of the present invention has the following general formula (
It is particularly preferable to use sensitizing dyes represented by S-I) to (S-VI). These sensitizing dyes may be used alone or in combination of two or more.

General formula (S-I) RI R2 (Xl).

In the formula, Zl and Z2 are tellurazole nucleus, penzotellazole nucleus, naphthotellazole nucleus, quinoline nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus. Represents the atomic group necessary to form the derived nucleus.

R' and R1 represent an alkyl group, and at least one of them is preferably substituted with a sulfo group or a carboxy group. Ll represents a methine group.

Xl represents an anion. nl represents 0 or l,
It is 0 when forming an inner salt.

General formula (S-n) (X2).

In the formula, z3. z' is a telllazole nucleus, a penzotelllazole nucleus, a naphthotellazole nucleus, a benzoxazole nucleus,
Represents a group of atoms necessary to form a nucleus derived from a naphthoxazole nucleus, benzimidazole nucleus, benzothiazole nucleus, naphthoimidazole nucleus, oxazolidine nucleus, oxazole nucleus, thiazolidine nucleus, and selenazolidine nucleus. R
", R' has the same meaning as R', R2. R represents a hydrogen atom, an alkyl group, or an aryl group. L2.L", L'
is synonymous with Ll. X2 has the same meaning as Xl.

n2 is synonymous with nl.

General formula (S-1) 1) Ro In the formula, Z5 is a tellurazole nucleus, a penzotellurazole nucleus,
Naphthotelazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
Represents a group of atoms necessary to form a nucleus derived from a quinoline nucleus, a pyridine nucleus, a thiazole nucleus, and a pyrrolidine nucleus. Z6
represents a group of atoms necessary to form a nucleus derived from a rhodanine nucleus, a 2-thioxooxazolidine nucleus, and a thiohydantoin nucleus. R6 represents an alkyl group.

General formula (S-IV) oxazolidine nucleus, inoxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazolidine nucleus, selenazolidine nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus,
Represents the atomic group necessary to form a nucleus derived from a pyrrolidine nucleus or a tetrazole nucleus. Zs represents an atomic group necessary to form a nucleus derived from a rhodanine nucleus, a thiohydantoin nucleus, a pyrazolone nucleus, a thiobarbyl nucleus, a pyrazolone nucleus, a 2-thioxooxazolidinone nucleus, and a barbyl nucleus. Ls and Ll are synonymous with Ll. R7 has the same meaning as R6.

General formula (S-V) R' In the formula, Z7 is a tellurazole nucleus, a penzotellurazole nucleus,
Naphthotellazole nucleus, oxazole nucleus, R'' where Z9 is tellurazole nucleus, penzotellazole nucleus,
Represents a group of atoms necessary to form a nucleus derived from a naphthotelazole nucleus, a thiazolidine nucleus, and a selenazolidine nucleus.

, 7: 10. Zll represents a group of atoms necessary to form a nucleus derived from a rhodanine nucleus.

R8 has the same meaning as R6.

General formula (S-VI) (X') fi where z 12. zll is oxazolidine nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazolidine nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazolidine nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, tellazole nucleus, pen Represents the atomic group necessary to form a nucleus derived from the zoterlazole nucleus and naphthotelazole nucleus.

R9 and RID have the same meaning as R' and R2. L7L"l
L'lL" is synonymous with Ll. X3X" is synonymous with Xl. n" and n" are synonymous with n. W represents a hydrogen atom, a carboxy group, or a sulfo group. p is 1 to 4
represents an integer.

General formulas (S-I) to (S-VI) will be explained in detail below.

R', R", R", R', R5, R', R'R", R"
, R'' is preferably a hydrogen atom, an unsubstituted alkyl group having 18 or less carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a substituted alkyl group (as a substituent, for example,
Carboxy group, sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxy carbonyl), alkoxy groups having 8 or less carbon atoms (e.g. methoxy, ethoxy, benzyloxy, phenethyloxy), monocyclic aryloxy groups having 1θ or less carbon atoms (e.g. phenoxy, p-tolyloxy), acyloxy groups having 3 or less carbon atoms groups (e.g. acetyloxy, propionyloxy), acyl groups having 8 or less carbon atoms (e.g. acetyl, propyl, benzoyl,
mesyl), carbamoyl groups (e.g. carbamoyl, N,
N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), carbon number 10
The following aryl groups (e.g. phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) substituted with I8 or less alkyl groups), aryl groups (e.g. phenyl, 2-naphthyl), substituted aryl groups ( For example 4-
carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl), heterocyclic groups (e.g. 2
-pyridyl, 2-thiazolyl).

Particularly preferred are unsubstituted alkyl groups (e.g. methyl, ethyl) and sulfoalkyl groups (e.g. 2-sulfoethyl, 3
-sulfopropyl, 4-sulfobutyl).

Also, R', R', R', R', R5, R'R7, Rs
, R', R'' and [[As the metal atoms that can be formed, alkali metals are particularly preferable, and as the organic compounds,
Pyridines, amines, etc. are preferred.

z', z2. z', z', z', z', z”Z 12.
Nuclei formed by Z13 include thiazole nuclei (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4.
5-diphenylthiazole), benzothiazole core (e.g. benzothiazole, 4-chlorobenzothiazole,
5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-
Bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethyl Benzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5゜6-dimethylbenzothiazole, 5,6-simethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole , 4-phenylbenzothiazole), naphthothiazole nucleus [e.g.
naphtho(2,1-d)thiazole, naphtho[1,2-d]
) thiazole, naphtho(2,3-dl thiazole, 5-
MethoxynaphthoC1,2-d]thiazole, 6-methoxynaphtho(1,2-d)thiazole, 7-nitoxynaphtho[2,1-d)thiazole, 8-methoxynaphtho[2
, 1-d) Thiazole, 5-methoxynaphtho[2,3-
d) thiazole)], thiazoline core (e.g. thiazoline, 4-methylthiazoline, 4-nitrothiazoline),
Oxazole nucleus (e.g. oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (e.g. benzoxazole), Oxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole,
5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-
Nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-
Nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-
dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole core (e.g., naphthoC2,1-d)oxazole, naphthyl-[1,2-d]oxazole, naphtho[ 2,3-d) oxazole, 5-nitronaphtho (
2,1-d) oxazole)), oxazoline nucleus (e.g. 4,4-dimethyloxazoline), selenazole nucleus (e.g. 4-methylselenazole,
4-nitroselenazole, 4-phenylselenazole)
, benzoselenazole core (e.g., benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro -6-nitrobenzoselenazole,
5,6-dimethylbenzoselenazole), naphthoselenazole core (e.g., naphtho(2,1-d]selenazole, naphtho[1°2-d]selenazole)), selenazoline core (e.g., selenazoline, 4-methyl selenazoline), telllazole core (e.g., tellurazole, 4-methyltelllazole, 4-phenyltelllazole), penzotelllazole core (e.g., penzotelllazole, 5-chloropenzotelllazole, 5- methylbenzotelllazole, 5゜6-dimethylbenzotelllazole, 6-medoxybenzotelllazole), naphthotelllazole core (e.g. naphtho[2,1-d)telllazole, naphtho[1,2-d]telllazole) )), tellazoline core (e.g. tellazoline, 4-methylselenazoline), 3,3-dialkylindolenine core (e.g. 3
, 3-dimethylindolenine, 3゜3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine,
3,3-dimethyl-6 nitroindolenine, 3,3-dimethyl-5 nitroindolenine, 3,3-dimethyl-5
-methoxyindolenine, 3,3.5-trimethylindolenine, 3,3.5-dimethyl-5-chloroindolenine), imidazole nucleus (imidazole nucleus (e.g. l
-alkylimidazole, 1-alkyl-4-phenylimidazole), benzimidazole nucleus (e.g. 1-
Alkylbenzimidazole, ■-alkyl-5-chlorobenzimidazole, l-alkyl-5,6-dichlorobenzimidazole, I-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, l-alkyl-5 -fluorobenzimidazole, ■-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-
Trifluoromethylbenzimidazole, 1-allyl-
5,6-dichlorobenzimidazole, l-allyl-5
-chlorobenzimidazole, l-arylbenzimidazole, ■-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole,
1-aryl-5-cyanobenzimidazole), naphthoimidazole core (e.g. 2-alkylnaphtho[1,
2-d] imidazole, 1-arylnaphtho[1,2-
d) imidazole), the alkyl group mentioned above has 1 to 1 carbon atoms;
8, for example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hydroxyalkyl groups (for example, 2-hydroxyethyl, 3-hydroxypropyl). Particularly preferred are methyl group and ethyl group.

The aforementioned aryl groups represent phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. ), pyridine nucleus (e.g. 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-
pyridine), quinoline nucleus (e.g. 2-quinoline, 3methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-
Quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-nitoxy-4
-quinoline, 6-nitro-4-quinoline, 8-chloro-
4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-
Methyl-4-quinoline, 6-medoxy-4-quinoline,
6-chloro-4-quinoline), isoquinoline core (e.g. 6-nitro-1-isoquinoline, 3゜4-dihydro-
1-isoquinoline, 6-nitro3-isoquinoline)),
You can choose from among tetrazole core, pyrrolidine core, etc.

The nuclei formed by Z 6 , Z 8 , ZIO, and Zll include 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidacillin-5-one,
Hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5
-one, 2-thioxoxazoline-2,4-dione,
Isoxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-
It can be selected from dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, barbital acid, 2-thiobarbital acid, and the like.

The substituent bonded to the nitrogen atom contained in the nucleus is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl , isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (
For example, aralkyl groups (e.g. benzyl, 2-phenylethyl), hydroxyalkyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl groups (e.g. 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl) , carboxymethyl group), alkoxyalkyl group (e.g. 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl), sulfoalkyl group (e.g. 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl) , 2-[
3-sulfopropoxy]ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl)
, sulfatoalkyl groups (e.g. 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (e.g. 2-(pyrrolidin-2-one-1-yl)ethyl, tetrahydrofurfuryl, 2- morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2
-methanesulfonylaminoethyl), allyl, aryl groups (e.g. phenyl, 2-naphthyl), substituted aryl groups (e.g. 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl), heterocyclic groups (e.g. , 2-pyridyl, 2-thiazolyl) are preferred.

L', L2. L3. L", L5.L', L'L@, L@
, LIO may be substituted with a methine group (substituted or unsubstituted alkyl group (e.g. methyl, ethyl), substituted or unsubstituted aryl group (e.g. phenyl) or halogen atom (e.g. chlorine atom, bromine atom) ), and may form a ring with another methine group, or may form a ring with an auxochrome.

x', x2. x3. Specifically, the anion represented by x' may be an inorganic anion or an organic anion, such as a halogen anion (e.g., fluorine ion, chloride ion, bromide ion, iodide ion), substituted arylsulfonate ion ( For example, p-) luenesulfonate ion, p-chlorobenzenesulfonate ion), aryl disulfonate ion (for example, l, 3-benzenedisulfonate ion, ■, 5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion) ), alkyl sulfate ion (e.g. methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion,
Examples include trifluoromethanesulfonic acid ion.

Specific examples of particularly preferred dyes are listed below.

S ■ 2 H5 2 H5 2 H5 2 H5 zHs 2 Hl (CH2), CH.

(CH2), SO2 C. H.

2 H5 tHs 2 H5 (Shi M2 C δ(J+K 2H5 C. H5 C2H.

2 HK 2 H5 2H5 2H5 2H5 2 Hi C,H.

(CH2), 5ol C, H3 2H5 (CHt), so.

2H5 C2H.

C2H6 2H5 2H5 C2H.

(CHtCH20)t(CHt)3SO3-(CHtC
H20)t(CI(t)3sOsNaC'r H5S (CHri4SO3(CH*n.803H(CH2),5O3(CHi)+5O3H(CH2),So.

(CH2)3SO3H’N (C2H4)3S-49 S-50 2H5 C,H.

(CH2), so.

2 M+ 2HI (CH2), SO2 2H5 (CH2), 5o3 (CH,), s□.

C) Fz Ut”2Fi to i2 S (CH2), So.

(CH2)t Sol Na So, K ot SO+Na S 2H5 (CH2)- 8O8 H 2 H.S. Hh OsNa CH2 OOH 2Hs C. H.

CH3 / CH2 -CH Hr 03Na CH2CH20H 8○, H-N (C2Ha).

CH2CHI OH C)12CH20H S-107 (CH2)3SO3 The red-sensitive silver halide emulsion layer of the present invention has the following general formula (
It is particularly preferable to use sensitizing dyes represented by P-I) to (PV).

General formula (P-I) R'(Xl)n'R' in formula 21
and Z2 is an oxazole nucleus, a benzoxazole nucleus,
Atoms necessary to form a naphthoxazole nucleus, an imidazole nucleus, a benzimidazole nucleus, a naphthoimidazole nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a nucleus derived from a naphthoselenazole nucleus represents. LL2 and R8 represent methine groups. R1 and R2 represent an alkyl group, and one of them is preferably an alkyl group substituted with a sulfo group or a carboxy group.X
l represents an anion, and nl represents the number necessary to neutralize the charge.

General Formula (P-m) In the formula, 23 represents an atomic group necessary to form a nucleus derived from a pyridine nucleus or a quinoline nucleus. Ql represents an atomic group necessary to form a 5- to 6-membered ring having an oxo group.

R4 and R5 are LL2. It has the same meaning as R8. R1 is R
It has the same meaning as 1 or R2. Note that at least one of the substituents contained in R3 and Ql preferably has a sulfo group or a carboxy group.

General Formula (pm) In the formula, 24 represents an atomic group necessary to form a nucleus derived from an oxazole nucleus, a benzoxazole nucleus, a thiazoline nucleus, or a selenazoline nucleus. Q2 has the same meaning as Q. R6,
L', L' and R9 are synonymous with L', R2, L'. R4 has the same meaning as R' or R2. In addition, R4
It is preferable that at least one of the substituents contained in Q2 has a sulfo group or a carboxy group.

General Formula (P-IV) In the formula, 25 represents an atomic group necessary to form a nucleus derived from an oxazole nucleus or a benzoxazole nucleus. Wl is 5
represents a group of atoms necessary to form a 6-membered heterocycle.

Q3 has the same meaning as Ql.

L 10 and L II are synonymous with L', R2, and L'.

R5 has the same meaning as R1 or R2. R6 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. In addition,
It is preferable that at least one of the substituents included in R5, R@ and Q3 has a sulfo group or a carboxy group.

Among these, preferred are cyanine dyes capable of forming so-called J-aggregates, among which cyanine dyes with the following general formula (P
-V) is preferred.

General formula (PV) R' (XJn2 R' where z', z
' represents an atomic group necessary to form a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a naphthoimidazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, and a naphthoselenazole nucleus.

However, neither z' nor z' becomes a benzoxazole nucleus. R7 and R8 are synonymous with R1 and R2,
It is preferable that at least one of them has a sulfo group or a carboxy group. R9 represents a hydrogen atom, an ethyl group, or a phenyl group. X2 has the same meaning as Xl, and R2 has the same meaning as nl.

Examples of the above-mentioned heterocyclic nucleus include thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (e.g. benzothiazole, 4-phenylthiazole), Chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5
Methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-
Methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-
Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-simethoxybenzothiazole,
5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole core (e.g. naphtho[2,1-
dlthiazole, naphtho[1,2-d)thiazole, naphtho[2,3-d)thiazole, 5-methoxynaphtho(
1,2-d:]thiazole, 6-methoxynaphtho[1,
2-dl thiazole, 7-nitronaphtho [2,ld]
Thiazole, 8-methoxynaphtho (C2,1-d) thiazole, 5-methoxynaphtho (2,3-dl thiazole etc.)), thiazoline nucleus (e.g. thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus ( Oxazole nucleus (e.g., oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4.5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (e.g., benzoxazole, 5
-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5 -Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4 , 6-dimethylbenzoxazole,
5-ethoxybenzoxazole), naphthoxazole core (e.g. naphtho[2,1-d)oxazole, naphthoEl, 2-d)oxazole, 5-methoxynaphtho(1,2-dloxazole, naphtho(2,3- dloxazole, 5-nitronaphtho[2,1-d)oxazole, etc.)), selenazole nucleus (selenazole nucleus (e.g. 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nidropenzoselenazole, 5chloro-6-nidropenzoselenazole, 5゜6-dimethylbenzoselenazole), naphthoselenazole core (e.g. naphthoC2,1-d)selenazole, naphtho(1,2-dl selenazole)), Selenazoline nucleus (e.g. selenazoline, 4-methylselenazoline), imidazole nucleus (imidazole nucleus (e.g.
■-alkylimidazole, 1-alkyl-4-phenylimidazole), benzimidazole nucleus (e.g. 1
-alkylbenzimidazole, ■-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, ■-alkyl-5-cyanobenzimidazole, 1-alkyl-5 -fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, ■-alkyl-6-chloro-5-cyanobenzimidazole, l-alkyl-6-chloro-5
-trifluoromethylbenzimidazole, 1-allyl-5゜6-dichlorobenzimidazole, 1-allyl 5
-chlorobenzimidazole, ■-arylhencyimidazole, ■-aryl-5-chlorobenzimidazole, ■-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole,
■-Aryl-5cyanobenzimidazole), naphthoimidazole nucleus (e.g., 2-alkylnaphtho(1,2
-dl imidazole, ■-arylnaphtho(1,2-d
) imidazole), the alkyl group mentioned above has 1 to 8 carbon atoms.
For example, unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl) are preferred. Particularly preferably a methyl group,
It is an ethyl group.

The aforementioned aryl groups represent phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. ), pyridine nucleus (e.g. 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-
pyridine), quinoline nucleus (e.g. 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-
Quinoline, 6-methyl-2-quinoline, 6-nitro-2
-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-nitoxy-4
-quinoline, 6-nitro-4-quinoline, 8-chloro-
4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-
Methyl-4-quinoline, 6-medoxy-4-quinoline,
6-chloro-4-quinoline), R', R1, R'', R', R', R7 and R' preferably have a carbon number of 18
The following unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or substituted alkyl groups (e.g., carboxy group, sulfo group, cyano group, halogen atom (e.g., fluorine atoms, chlorine atoms, and bromine atoms.

), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl)
, an alkoxy group having 8 or less carbon atoms (e.g. methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (e.g. phenoxy, p-tolyloxy), an acyloxy group having 3 or less carbon atoms (e.g. acetyloxy, propionyloxy), acyl groups having 8 or fewer carbon atoms (e.g. acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (e.g. carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl groups), aryl groups having 10 or less carbon atoms (e.g. phenyl, 4-chlorophenyl, 4-methylphenyl, α-subbutyl) An alkyl group having 18 or less carbon atoms substituted with is preferred. ) can be mentioned.

The nucleus formed by Q', Q2 and Q8 is illustrated.

2-pyrazolin-5-one, pyrazolidine-3°5-dione, imidacillin-5-one, hydantoin, 2- or 4-thiohydantoin, 2-iminooxazolidine-
4-one, 2-oxazolin-5-one, 2-thioxazolidine-2,4-dione, inoxazolin-5-one, 2-thiazolin-4-one, thiazolidin-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, inrhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indolin-2-one, indolin-3-one, indacillin-3-one,
2-oxoindacillinium, 3-oxoindacillinium, 5,7dioxo6,7-dihydrothiazolo[3
,2-a]pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1.3
-dioxane-4,6-dione, barbylic acid, 2-
Thiobarbylic acid, chroman-2°4-dione, indacillin-2-one, or pyrido[1,2-a)pyrimidine-1,3-dione core.

The heterocycle formed by Wl is one of the above, with the oxo group or thioxo group at an appropriate position removed from those whose heterocycle structures match.

The substituent bonded to the nitrogen atom contained in Q', Q2.0'' and R6 are hydrogen atoms, alkyl groups having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (for example, methyl , ethyl, propyl, isopropyl, butyl,
isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (e.g. aralkyl groups (e.g. benzyl, 2-phenylethyl), hydroxyalkyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl groups (e.g. , 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (
For example, 2-methoxyethyl, 2-(2-methoxyethoxy)ethyl), sulfoalkyl groups (e.g. 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-
Sulfobutyl, 2-[3-sulfopropoxy]ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (e.g. 3-sulfatopropyl, 4-sulfatobutyl), hetero Ring-substituted alkyl groups (e.g. 2-(pyrrolidine-
2-on-1-yl)ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl), allyl group, aryl group (e.g. phenyl, 2-naphthyl) , substituted aryl groups (e.g. 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3
-methylphenyl), heterocyclic groups (e.g. 2-pyridyl,
2-thiazolyl) is preferred.

L', L2. L', L', L5. L', L'L", L
', L'', J= and Lll are methine groups (substituted or unsubstituted alkyl groups (e.g. methyl, ethyl), substituted or unsubstituted aryl groups (e.g. phenyl), or halogen atoms (e.g. chlorine atom, bromine atom). ), and may also form a ring with another methine group, or may form a ring with an auxochrome.

Anions represented by Xl and X2 are illustrated. For example, halogen anions (e.g. fluoride ions, chloride ions,
Bromine ion, iodine ion), substituted arylsulfonate ion (e.g. p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g. 1,3-benzenedisulfonate ion, l, 5-naphthalene) Disulfonic acid ion, 2,6
- naphthalene disulfonate ion), alkyl sulfate ion (e.g. methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. .

Preferably it is an iodine ion.

Specific examples of particularly preferred dyes are listed below.

−Ilsan C2H.

(CH2)45ol (CH2)3 So.

C2H.

2H5 (CH2), So.

(CH2), SO.

(CH2)+ SO+ H-NEt+ 2Hs (CH2), So.

(CH2)2 CH.

(CH2), 5ol (CH2)3 so.

CH2CH,OH 2 H5 CH3 r　Hs r　Hi r (CH2)h　S(J+　Na P-36 P-38 2H5 C,H.

C2H.

2H5 (, Fith SUh Of the coupler skeletons represented by the general formula [I] used in the present invention, preferred are IH-imidazo[1,2-
b) Pyrazole, IH-pyrazolo [1,5-亙] [
1,2,4] Triazole, IH-pyrazolo[5,1
-±)(1,2,4) triazole and IH-pyrazolo(1,5-d)tetrazole, with formulas CM-13, CM-■], CM-1[[) and CM-
■).

(M-[) (M-n) (M-1)1) CM-IV) Substituents Rz, R1 in these formulas! , R+i and X will be explained in detail.

R1) is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, an anilino group , ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyl Oxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group,
It represents an azolyl group, and R1+ may be a divalent group forming a bis body.

More specifically, RI 1 is each a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom), an alkyl group (e.g., a linear or branched alkyl group having 1 to 32 carbon atoms,
Aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, such as methyl, ethyl, propyl, isopropyl, t-butyl,
tridecyl, 2-methanesulfonylethyl, 3-(3-
pentadecylphenoxy)propyl, 3-(4-(2
-C4-(4-hydroxyphenylsulfonyl)phenoxy] dodecanamido)phenyl)propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-(2,4-di-L-amylphenoxy)propyl), aryl group ( For example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic groups (e.g. 2-
furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2- methanesulfonyl ethoxy), aryloxy groups (e.g., phenoxy, 2-methylphenoxy, 4
-1-butylphenoxy, 3-nitrophenoxy, 3-
t-butyloxycarbamoylphenoquine, 3-methquinecarbamoyl), acylamino groups (e.g. acetamide, henzamide, tetradecaneamide, 2-(2,
4-di-t-amylphenoxy)butanamide, 4-(
3-t-butyl-4-hydroxyphenylcy)butanamide, 2-+4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide), alkylamino groups (e.g. methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino) ), anilino groups (e.g. phenylamino, 2-chloroanilino, 2
-Chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-(α(3-t-butyl-4-hydroxyphenoxy)dodecaneamide) ) anilino), ureido groups (e.g. phenylureido, methylureido, N,N-dibutylureido), sulfamoylamino groups (e.g. N,N,-dipropylsulfamoylamino, N-methyl-N-decylsulfamino), famoylamino), alkylthio groups (e.g. methylthio,
Octylthio, Tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4-t-
butylphenoxy)propylthio), arylthio group [
For example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-
carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino groups (e.g.
methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide groups (e.g. methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, P-)luenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butyl Hensensulfonamide), carbamoyl groups (e.g. N-ethylcarbamoyl, N,N-dibutylcarno(
moyl, N(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, N-]3(
2,4-dimo-amylphenoxy)propyl)carbamoyl), sulfamoyl groups (e.g., N-ethylsulfamoyl, NN-dipropylsulfamoyl, N-(
2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), sulfonyl group (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (for example,
methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl)
, heterocyclic oxy groups (e.g., 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),
Ab groups (e.g., phenylazo, 4-methoxyphenylazo, 4 pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy groups (e.g., acetoxy), carbamoyloxy groups (e.g., N- methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy groups (e.g. trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (e.g. phenoxycarbonylamino), imide groups (e.g. N-succinimide, N-phthalimide) , 3-octadecenylsuccinimide), heterocyclic thio groups (e.g., 2-hendithiazolylthio, 2,4-di-phenoxy-13,5-triazole-6-thio, 2-pyridylthio), sulfinyl groups ( For example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxyprobylsulfinyl), phosphonyl groups (e.g., phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl)
, aryloxycarbonyl groups (e.g. phenoxycarbonyl), acyl groups (e.g. acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (e.g. imidazolyl, pyrazolyl, 3-chloro-pyrazole-1) -yl, triazolyl), and among these substituents, groups that can have further substituents further have an organic substituent or halogen atom connected via a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. It's okay.

Among these substituents, preferable R1) include an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Examples include an alkylthio group, a ureido group, a urethane group, and an acylamino group.

R1□ is the same group as the substituent exemplified for R1, preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group,
They are sulfamoyl group, sulfinyl group, acyl group and cyano group.

R1ff is a group having the same meaning as the substituent exemplified for R1+, and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
These include an alkylthio group, an alkylthio group, an alkoxycarbonyl group, a carbamoyl group, and an acyl group, and more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, and an arylthio group.

X represents a hydrogen atom or a group capable of leaving in the reaction with the oxidized product of the aromatic primary amine color developing agent.
Aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group,
Alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5- or 6-membered nitrogen-containing heterocyclic group,
Examples include an imide group and an arylazo group, and these groups may be further substituted with a group allowed as a substituent for R1).

More specifically, halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), alkoxy groups (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy groups ( For example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy groups (e.g., acetoxy, tetrazoka yloxy, benzoyloxy), alkyl or arylsulfonyloxy groups (e.g. eva, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (e.g. dichloroacetylamino, heptafluorobutyrylamino), alkyl or arylsulfonamide groups (e.g. dichloroacetylamino, heptafluorobutyrylamino), For example, methanesulfonamino, trifluoromethanesulfonamino, P-)luenesulfonylamino),
Alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (e.g. dodecylthio, 1-carboxydodecylthio, phenylthio) , 2-butoxy-5t-octylphenylthio, tetrazolylthio), carbamoylamino groups (e.g., N-methylcarbamoylamino, N
-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic groups (e.g., imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2
-oxo-1-pyridyl), imido groups (e.g. succinimide, hydantoinyl), and -luazo groups (e.g. phenylazo, 4-methoxyphenylazo). In addition to these, X may also take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or ketone as a leaving group bonded via a carbon atom. Further, X may contain photographically useful groups such as development inhibitors and development accelerators.

Preferably, X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position via a nitrogen atom.

Examples of magenta coupler compounds represented by general 2N) are illustrated below, but are not limited thereto.

(M-1) (M-2) (M-3) (n) CaHq 0 (M-4) (M-7) (M-5) (M-8) CsLt(t) (M-6) (M-9) CsH1? (t) CaH+7(t) (M-10) (M-1)) (M (M (M-12) CsHl? (t) (M-18) (M-19) (M-20) (M (M-22) (M-23) C2°Fl.

(M (M (M-29) (M (M-25) Cs41+t(t) (M-26) Bond (M-31) (M-34) Bond-33) (M-35) General formula (Ill References are listed below that describe the synthesis of the couplers represented.

Compounds of formula [M-I] are disclosed in U.S. Pat. No. 4,500°630.
Compounds of the formula [:M-Ill, such as U.S. Pat.
No. 40,654, No. 4,705,863, JP-A-61
-65245, 62-209457, 62-2
No. 49155, compounds of the formula [M-I[I] are disclosed in Japanese Patent Publication No. 47-2741), U.S. Pat.
It can be synthesized by the method described in No. 52, etc.

The magenta coupler represented by the general formula (I) of the present invention is added to the green-sensitive emulsion layer and/or its adjacent layer, and the total amount added is 0.01 to 1.0 g/rrr, preferably 0. .05-0.8g/resistant, more preferably O,
It is 1 to 0.5 g/nr.

The method for adding the magenta coupler of the present invention into the light-sensitive material is similar to the method for other couplers described below, but the amount of the high-boiling organic solvent used as a dispersion solvent is determined based on the total coupler added to the magenta coupler-containing layer. 0 to 4 as weight ratio
．． 0, preferably from 0 to 2.0, preferably from 0.1 to 1.5, more preferably from 0.3 to 1.5. O
It is.

/ The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer, which is a blue-chromic layer, a green-sensitive layer, and a red-sensitive layer, on the support. There are no particular limitations on the number of layers and non-photosensitive layers and the order of the layers. A typical example is a support with a small number of light-sensitive layers consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. It is a photographic light-sensitive material, and the light-sensitive layer is a unit light-sensitive layer that is sensitive to blue light, green light, or red light. The color layers are arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer.However, depending on the purpose, the above arrangement order may be reversed or the same layer may be used. The arrangement may be such that different photosensitive layers are sandwiched between color sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A-61-43748 and JP-A-59-1.
) No. 3438, No. 59-1) No. 3440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used6
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
1) No. 2751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, a low sensitivity blue sensitive layer (BL) / a high sensitivity blue sensitive layer (BL) / a high sensitivity green sensitive layer (Gl+) / a low sensitivity green sensitive layer (GL) /
High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL)
), or BH/BL/GL/GW/RH/RL, or 81(/BL/IJ/GL/RL/l?I(
They can be installed in the following order:

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
) They can also be arranged in the order of I/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/FiL/GH/RH may be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is distributed, and the photosensitivity decreases sequentially toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-irradiation emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on 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 silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) 81) 17643
(December 1978), pp. 22-23, “■, Emulsion preparation and
d types)”, and the same Nil 1B716
(January 1979), 648 pages, Kaimagai 3071
05 (January 1989), pp. 863-865, and the graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafkides, Chemie e
t Ph1sique PhotographqLI
e+ Paul Mor+tel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G,
F, Duffin Photographic Em
Ulsion Chemistry (Focal
Press.

(1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelil)
vanetal,, Making and Coat
ing Photographic Emulsion
, Focal Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering)
, Vol. 14, pp. 248-257 (1970);
U.S. Patent No. 4.434.226, U.S. Patent No. 4,414.31
No. 0, No. 4,433,048, No. 4,439,520
and British Patent No. 2.1)2.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The above-mentioned emulsions may be of the surface latent image type that forms latent images primarily on the surface, of the internal latent image type that forms inside the grains, or of the type that has latent images both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, the core/shell type internal latent image type emulsion may be a core/shell type internal latent image type emulsion described in JP-A-63-264740. No. 59-133542.

The thickness of the shell of this emulsion varies depending on the development process, etc., but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure NcL.
17643, same NIL 18716 and rotation magnet 3071
05, and the relevant parts are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains with puffed grain surfaces as described in U.S. Pat. No. 4,082,553, U.S. Pat. No. 4,626,4
Silver halide grains and colloidal silver with covered grain interiors described in No. 98 and JP-A No. 59-214852 are preferably used in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. Can be used.

Silver halide grains that have their interiors or surfaces covered are defined as - (
A method for preparing silver halide grains in which the interior or surface of silver halide grains can be developed (in a non-imagewise manner) is described in U.S. Pat. No. 4,626,498 and JP-A-59 -214852.

The silver halide forming the inner core of the core/shell type silver halide grains may have the same or different halogen composition. As the silver halide, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these diffused silver halide grains,
The average particle size is preferably 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm. There are no particular limitations on the shape of the grains, and they may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or number of silver halide grains is within the range of the average grain size).
40% or less) is preferable.

In the present invention, it is preferable to use non-light-sensitive fine-grain silver halide. Non-light-sensitive fine-grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, but is not exposed to light during the development process. These are fine silver halide grains that are not substantially developed 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 if necessary, preferably silver iodide of 0.5 mol %. It contains ~10 mol%.

The fine grain silver halide preferably has an average particle size (average (i) of the circle equivalent diameter of the projected area) of 0.01 to 0.5μ,
．． 02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized (and spectral sensitization is also unnecessary. It is preferable to add a known stabilizer such as a benzothiazolium-based compound, a benzothiazolium-based compound, a mercapto-based compound, or a zinc compound. Colloidal silver can preferably be contained in this fine-grain silver halide grain-containing layer.

The coating silver amount of the photosensitive material of the present invention is preferably 6.0 g/m or less, most preferably 4.5 g/nf or less.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

The photosensitive material of the present invention includes U.S. Pat. No. 4,740,454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A-1-283551.

A compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof irrespective of the amount of developed silver produced during the development process, which is described in JP-A-1-106052, is added to the light-sensitive material of the present invention. It is preferable to contain.

A dye dispersed in the photosensitive material of the present invention by the method described in International Publication No. 088104794, Japanese Patent Application Publication No. 1-502912, or EP 317,308^, U.S. Patent No. 4
, 420,555 and JP-A-1-259358.

Various color couplers can be used in the present invention, specific examples of which are listed in Research Disclosure N.
fl 17643, ■-C-G, and Koji 30710
5, is described in the patent described in ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, British Patent No. 4.314,
No. 023, No. 4, 51). No. 649, European Patent No. 24
No. 9,473A, etc. are preferred.

Magenta couplers other than those represented by general formula (1) of the present invention include US Pat. No. 4,310,619;
4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, European Patent No. 3,725,
No. 067, JP-A-60-35730, JP-A No. 55-1) 8
-034, No. 60-185951, U.S. Patent No. 4,
Particularly preferred are those described in No. 556,630, International Publication No. WO38104795, and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4,296.200, No. 2,369.9
No. 29, No. 2.801.171, No. 2,772,
No. 162, No. 2,895,826, No. 3,772
．． No. 002, No. 3,758,308, No. 4,33
4.01), 4,327,173, West German Patent Publication No. 3329.729, European Patent No. 121,365A
No. 249453A, U.S. Patent No. 3,446,6
No. 22, No. 4,333.999, No. 4,775,
No. 616, No. 4,451.559, No. 4,427
, No. 767, No. 4,690,889, No. 4.25
No. 4212, No. 4,296.199, JP-A-61-
Preferably, those described in JP-A-64-553, JP-A-64-554, and JP-A-64-555 are preferred.
Pyrazoloazole couplers described in No. 64-556 and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576°910, British Patent No. 2.102.
No. 137, European Patent No. 341°188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96,570 and German Patent Publication No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Sou 17643.
-G term, ■-G term of rotation magnet 307105, U.S. Patent No. 4,
163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling described in U.S. Pat. No. 4,774.181, and U.S. Pat. No. 4,777
．． It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 120.

Compounds that release photographically useful residues upon coupling are also preferred (and can be used) in the present invention.

DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F term and rotation 307105, ■-F
Patents described in Sections, JP-A No. 57-151944, JP-A No. 57-154234, JP-A No. 60-184248, JP-A No. 6
No. 3-37346, No. 63-37350, U.S. Patent 4
, 248.962 and 4,782,012 are preferred.

British Patent No. 2.097.140, British Patent No. 2.097.140 is a coupler that releases a nucleating agent or a development accelerator imagewise during development.
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.
Also, JP-A-60-107029, JP-A No. 60-2523
Also preferred are compounds that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized developing agents as described in Japanese Patent Application Laid-open Nos. 144940 and 1999 and 1-45687.

Other compounds that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc., U.S. Pat. , 4,310.6L8, etc., JP-A-60-185950,
DIR redox compound releasing coupler described in JP-A-62-24252 etc., DIR coupler releasing coupler, -1
DIR Coupler-Releasing Redox Compound or DIR Redofux-Releasing Redox Compound, European Patent No. 173゜3
No. 02A, a coupler releasing a dye that recovers color after separation as described in No. 313,308A, R, D, 1) 449;
No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Patent No. 4.555.47
Ligand releasing coupler described in No. 7 etc., JP-A-63-7
Couplers that emit leuco dyes as described in US Pat. No. 5,747, and couplers that emit fluorescent dyes as described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl) phthalate, bis(2,4-di-t-amyl phenyl) phthalate, (2,4-di-t-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, etc.)
-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amide II (N,N-
diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2
, 4-di-tert-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-tert-octylaniline, etc.)
, hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.).

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are disclosed in U.S. Pat. etc. are listed.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
- It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various colored fluorescent materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal vapor.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, k 17643, page 28, same amount 18716, 64
7 pages right paddle to 648 pages left paddle, and 81) 30710
5, page 879.

In the photosensitive 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, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. is particularly preferable, and the film swelling rate TI/□ is preferably 30 seconds or less, more preferably 20 seconds or less. Film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days). However, the membrane swelling rate TI/□ can be measured according to techniques known in the art. For example, Photography Science and Engineering (Photogr, Sci, Eng,) by A. Green et al.
It can be measured by using a swellometer (swelling membrane) of the type described in Volume 19, No. 2, pages 124-129.
T1/2 is defined as the time required to reach the saturated film thickness of 172, with 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds as the saturated film thickness.

The membrane swelling rate TI7□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above, using the formula: (maximum swollen film thickness -
A total of 1 can be obtained according to (film thickness)/film thickness.

The photosensitive material of the present invention has a hydrophilic colloid layer C having a total dry film thickness of 2 μm to 20 μm on the opposite side to the side having the emulsion layer.
It is preferable to provide a back layer (referred to as a back layer), which includes the aforementioned light absorbers, filter dyes, ultraviolet absorbers, static inhibitors, hardeners, binders, plasticizers,
It is preferable to contain a lubricant, a coating aid, a surface active agent, etc. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention can be produced by the conventional method described in the above-mentioned RD, No. 17643, pages 28-29, No. 18716, 651 left column to right column, and No. 307105, pages 880-881. It can be developed by

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts or ρ-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-
Nβ-hydroxyethylaniline sulfate is preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pi buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or anticapri agents such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. Also, if necessary, add hydroxylamine, diethylhydroxylamine, 1liiL! ! salts, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, ■-phenyl3. Auxiliary developing agents such as pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N, N, N,
N-tetramethylenephosphonic acid, ethylene glycol (
Representative examples include O-hydroxyphenylacetic acid) and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (II[), such as amino acids 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, etc. can be used. Among these, aminopolycarboxylic acid iron (1) complex salts including ethylenediaminetetraacetate iron (I[[) complex salt and 1,3-diaminopropanetetraacetate iron (I[[) complex salt) complex salt require rapid processing and environmental pollution. Preferable from the viewpoint of prevention, iron aminopolycarboxylate (I[
[) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (II
[) The pH of bleach or bleach-fix solutions using complex salts is usually 4.
．． 0-8, but lower p for faster processing
)l can also be used.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, Research Disclosure No. k17129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in Japanese Patent Publication Nos. 45-8506, 52-20832 and 53-32735, U.S. Pat. No. 3,706,561; West German Patent No. 1. 127,71
No. 5, iodide salts described in JP-A-58-16,235;
Polyoxyethylene compounds described in West German Patent No. 966.410 and West German Patent No. 2.748.430;
Polyamine compounds described in No. 836; other JP-A-49-
No. 40,943, No. 49-59.644, No. 53-9
No. 4.927, No. 54-35, 727, No. 55-26
, No. 506, the compound described in No. 58-163.940;
Bromide ion etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in U.S. Pat.
．． The compounds described in U.S. Pat. No. 630 are preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pea) of 2.
~5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. Preservatives for fixers and bleach-fix solutions are preferably sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294769A. For the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids.

In the present invention, the fixer or bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for p adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole. It is preferable to add imidazoles such as 0.1 to 10 mol/l.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring be as strong as possible.A specific method for strengthening the stirring is to impinge a jet of processing liquid on the emulsion surface of the photosensitive material as described in JP-A-62-183460. Method and JP-A-62-183
No. 461 uses a rotating means to increase the stirring effect, and furthermore, by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface, the stirring effect is further improved. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. It is highly effective in preventing performance deterioration of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention undergoes a water washing and/or stabilization process after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and TeIe-vi
sion Engineers Volume 64, P, 248
-253 (May 1955 issue).

According to the multi-stage interflow method described in the above-mentioned document, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method of reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used for extremely effective growth. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents," (1986) Sankyo Publishing, Hygiene. Technical extras “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Society of Industrial Technology, Japan Antibacterial and Antifungal Science ``Encyclopedia of Antibacterial and Antifungal Agents'' (
It is also possible to use the fungicides described in (1986).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 5B-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of the dye stabilizer that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process.

In a process using an automatic processor or the like, when each of the above-mentioned processing liquids is reduced to mm due to evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure Law 14, 85
0 and Schiff base-type compounds described in Circular 15.159,
Aldol compounds described in U.S. Pat. No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
~Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547, and No. 58-1) No. 5438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

on a subbed cellulose triacetate film support.
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/rd unit, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the halogen in the same layer The coating amount per mole of silveride is shown in moles.

(Sample 101) 1st layer (antihalation layer) black colloidal silver gelatin 2nd layer (middle layer) 2.5-di-t-pentadecyl hydroquinone X-1 X-3 X-12 B5-1 1 (BS-2 gelatin 3rd layer (1st red-sensing chyloid layer) Emulsion A Emulsion B Exacerbation pigment P-24 Silver Silver Silver 0.18 1.40 0.18 0.070 0.020 2, OX 10-3 0.060 o,os.

0.10 0.020 1.04 0.25 0.25 2.8X10-' Sensitizing dye P-16 Sensitizing dye P-3 X-2 X-10 B5-1 gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye P-24 Exacerbation pigment P-16 Sensitizing dye P-3 X-2 X-3 X-10 1,2X10-' 3.8X10-' 0.34 0.020 0.070 0.050 0.070 0.060 0.87 Silver 1.00 2.5xlO-' 1.0X10-' 3.3xlO-' 0.40 0.050 0.015 0.070 o,os.

O,070 gelatin 5th layer (3rd red chyle layer) emulsion Sensitizing dye P-24 Exacerbation pigment P-16 Exacerbation pigment P-3 X-2 X-3 X-4 )(BS-1 B5-2 gelatin 6th layer (middle layer) X-5 B5-1 gelatin 7th layer (first green milk layer) Emulsion A Emulsion B Sensitizing dye 5-9 1.30 Silver 1.60 1, lX10-' 7.0X10-' 2.4 X to-’ 0.097 0.010 0.080 0.22 0.10 1.63 0.040 0.020 O, S.O. Silver 0.15 Silver 0.15 5.3X10-' Sensitizing dye 5-45 Sensitizing dye 5-46 X-1 X-6 X-7 X-8 B5-1 ES-3 gelatin 8th layer (second green emulsion layer) Emulsion C Exacerbation dye S-9 Sensitizing dye 5-46 Sensitizing dye 5-10 X-6 X-7 X-8 )(BS-1 1 (BS-3 gelatin 1.7 x 10-' 6.4XIO530 0.021 0.26 0.030 0.025 0.10 0.010 0.63 Silver 0.45 2.7X10-5 3.9X10-' 1.0X10-' 0.094 0.026 0.018 0.16 8.0X10-' 0.50 9th layer (3rd green emulsion layer) Emulsion E Exacerbation pigment s-g Sensitizing dye 5-45 Sensitizing dye 5-46 X-1 EX　X　-1) )fBs-1 B5-2 gelatin io layer (yellow filter layer) yellow colloidal silver X-5 B5-1 gelatin 1st) layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F sensitizing dye person Silver 1.31 2.7X10-' 8.0X104 2.9XIQ-' 0.025 0.13 0.25 1.54 Silver 0.050 o, oa.

O,030 0,95 Silver 0.080 Silver 0.070 Silver 0.070 3.5XIQ-IX-8 X-9 B5-1 Gelatin 12th layer (second blue milk layer) Emulsion G Sensitizing dye A X-9 X-IQ 1 (BS-1 Gelatin 13th layer (third blue emulsion layer) Emulsion H Sensitizing dye A 042 0,28 1,10 Silver 0.45 2, IXIQ-' 0.15 ?, 0X10-Go 0,050 0.78 !! 0.77 2.2 X 10-' 0.20 0.070 0. 69 Silver 0.20 U -50,17 HB S -15,0XlO-" Gelatin 1.00 No. 15
Layer (second protective layer) H-10,40 B-1 (diameter 1.7 μm) 5.0xl
O-”B-2 (diameter 1.7 μm) 0
．． 10B -30,10 SC-10,20 Gelatin 1.20 Furthermore,
In order to improve preservability, processability, pressure resistance, anti-mold/bacterial properties, antistatic properties, and applicability in all layers, w-1, w-2,
w-3, B-4, B-5, F-LF-2, F-3, F-
4, F-5, F-5, F-7, F-g, F-9, F-1
0, F-1), F-12, F-13 and iron salts, lead salts,
Contains gold salt, platinum salt, iridium salt, and rhodium salt.

X X-2 X-3 0M X-7 X-8 X-9 l I X X X-6 X X-12 C, H, ff(n) CJ50SO+O B.S. ■ tricresyl phosphate B.S. Di-n-butyl phthalate (t)CJb Sensitizing dye A C CH.

■ χ: y -70:30 (wt%) CH,=CH-original 1! CH2CIJNHCHtCH
z=CI(-3oICI(I C0NHCH2n-2
~4 F-13 CI (pe arc part a) Next, the sensitizing dyes of the third layer, fourth layer, fifth layer, seventh layer, eighth layer, and ninth layer of sample 101, and the seventh layer and the 8 layers,
Samples 102 to 1) were prepared in exactly the same manner as Sample 101 except that the couplers EX-6 and EX-1) in the ninth layer were changed as shown in Table 1. Naori puller change is equimolar to EX-6, EX
-1) was carried out at 0.6 times the molar amount.

After processing the obtained sample for camera photography, a Macbeth color chart was separately illuminated with sunlight (color temperature was 5850°) and a regular white fluorescent lamp specified by JIS. , photographed.

These were subjected to the color development treatment shown below.

color development bleached white Water washing fixed arrival Water washing stability 3 minutes 15 seconds 6 minutes 30 seconds 2 minutes 10 seconds 4 minutes 20 seconds 3 minutes 15 seconds 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g-Hydroxyethylidene-1,l-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide
1.3 ■ Hydroxylamine sulfate 2.4
g4-(N-ethyl-N-β-hydroxyethylamine) 2-methylaniline sulfate Add 4.5g water
1. On! pHl0.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid dichloride 100.0g Thorium chloride ammonium bromide Ammonium nitrate Add water ■ 0°150°10°l.

pH6゜ Fixer Ethylenediaminetetraacetic acid dibasic acid thorium salt sodium sulfite Ammonium thiosulfate aqueous solution (70%) sodium bisulfite add water ■.

4゜ ■　75゜ 4゜ l.

pH 6゜ Stabilized liquid Formalin (40%) Polyoxyethylene-p-7nononylphenyl ether (average degree of polymerization 10) Add water to 2゜0゜1゜g g Further, transfer the processed negative film to color photographic paper. A photograph was obtained at an enlargement rate of 6.7 times. This photograph was used to evaluate color change and green saturation.

The results are shown in Table-1.

The evaluation was visually performed on the color tone of a gray plate with an optical density of 0.7 taken under fluorescent light and the saturation of green when photographed under sunlight.

As is clear from the results in the table, the combination of the present invention was able to improve the color change under fluorescent light without impairing the saturation of green color.

〇－ g 4,

[Brief explanation of drawings]

FIG. 1 shows absorption spectra of blue, green, and red optical filters used for density measurement.

Claims (1)

[Claims] (1) A silver halide color photograph having one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support, and having an ISO sensitivity of S. In the photosensitive material, the photosensitive material is 2/Slu
58 measured after uniform exposure with white light of x sec
The sensitivity of the green-sensitive silver halide emulsion layer (S_G^5^3^0) and the sensitivity of the red-sensitive silver halide emulsion layer (S_R^5^3^0) to monochromatic light of 0 nm are -0.3≦S_G ^
5^3^0-S_R^5^3^0≦0.3, and a silver halide characterized by containing a coupler represented by the following general formula [I] in the green-sensitive silver halide emulsion layer. Photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_1 represents a hydrogen atom or a substituent. Z represents a nonmetallic atomic group necessary to form a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a fused ring). X represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent.