JP2003202646A - Image forming method using silver halide color photographic sensitive material and silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low cost and high quality digital color printing system having compatibility with conventional analog exposure systems and to provide an image forming method using the printing system. <P>SOLUTION: In the image forming method using a silver halide color photographic sensitive material having a color mixture preventing layer and a protective layer, a blue-sensitive silver halide emulsion containing at least one of the blue-sensitive sensitizing dyes of formula (I) and having ≥90 mol% silver chloride content is comprised in a silver halide emulsion layer containing a yellow dye forming coupler and exposure is carried out with a blue semiconductor laser having a wavelength 30-60 nm shorter than the wavelength at which the blue-sensitive silver halide emulsion has the spectral absorption maximum. In the formula, Y is a benzene ring or a heterocycle; R<SP>1</SP>and R<SP>2</SP>are each alkyl, aryl or the like; V<SP>1</SP>-V<SP>4</SP>are each H, a substituent or the like; L is methine; and M is a counter ion. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a color photographic light-sensitive material, and more particularly to an image forming method for obtaining a high quality image at a low cost.

[0002]

2. Description of the Related Art Recent advances in laser light sources have been remarkable. Previously, the laser was expensive and required a large-scale device, but nowadays, a laser light source can be obtained with a small device at a low cost, and it is stable. This is because the development of semiconductor lasers for DVDs and the like continues to be actively carried out in the electronic industry, and shorter wavelength lasers are being developed in order to record information at higher density. Therefore, laser light sources having various wavelengths from short wave to long wave have been obtained. The description of the blue semiconductor laser light source is 2001
March Nichia presented at the 48th Joint Lecture Meeting on Applied Physics.

On the other hand, in the field of color printing using color photographic paper, digitization has spread remarkably. For example, in the digital exposure method by laser scanning exposure, direct printing is performed from a conventionally processed color negative film by a color printer. Compared to the analog exposure method used, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that a high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color printing paper. Further, with the rapid spread of digital cameras, it is also an important factor that color prints with high image quality can be easily obtained from these electronic recording media, and it is considered that this will lead to a further dramatic spread.
JP-A-11-84284 and JP-A-2001-75219 describe in detail a digital exposure method and an image forming method using the same.

Therefore, it is desired to realize an inexpensive high-quality color printing system by combining an inexpensive laser light source and a digital exposure system. However, inexpensive laser sources and color printing systems are not always in sync.
In the development of semiconductor lasers, laser wavelengths are becoming shorter every moment due to high-density information recording, so it is expected that inexpensive semiconductor lasers will move toward shorter wavelengths in terms of productivity in the future. When the spectral maximum wavelength of the color printing paper is moved according to the laser light source, there arises a problem that compatibility with the analog exposure method is lost. Even if compatibility is ignored and the spectral maximum wavelength of color photographic paper is set according to the laser light source wavelength that is currently supplied, it is a very realistic measure to deal with the situation where the laser light source wavelength constantly changes. But not for practical use.

There are generally exposure wavelengths that are also suitable for color photographic paper. So far, generally, wavelengths near the spectral maximum wavelength of color printing paper have been selected. This is because exposure at a wavelength different from the spectral maximum wavelength causes a decrease in photographic sensitivity. A more serious problem was surprisingly present. It was found to be sensitive to changes in the exposure environment (especially temperature changes). That is, when exposure is performed at a wavelength different from the spectral maximum wavelength, the photographic sensitivity changes depending on the environmental temperature during exposure, and an image of constant quality cannot be obtained. The sensitivity can be reduced by increasing the exposure amount and the exposure power, but the sensitivity fluctuation due to the fluctuation of the exposure environment could not be reduced. In Japanese Patent Laid-Open No. 2001-75219, the spectral maximum wavelength and the exposure light source wavelength are specified, but the exposure light source wavelength included in the spectral maximum wavelength region is specified, and the present invention is not disclosed at all.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to use an inexpensive laser light source, to be compatible with the conventional analog exposure system, and to maintain a constant quality even when the exposure environment temperature fluctuates. An object of the present invention is to provide an image forming method using a high quality digital color printing system and a silver halide color photographic light-sensitive material used therefor.

[0007]

The present invention can be achieved by the following means. (1) Halogenation having at least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer on a support. In the method of forming an image using a silver color photographic light-sensitive material, the yellow dye-forming coupler-containing silver halide emulsion layer contains a chloride containing at least one of the blue-sensitive sensitizing dyes represented by the general formula (BI). An image characterized by containing a blue-sensitive silver halide emulsion of 90 mol% or more of silver, and exposing using a blue semiconductor laser having a short wavelength of 30 nm to 60 nm with respect to the spectral maximum wavelength of the blue-sensitive silver halide emulsion. Forming method. General formula (BI)

[0008]

[Chemical 9]

In the formula, Y forms a benzene ring or a heterocycle.
Represents a group of atoms necessary for
It may be condensed with a heterocycle or may have a substituent. R
¹And R²Is an alkyl group, an aryl group or a heterocyclic group
Represent V¹, V², V³And V ^FourIs a hydrogen atom or a substituent
Represents two adjacent substituents linked to each other until saturated.
It does not form an unsaturated fused ring. L is methine
Represents a group. M is a counter ion, m is the charge in the molecule
Represents a number of 0 or more necessary for summing. (2) The support contains at least a yellow dye-forming coupler.
Silver halide emulsion layer, containing magenta dye forming coupler
Silver halide emulsion layer, halo containing cyan dye forming coupler
Halo having silver genide emulsion layer, color mixing prevention layer and protective layer
Method of forming image using silver genide color photographic light-sensitive material
In, the silver halide containing the cyan dye-forming coupler
The emulsion layer contains a red-sensitized sensitized color represented by the general formula (RI).
90 mol% or more of silver chloride containing at least one element
A red-sensitive silver halide emulsion containing a red-sensitive silver halide emulsion;
40 nm to 80 nm shorter than the maximum spectral wavelength of silver emulsion
Characterized by exposing using a red semiconductor laser of wavelength
Image forming method. General formula (RI)

[0010]

[Chemical 10]

In the formula, Z ¹ represents a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ are
It represents a methine group and may be substituted or may form a 5- or 6-membered ring with another methine group. R ¹ and R ² represent an alkyl group which may be the same or different and may have a substituent, and R ¹ is L ¹ and R ² is linked to L ⁵ and is a 5- or 6-membered member. You may form a ring. V ¹ , V ² , V ³ ,
V ⁴ , V ⁵ , V ⁶ , V ⁷ and V ⁸ are each a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group. , Amino group, acylamino group, alkoxy group, alkylthio group,
Two, which represent an alkylsulfonyl group, a sulfo group, an aryloxy group or an aryl group, and which are bonded to adjacent carbon atoms in V ^{1 to} V ⁸ may form a condensed ring with each other. Y ¹ represents a charge-balancing counterion, and s represents a value necessary to neutralize a charge of 0 or more. (3) Halogenation having at least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer on the support. In the method of forming an image using a silver color photographic light-sensitive material, the yellow dye-forming coupler-containing silver halide emulsion layer contains a chloride containing at least one of the blue-sensitive sensitizing dyes represented by the general formula (BI). The cyan dye-forming coupler containing a blue-sensitive silver halide emulsion containing 90 mol% or more of silver and exposed by using a blue semiconductor laser having a short wavelength of 30 nm to 60 nm with respect to a spectral maximum wavelength of the blue-sensitive silver halide emulsion. The silver halide emulsion layer containing silver chloride containing at least one of the red-sensitive sensitizing dyes represented by formula (RI) Image formation characterized by containing 0 mol% or more of a red-sensitive silver halide emulsion and exposing using a red semiconductor laser having a short wavelength of 40 nm to 80 nm with respect to the spectral maximum wavelength of the red-sensitive silver halide emulsion. Method. General formula (BI)

[0012]

[Chemical 11]

In the formula, Y forms a benzene ring or a heterocycle.
Represents a group of atoms necessary for
It may be condensed with a heterocycle or may have a substituent. R
¹And R²Is an alkyl group, an aryl group or a heterocyclic group
Represent V¹, V², V³And V ^FourIs a hydrogen atom or a substituent
Represents two adjacent substituents linked to each other until saturated.
It does not form an unsaturated fused ring. L is methine
Represents a group. M is a counter ion, m is the charge in the molecule
Represents a number of 0 or more necessary for summing. General formula (RI)

[0014]

[Chemical 12]

In the formula, Z ¹ represents a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ are
It represents a methine group and may be substituted or may form a 5- or 6-membered ring with another methine group. R ¹ and R ² represent an alkyl group which may be the same or different and may have a substituent, and R ¹ is L ¹ and R ² is linked to L ⁵ and is a 5- or 6-membered member. You may form a ring. V ¹ , V ² , V ³ ,
V ⁴ , V ⁵ , V ⁶ , V ⁷ and V ⁸ are each a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group. , Amino group, acylamino group, alkoxy group, alkylthio group,
Two, which represent an alkylsulfonyl group, a sulfo group, an aryloxy group or an aryl group, and which are bonded to adjacent carbon atoms in V ^{1 to} V ⁸ may form a condensed ring with each other. Y ¹ represents a charge-balancing counterion, and s represents a value necessary to neutralize a charge of 0 or more. (4) Blue, green, and red exposure time is 5μ per pixel
Exposure is performed at a resolution of 200 dpi or more for 2 seconds or less, and then development processing is performed at a total wet time of 100 seconds or less and a developer temperature of 40 ° C. or more, (1) to (3). The image forming method according to item 1. (5) The image forming method according to any one of items (1) to (4), wherein the development process is performed within 10 seconds after the exposure. (6) The silver halide grain contained in the blue-sensitive silver halide emulsion is characterized in that 50% or more of the projected area is a tabular grain having an aspect ratio of 2 or more (1) to (5).
The image forming method according to any one of items. (7) Halogenated having at least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer on the support. In the method of forming an image using a silver color photographic light-sensitive material, the yellow dye-forming coupler-containing silver halide emulsion layer contains a chloride containing at least one of the blue-sensitive sensitizing dyes represented by the general formula (BI). A laser containing a blue-sensitive silver halide emulsion of 90 mol% or more of silver, and the spectral maximum wavelength of the blue-sensitive silver halide emulsion is a long wavelength of 30 nm to 60 nm with respect to the exposure wavelength of a blue exposure light source. Silver halide color photographic light-sensitive material for exposure. General formula (BI)

[0016]

[Chemical 13]

In the formula, Y forms a benzene ring or a heterocycle.
Represents a group of atoms necessary for
It may be condensed with a heterocycle or may have a substituent. R
¹And R²Is an alkyl group, an aryl group or a heterocyclic group
Represent V¹, V², V³And V ^FourIs a hydrogen atom or a substituent
Represents two adjacent substituents linked to each other until saturated.
It does not form an unsaturated fused ring. L is methine
Represents a group. M is a counter ion, m is the charge in the molecule
Represents a number of 0 or more necessary for summing. (8) The support contains at least a yellow dye-forming coupler.
Silver halide emulsion layer, containing magenta dye forming coupler
Silver halide emulsion layer, halo containing cyan dye forming coupler
Halo having silver genide emulsion layer, color mixing prevention layer and protective layer
Method of forming image using silver genide color photographic light-sensitive material
In, the silver halide containing the cyan dye-forming coupler
The emulsion layer contains a red-sensitized sensitized color represented by the general formula (RI).
90 mol% or more of silver chloride containing at least one element
A red-sensitive silver halide emulsion containing a red-sensitive silver halide emulsion;
The spectral maximum wavelength of the silver emulsion is relative to the exposure wavelength of the red exposure light source.
It has a long wavelength of 40 nm to 80 nm.
Silver halide color photographic light-sensitive material for laser exposure. General formula (RI)

[0018]

[Chemical 14]

In the formula, Z ¹ represents a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ are
It represents a methine group and may be substituted or may form a 5- or 6-membered ring with another methine group. R ¹ and R ² represent an alkyl group which may be the same or different and may have a substituent, and R ¹ is L ¹ and R ² is linked to L ⁵ and is a 5- or 6-membered member. You may form a ring. V ¹ , V ² , V ³ ,
V ⁴ , V ⁵ , V ⁶ , V ⁷ and V ⁸ are each a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group. , Amino group, acylamino group, alkoxy group, alkylthio group,
Two, which represent an alkylsulfonyl group, a sulfo group, an aryloxy group or an aryl group, and which are bonded to adjacent carbon atoms in V ^{1 to} V ⁸ may form a condensed ring with each other. Y ¹ represents a charge-balancing counterion, and s represents a value necessary to neutralize a charge of 0 or more. (9) Halogenated having at least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer on the support. In the method of forming an image using a silver color photographic light-sensitive material, the yellow dye-forming coupler-containing silver halide emulsion layer contains a chloride containing at least one of the blue-sensitive sensitizing dyes represented by the general formula (BI). The cyan dye-forming coupler contains a blue-sensitive silver halide emulsion containing at least 90 mol% of silver, and the spectral maximum wavelength of the blue-sensitive silver halide emulsion is a long wavelength of 30 nm to 60 nm with respect to the exposure wavelength of a blue exposure light source. The silver halide emulsion layer containing the general formula (R
-I) containing a red-sensitive silver halide emulsion of 90 mol% or more of silver chloride containing at least one red-sensitive sensitizing dye, and the spectral maximum wavelength of the red-sensitive silver halide emulsion is that of a red exposure light source. A silver halide color photographic light-sensitive material for laser exposure, which has a long wavelength of 40 nm to 80 nm with respect to the exposure wavelength. General formula (BI)

[0020]

[Chemical 15]

In the formula, Y forms a benzene ring or a heterocycle.
Represents a group of atoms necessary for
It may be condensed with a heterocycle or may have a substituent. R
¹And R²Is an alkyl group, an aryl group or a heterocyclic group
Represent V¹, V², V³And V ^FourIs a hydrogen atom or a substituent
Represents two adjacent substituents linked to each other until saturated.
It does not form an unsaturated fused ring. L is methine
Represents a group. M is a counter ion, m is the charge in the molecule
Represents a number of 0 or more necessary for summing. General formula (RI)

[0022]

[Chemical 16]

In the formula, Z ¹ represents a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ are
It represents a methine group and may be substituted or may form a 5- or 6-membered ring with another methine group. R ¹ and R ² represent an alkyl group which may be the same or different and may have a substituent, and R ¹ is L ¹ and R ² is linked to L ⁵ and is a 5- or 6-membered member. You may form a ring. V ¹ , V ² , V ³ ,
V ⁴ , V ⁵ , V ⁶ , V ⁷ and V ⁸ are each a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group. , Amino group, acylamino group, alkoxy group, alkylthio group,
Two, which represent an alkylsulfonyl group, a sulfo group, an aryloxy group or an aryl group, and which are bonded to adjacent carbon atoms in V ^{1 to} V ⁸ may form a condensed ring with each other. Y ¹ represents a charge-balancing counterion, and s represents a value necessary to neutralize a charge of 0 or more.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
Reveal The blue exposure light source of the present invention has a blue-sensitive spectral maximum wavelength.
In contrast, it is a shortwave semiconductor laser of 30 nm to 60 nm.
It Preferably, it is 35 nm to the maximum wavelength of blue-sensitive spectrum.
55 nm short-wave semiconductor laser, more preferably
Blue-sensitive spectrum 40 to 50 nm short wavelength half of the maximum wavelength
It is a conductor laser. In other words, the spectral maximum of 480 nm
Then, the semiconductor laser of 420 nm to 450 nm is exposed.
That is. For blue semiconductor lasers, 2001 March
Announced Nichia Chemistry at the 48th Joint Lecture on Applied Physics
There is a detailed description. The red and green exposure light sources of the present invention
Gas lasers, light emitting diodes, semiconductor lasers
ー 、 Solid laser using semiconductor laser as excitation light source
Second harmonic generation light source (S
A monochromatic high density light source such as HG) is preferred. System
Compact and inexpensive semiconductor laser, S
More preferably an HG light source, especially compact
To design a device that is cheap, inexpensive, has a long life and is highly stable
Is preferably a semiconductor laser light source. Of the present invention
The red exposure light source is 40 nm to the maximum wavelength of the red-sensitive spectrum.
80 nm short wavelength red semiconductor laser is preferred
Good These are already on the market, and specifically, Al
GaInP (oscillation wavelength of about 680 nm: Thailand manufactured by Matsushita Electric Industrial Co., Ltd.
No. LN9R20), (oscillation wavelength about 650 nm:
Hitachi type No. HL6501MG), (oscillation wavelength approx.
685nm: Mitsubishi ML101J10), GaAlAs
(Oscillation wavelength 780 nm: Hitachi HL7859MG) etc.
It is preferably used. The green exposure light source of the present invention is a laser
-A light source is preferable, for example, a semiconductor laser GaAlA
YV with s (oscillation wavelength 808.7 nm) as the excitation light source
O_FourInversion of solid-state laser (oscillation wavelength 1064 nm)
LiNbO with main structure₃By SHG crystal
532nm green laser etc.
It is preferable to use. In the present invention, a clear image
To obtain, it is necessary to expose at a resolution of 200 dpi or more.
Preferably, it is more preferably 400 dpi or more,
It is preferably 600 dpi or more. "Dpi"
Is "pixels per inch". Such a scan
The exposure time in exposure was set to a pixel density of 400 dpi.
If the pixel size is defined as the exposure time,
The preferred exposure time is 10 ^-FourLess than a second, more preferably
Is 10^-6It is less than a second.

The total wetting time in the present invention is the time from the moment of immersing the light-sensitive material in the developing solution to the completion of the washing step through the bleach-fixing solution after exposure of the light-sensitive material (time immediately before moving to the drying step). is there. Maximum total wet time is 18
0 seconds (preferably 180 seconds to 10 seconds), but 100
7 seconds or less (preferably 100 seconds to 10 seconds), and 7
It is more preferably 0 seconds or less (preferably 70 seconds to 15 seconds). In addition, the development time is 45 seconds at the maximum (preferably 45 seconds to 3 seconds), but is preferably 30 seconds or less (preferably 30 seconds to 3 seconds), and 20 seconds or less (preferably 20 seconds to 3 seconds) is more preferable, and 5 seconds or more and 15 seconds or less is particularly preferable.

The temperature of the developing solution is in the range of 30 ° C to 60 ° C, preferably 40 ° C to 50 ° C.

From the viewpoint of productivity, it is preferable from the viewpoint of productivity that the time from the exposure to the immersion in the developing solution is preferably within 10 seconds (preferably 10 seconds to 1 second). preferable.

In the present invention, the blue-sensitive silver halide emulsion in the light-sensitive material must contain at least one blue-sensitive spectral sensitizing dye represented by the general formula (BI). Most preferably, all the blue-sensitive spectral sensitizing dyes in the blue-sensitive silver halide emulsion are the blue-sensitive spectral sensitizing dyes represented by formula (BI). Hereinafter, the compound represented by formula (BI) of the present invention will be described in detail.

In the present invention, when a specific moiety is referred to as a “group”, the moiety is substituted with one or more (up to the maximum possible number) of substituents even if the moiety is not itself substituted. Means that you can For example, "alkyl group" means a substituted or unsubstituted alkyl group. Further, the substituent that can be used in the compound of the present invention includes any substituent regardless of the presence or absence of substitution.

When the substituent is V, the substituent represented by V is not particularly limited, and examples thereof include a halogen atom, an alkyl group [(including a cycloalkyl group and a bicycloalkyl group), and an alkenyl group (a cycloalkenyl group). , Including a bicycloalkenyl group) and an alkynyl group], an aryl group, a heterocyclic group (also referred to as a heterocyclic group),
Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group A), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group,
Alkyl and aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups , Carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phospho groups, silyl groups, hydrazino groups, ureido groups, and other known substituents. Take as an example.

More specifically, V is a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group [straight chain,
It represents a branched or cyclic substituted or unsubstituted alkyl group.
They are alkyl groups (preferably C1-C30 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2
-Chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group ( Preferably 5 to 3 carbon atoms
A substituted or unsubstituted bicycloalkyl group of 0, such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), and a tricyclo structure having many ring structures. Includes. The alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below includes the following alkenyl group, cycloalkenyl group, bicycloalkenyl group, alkynyl group and the like in addition to the alkyl group having such a concept. ], An alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms). Cycloalkenyl groups such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl groups (substituted or unsubstituted bicycloalkenyl groups, preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms) Groups such as bicyclo [2,2,1] hept-2-ene-
1-yl, bicyclo [2,2,2] oct-2-ene-
4-yl). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably 6 carbon atoms)
~ 30 substituted or unsubstituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o
-Hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, More preferably, it has 3 to 30 carbon atoms.
A 5- to 6-membered aromatic heterocyclic group such as 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl, still 1-methyl-2-pyridinio, 1-methyl-2
A cationic heterocyclic group such as quinolinio),

Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 3 carbon atoms)
0 substituted or unsubstituted alkoxy group, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy, aryloxy group (preferably substituted or unsubstituted with 6 to 30 carbon atoms). Aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably C3-20 silyloxy groups such as trimethylsilyloxy). , T-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, for example, 1-phenyltetrazole-5-oxy, 2
-Tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and 6 carbon atoms)
30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p
-Methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N , N-di-n-
Octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy). , N-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably having 7 to 7 carbon atoms).
30 substituted or unsubstituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

Amino group (preferably amino group, carbon number 1)
˜30 substituted or unsubstituted alkylamino group, substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N
-Methylanilino, diphenylamino), an ammonio group (preferably an ammonio group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an aryl group, an ammonio group substituted with a heterocycle, for example, trimethylammonio, triethylammonio, diphenylmethylammonio E), an acylamino group (preferably a formylamino group, a carbon number of 1 to 3)
0 substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri -N-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxy). Carbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) phenoxycarbonylamino), sulfamoylamino group (preferably having 0 to 10 carbon atoms). 0 substituted or unsubstituted sulfamoylamino group, such as sulfamoylamino, N,
N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted carbon atoms having 6 to 30 carbon atoms, or Unsubstituted arylsulfonylamino groups such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-
Trichlorophenylsulfonylamino, p-methylphenylsulfonylamino),

A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably substituted or unsubstituted having 6 to 30 carbon atoms). Arylthio group such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio, a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl group (preferably having a carbon number of 0 to 30)
A substituted or unsubstituted sulfamoyl group, for example N-
Ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl) A sulfo group, an alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl,
p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl, ethylsulfonyl, Phenylsulfonyl, p
-Methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or 4 to 30 carbon atoms) A heterocyclic carbonyl group bonded to a carbonyl group at a substituted or unsubstituted carbon atom of, for example, acetyl, pivaloyl,
2-chloroacetyl, stearoyl, benzoyl, p-
n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl). , M
-Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxy). Carbonyl), carbamoyl group (preferably having 1 carbon atom)
~ 30 substituted or unsubstituted carbamoyl group, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

Aryl and heterocyclic azo groups (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo,
5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide,
N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably having 2 to 30 carbon atoms). A substituted or unsubstituted phosphinyl group,
For example, phosphinyl, dioctyloxyphosphinyl,
Diethoxyphosphinyl), phosphinyloxy group (preferably substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphini Ruamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a phospho group, a silyl group (preferably having 3 to 30 carbon atoms). Thirty
A substituted or unsubstituted silyl group such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms such as trimethylhydrazino), a ureido group. (Preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N-dimethylureido).

Further, two V's are linked to each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle. These can be further combined to form a polycyclic condensed ring. For example, a benzene ring. , Naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring,
Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, carbazole ring, phenanthridine ring, Examples thereof include an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiine ring, a phenothiazine ring and a phenazine ring. It is also possible to adopt a structure in which) is condensed.

Among the above-mentioned substituents V, those having a hydrogen atom may be substituted with the above-mentioned substituent after removing the hydrogen atom. Examples of such composite substituents include acylsulfamoyl groups, alkyl and arylsulfonylcarbamoyl groups. Examples thereof include methylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl, acetylsulfamoyl and benzoylsulfamoyl groups.

The methine dye represented by formula (BI) of the present invention will be described in detail below. When Y is an atomic group necessary for forming a benzene ring, another 5
It may be condensed with a 6-membered carbon ring or heterocycle to form, for example, a naphthalene ring, anthracene ring, phenanthrene ring, indole ring, benzofuran ring or benzothiophene ring. When Y is a group of atoms necessary for forming a heterocycle, Y is a 3- to 8-membered compound having at least one hetero atom such as nitrogen, oxygen, sulfur, phosphorus, selenium or tellurium atom in the ring. It means a ring, preferably a 5- to 6-membered heterocycle. The 5-membered unsaturated heterocycle formed by Y is a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a furan ring, an oxazole ring, an isoxazole ring, a thiophene ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, and a selenophene ring. , A selenazole ring, an isoselenazole ring, a tellurophen ring, a tellurazole ring, an isotellurazole ring, and the like, and a 6-membered unsaturated heterocycle includes a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyran ring, a thiopyran ring, and the like. It is possible,
Fused with another 5- or 6-membered carbocycle or heterocycle,
For example, an indole ring, a benzofuran ring, a benzothiophene ring, or a thienothiophene ring can be formed. Further, unsaturated heterocycles in which some of the double bonds in these heterocycles are hydrogenated (eg, pyrroline ring, pyrazoline ring, imidazoline ring, dihydrofuran ring, oxazoline ring, dihydrothiophene ring, thiazoline ring), or all May be a hydrogenated saturated heterocycle (eg, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, tetrahydrofuran ring, oxazolidine ring, tetrahydrothiophene ring, thiazolidine ring).

The ring formed by Y is preferably a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring or a benzothiophene ring, more preferably a benzene ring, a pyrrole ring or a thiophene ring. Or, it is a furan ring, more preferably a benzene ring or a thiophene ring.

In the general formula (BI), when the ring formed by Y is selected from a pyrrole ring, a furan ring and a thiophene ring, the direction of condensation of the ring Y is arbitrary, but a case of a thiophene ring is exemplified. Taking the above, a thieno [3,2-d] thiazole type in which the sulfur atom of the thiophene ring is on the same side as the thiazole ring sulfur atom with respect to the condensed carbon-carbon bond, or a thieno [3,2-d] thiazole type on the side opposite to the thiazole ring sulfur atom 2,3-d]
Of the thiazole type and the thieno [3,4-d] thiazole type condensed at the 3,4 positions of the thiophene ring, the former two are preferable. When long-wave spectral absorption is required as the sensitizing dye, thieno [2,3-d] thiazole type is particularly preferable.

The ring formed by Y may have a substituent, and the above-mentioned substituent represented by V can be mentioned as an example. Preferred as the substituent V is the above-mentioned alkyl group,
An aryl group, an aromatic heterocyclic group, an alkoxy group, an alkylthio group, a cyano group, and a halogen atom. It is particularly preferable to have a substituent on the ring formed by Y, and the substituent is an alkyl group (for example, methyl), an aryl group (for example, phenyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), an alkoxy group. (Eg methoxy), alkylthio group (eg methylthio), cyano group, halogen atom (eg fluorine, chlorine, bromine, iodine) are preferred, more preferably halogen atom, and particularly preferably chlorine atom or bromine atom. is there.

Examples of the substituent represented by V ¹ , V ² , V ³ and V ⁴ include the respective substituents represented by V above. V ¹ and V ⁴
Is preferably a hydrogen atom, and V ² and V ³ are a hydrogen atom or an alkyl group (eg, methyl), an aryl group (eg, phenyl), an aromatic heterocyclic group (eg, 1-pyrrolyl), an alkoxy group (eg, methoxy). , An alkylthio group (eg, methylthio), a cyano group, and a halogen atom (eg, fluorine, chlorine, bromine, iodine) are preferable. V ³ is more preferably a hydrogen atom, and V ² is more preferably a halogen atom, particularly preferably a chlorine atom or a bromine atom.

The alkyl group represented by R ¹ and R ² may be unsubstituted or substituted and has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (for example, an unsubstituted alkyl group). , Methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, hexyl, octyl, dodecyl,
Octadecyl), or 1 to 18 carbon atoms, preferably 1
~ 7, particularly preferably 1 to 4 substituted alkyl groups {As the substituent, each substituent represented by V (aryl group, unsaturated hydrocarbon group, carboxy group, sulfo group, sulfato group, cyano group, Halogen atom (eg fluorine, chlorine, bromine, iodine), hydroxy group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, sulfamoyl Group, a heterocyclic group, an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonylsulfamoyl group, and the like, which may be further substituted).

The aryl group represented by R ¹ and R ² may be unsubstituted or substituted and has 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms.
An unsubstituted aryl group (for example, phenyl, 1-naphthyl), or having 6 to 26 carbon atoms, preferably 6 to 2 carbon atoms
1, more preferably a substituted aryl group having 6 to 16 carbon atoms (as the substituent, each substituent represented by V (alkyl group and aryl group, unsaturated hydrocarbon group, carboxy group, sulfo group, sulfato group A cyano group, a halogen atom (for example, fluorine, chlorine, bromine, iodine), a hydroxy group, a mercapto group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, Carbamoyl group, sulfamoyl group, heterocyclic group,
Alkylsulfonylcarbamoyl group, acylcarbamoyl group, acylsulfamoyl group, alkylsulfonylsulfamoyl group and the like, which may be further substituted), and is preferably a phenyl group.

The heterocyclic group represented by R ¹ and R ² may be unsubstituted or substituted and has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Substituted heterocyclic group (for example, pyrrole, furan, thiophene), or C1 to C26, preferably C1 to C2
1, more preferably a substituted heterocyclic group having 1 to 16 carbon atoms (the substituent includes each substituent represented by V above).

R ¹ and R ² are preferably an acid group or a group having a dissociative proton (specifically, a carboxyl group,
Sulfo group, phosphonic acid group, boronic acid group, or -CO
_{NHSO 2 -, - SO 2 NHSO} 2 -, - CONHCO
-, - a group SO ₂ NHCO-, etc.} is substituted, more preferably an alkyl group substituted by a group having the above acid group or dissociative proton, more preferably a carboxyl group, a sulfo group, an alkylsulfonyl A carbamoyl group (eg methanesulfonylcarbonyl), an acylcarbamoyl group (eg acetylcarbamoyl), an acylsulfamoyl group (eg acetylsulfamoyl),
A substituted alkyl group containing any of an alkylsulfonylsulfamoyl group (eg, methanesulfonylsulfamoyl). Particularly preferably, carboxymethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-
It is a sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group. Furthermore, R ¹ ,
Most preferably, one of R ² is a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group or a 4-sulfobutyl group, and the other is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group.

The methine group represented by L may have a substituent, and examples of the substituent include the respective substituents represented by V above, but it is preferably unsubstituted.

M in the general formula (BI) is included in the formula to indicate the presence of a cation or anion when necessary to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its substituents and the environment in solution (pH, etc.). Typical cations are inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg calcium ion), ammonium ions (eg, Examples thereof include organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5,4,0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, a halide anion (eg, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (eg p- Toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion,
2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Is mentioned. In addition, ionic polymers or other dyes having an opposite charge to the dye may be used. Preferred cations are sodium ion, potassium ion, triethylammonium ion,
Tetraethylammonium ion, pyridinium ion, ethylpyridinium ion, and methylpyridinium ion. Preferred anions are perchlorate ion, iodide ion, bromide ion and substituted aryl sulfonate ion (eg p-toluene sulfonate ion).
m represents a number of 0 or more necessary to balance the charge, and is 0 when forming an intramolecular salt. Preferably 0 or more 4
The following numbers.

Specific examples of the compound represented by formula (BI) of the present invention are shown below, but the present invention is not limited thereto. In addition to the following, Japanese Patent Application No. 2001-11828
It can also be selected from the methine dyes S-1 to S-158 described in No. 1 specification.

[0050]

[Chemical 17]

[0051]

[Chemical 18]

[0052]

[Chemical 19]

[0053]

[Chemical 20]

[0054]

[Chemical 21]

[0055]

[Chemical formula 22]

[0056]

[Chemical formula 23]

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

In the present invention, the red-sensitive silver halide emulsion in the light-sensitive material preferably contains at least one red-sensitive spectral sensitizing dye represented by the general formula (R-I). Most preferably, all the red-sensitive spectral sensitizing dyes in the red-sensitive silver halide emulsion are the red-sensitive spectral sensitizing dyes represented by formula (RI). The general formula (R
The sensitizing dye represented by -I) will be described in detail. Z
₁ is preferably a sulfur atom, and Z ₂ is preferably an oxygen atom or a sulfur atom. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each independently represent a methine group, such as a substituted or unsubstituted alkyl group (eg methyl, ethyl), a substituted or unsubstituted aryl group (eg phenyl) or It may be substituted with a halogen atom (eg chlorine, bromine). Further, the methine groups may form a 5- or 6-membered carbon ring, and it is particularly preferable that L ₂ and L ₄ form a 6-membered ring.

R ₁ and R ₂ represent the same or different alkyl groups, preferably an unsubstituted alkyl group having 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl). , Octadecyl) and substituted alkyl groups (as a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, bromine, etc.), a hydroxy group, a carbon number of 2 to 2
8 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), alkoxy groups having 1 to 8 carbon atoms (eg methoxy, ethoxy, benzyloxy, phenethyloxy), monocyclic rings having 6 to 10 carbon atoms An aryloxy group of the formula (eg, phenoxy, p-tolyloxy), an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy, propionyloxy), an acyl group having 2 to 8 carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), Carbamoyl group having 1 to 8 carbon atoms (for example, carbamoyl, N, N
-Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group having 0 to 8 carbon atoms (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), an aryl having 6 to 10 carbon atoms Groups (eg phenyl,
4-chlorophenyl, 4-methylphenyl, α-naphthyl) and other substituted alkyl groups having 18 or less carbon atoms. Particularly preferred are unsubstituted alkyl groups (eg methyl, ethyl) and sulfoalkyl groups (eg 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl). R ₁ may be linked to L ₁ and / or R ₂ may be linked to L ₅ to form a 5- or 6-membered carbocycle.

V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ and V ₈ are each a hydrogen atom, a halogen atom (eg fluorine, chlorine, bromine), an unsubstituted alkyl group, More preferably, an unsubstituted alkyl group having 1 to 10 carbon atoms (eg methyl, ethyl), a substituted alkyl group, more preferably a substituted alkyl group having 1 to 18 carbon atoms (eg benzoyl,
α-naphthylmethyl, 2-phenylethyl, trifluoromethyl), an acyl group, more preferably 2 to 10 carbon atoms.
An acyl group (eg acetyl, benzoyl, mesyl),
Acyloxy group, more preferably an acyloxy group having 2 to 10 carbon atoms (eg acetyloxy group), an alkoxycarbonyl group, more preferably an alkoxycarbonyl group having 2 to 10 carbon atoms (eg methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl). A substituted or unsubstituted carbamoyl group having 1 to 10 carbon atoms (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), 0 carbon atoms
10 substituted or unsubstituted sulfamoyl groups (eg, sulfamoyl, N, N-dimethylsulfamoyl,
Morpholinosulfonyl, piperidinosulfonyl), carboxy group, cyano group, hydroxy group, amino group, acylamino group, more preferably an acylamino group having 2 to 8 carbon atoms (for example, acetylamino), an alkoxy group, more preferably 1 carbon atom An alkoxy group having 10 to 10 (for example, methoxy, ethoxy, benzyloxy), an alkylthio group, more preferably an alkylthio group having 1 to 10 carbon atoms (for example, ethylthio), an alkylsulfonyl group, preferably an alkylsulfonyl group having 1 to 10 carbon atoms ( (Eg, methylsulfonyl), a sulfonic acid group, an aryloxy group, preferably an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy), an aryl group, preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, tolyl). Represent. Also,
Two of V _{1 to} V ₈ which are bonded to adjacent carbon atoms may be bonded to each other to form a condensed ring. For example, as the condensed ring, a benzene ring and a heterocycle (for example, pyrrole, thiophene, furan, pyridine, imidazole,
Triazole and thiazole).

(Y ¹ ) _S is included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye.
Therefore, s can take an appropriate value of 0 or more as required. Whether a dye is a cation, an anion, or has no net ionic charge depends on its auxochrome and substituents. The counter ion (Y ¹ ) _S is
It can be easily replaced after the dye is manufactured. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be either an inorganic or organic anion, for example a halogen anion (eg a fluorine ion). , Chloride ion, bromide ion, iodine ion), substituted aryl sulfonate ion (eg p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (eg 1,3-benzene disulfonate ion, 1 , 5-naphthalene disulfonate ion,
2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion And so on. Preferred are p-toluenesulfonate ion and iodine ion.

The specific examples of the compounds represented by formula (RI) are shown below, but the invention is not limited thereto.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Chemical formula 26]

The addition amount of each of the spectral sensitizing dyes represented by the general formulas (BI) and (RI) varies depending on the shape and size of the silver halide grains used, but is preferably halogenated. 1.0 × 10 ⁻⁷ mol to 1.0 × 1 per mol of silver
It is in the range of 0 ^-2 mol, more preferably 5.0 x 10 ^-7.
To 1.0 × 10 ⁻² mol, and more preferably,
It is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 0 ⁻³ mol.

The compounds represented by the general formulas (BI) and (RI) of the present invention are described in "Heterocyclic Compou" by FM Hamer.
nds-Cyanine Dyes and Related Compounds, '' John Wil
ey & Sons-New York, London, 1964,
DMS Turmer `` Heterocyclic Compounds-Special topi
cs in heterocyclic chemistry ”, Chapter 18, 14
S., pp. 482-515, John Wiley & Sons-New York, London, 1977, "Rodd's Chemist.
ry of Carbon Compounds "2nd Ed. vol.IV, part B, 1
977, Chapter 15, 369-422, Elsevier S
Published by cience Publishing Company Inc., New York,
It can be synthesized based on the method described in.

The compounds represented by formulas (BI) and (RI) of the present invention may be used in combination with other sensitizing dyes other than those of the present invention in the same emulsion used. The dye used is preferably a cyanine dye, a merocyanine dye,
Examples thereof include rhodacyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, allopolar dye, hemicyanine dye and styryl dye. More preferably a cyanine dye, a merocyanine dye, a rhodacyanine dye,
Particularly preferred is a cyanine dye. For more information on these dyes, see FM Hemer, “Heterocyclic Compounds-
Cyanine Dyes and Related Compounds, '' John Wiley &
Sons-New York, London, 1964, D.
Heterocyclic Compounds-Special topics by M. Sturmer
in heterocyclic chemistry ", Chapter 18, Section 14,
Pp. 482-515. Preferred general formulas for the dyes are shown in the general formulas described in U.S. Pat. No. 5,994,051, pages 32 to 44, and in the US Pat. Examples include sensitizing dyes. Also, a preferred cyanine dye,
The general formulas of merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,694, columns 21 to 22 (XI),
Those shown in (XII) and (XIII) (however, n ₁₂ ,
The number of n ₁₅ , n ₁₇ , and n ₁₈ is not limited and is an integer of 0 or more (preferably 4 or less). ) Is mentioned.

Although one kind of these sensitizing dyes may be used,
Two or more kinds may be used, and a combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545 and 2,977,22.
No. 9, No. 3,397,060, No. 3,522, 0
No. 52, No. 3,527, 641, No. 3,617,
No. 293, No. 3,628,964, No. 3,66
No. 6,480, No. 3,672,898, No. 3,6
79,428, 3,303,377, 3,
769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 1,344,281, 1,507,80.
No. 3, Japanese Patent Publication No. 43-49336, No. 53-12375.
No. 5, JP-A Nos. 52-110618 and 52-10992.
No. 5 and the like.

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

Supersensitizers useful in spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts). , And a combination of a supersensitizer and a sensitizing dye are described in, for example, US Pat.
No. 664, No. 3,615, 613, No. 3,61
No. 5,632, No. 3,615, 641, No. 4,5
96,767, 4,945,038, 4,
965,182, 4,965,182, 2,933,390, 3,635,721, 3,743,510, 3,617,295,
No. 3,635,721, etc., and the method described in the above-mentioned patent is also preferable for its usage.

The sensitizing dye used in the present invention (also for other sensitizing dyes and supersensitizers) can be directly dispersed in the emulsion. Also, these are first of all suitable solvents, such as methyl alcohol, ethyl alcohol,
It may be dissolved in methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be coexistent. Ultrasonic waves can also be used for dissolution. As a method of adding this compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid to prepare a dispersion of this compound. Is added to the emulsion, as described in JP-B-46-24185 and the like, a method of dispersing in a water-soluble solvent and adding the dispersion to the emulsion, U.S. Pat. No. 3,822,13.
No. 5, a method of dissolving a compound in a surfactant and adding the solution to an emulsion, JP-A-51-74624.
As described in JP-A No. SHO-50-, a method of dissolving with a compound for red-shifting and adding the solution to an emulsion is disclosed.
As described in No. 80826, a method in which a compound is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used. In addition, the method described in US Pat. Nos. 2,912,343, 3,342,605, 2,996,287, and 3,429,835 can be used for addition to the emulsion. .

Examples of the organic solvent for dissolving the sensitizing dye used in the present invention include methyl alcohol, ethyl alcohol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, benzyl alcohol, fluorine alcohol, methyl. Examples thereof include cellosolve, acetone, pyridine, and a mixed solvent thereof.

When the sensitizing dye of the present invention is dissolved in water, the above organic solvent or a mixed solvent thereof, it is also preferable to add a base. The base may be either an organic base or an inorganic base, and examples thereof include amine derivatives (for example, triethylamine and triethanolamine), pyridine derivatives, sodium hydroxide, potassium hydroxide, sodium acetate and potassium acetate. As a preferable dissolution method, a method of adding a dye to a mixed solvent of water and methanol and further adding triethylamine in an equimolar amount to the dye can be mentioned.

The grain shape of the silver halide emulsion of the present invention is not particularly limited, but it is a cubic or tetradecahedral crystal grain having substantially {100} faces (these grains have rounded apexes and higher grains). It may have the following planes), octahedral crystal grains, and tabular grains having an aspect ratio of 2 or more whose main surface is a {100} plane or a {111} plane. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. In the present invention, the blue-sensitive silver halide emulsion is more preferably tabular grains having an aspect ratio of 2 or more.

The silver halide emulsion of the present invention needs to have a silver chloride content of 90 mol% or more, and from the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more, and 95 mol% or more. % Or more is more preferable. The silver bromide content is preferably 0.1 to 7 mol% and more preferably 0.5 to 5 mol% because it has a high contrast and excellent latent image stability. The silver iodide content is preferably from 0.02 to 1 mol%, more preferably from 0.05 to 0.50 mol%, and still more preferably from 0.
Most preferably, it is 07 to 0.40 mol%. The silver halide grains of the present invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above halogen composition.

The silver halide grains of the present invention can have a silver bromide-containing phase and / or a silver iodide-containing phase.
Here, the silver bromide- or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than that of the surrounding area. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide- or silver iodide-containing phase may form a layer having a substantially constant width in a certain portion within the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and further preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide- or silver iodide-containing phases may be present in each grain in a layered form, and the respective silver bromide or silver iodide content may differ.
Each must have at least one contained phase.

The silver bromide-containing phase or silver iodide-containing phase of the silver halide emulsion of the present invention is preferably layered so as to surround the grains. The silver bromide-containing phase or the silver iodide-containing phase formed in a layer so as to surround the grains is
One of the preferred embodiments is to have a uniform concentration distribution in the orbital direction of the particles in each phase. However, in the silver bromide-containing phase or the silver iodide-containing phase that is layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the orbiting direction of the grain, and the concentration distribution May have. For example, when the layer has a silver bromide-containing phase or a silver iodide-containing phase near the surface of the grain so as to surround the grain, the concentration of silver bromide or silver iodide at the corner or edge of the grain is different from that on the main surface. There are cases.
Further, apart from the silver bromide-containing phase and the silver iodide-containing phase which are layered so as to surround the grain, the silver bromide-containing phase which is completely isolated and exists in a specific part of the surface of the grain and does not surround the grain. Alternatively, there may be a silver iodide-containing phase.

When the silver halide emulsion of the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered form so as to have a maximum silver bromide concentration inside the grain. . When the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in layers so that the grain surface has a maximum silver iodide concentration. Such a silver bromide-containing phase or a silver iodide-containing phase is composed of 3% or more and 30% or less of the grain volume in terms of increasing the local concentration with a smaller silver bromide or silver iodide content. Preferably 3% or more 1
It is more preferable that the amount of silver is 5% or less.

The silver halide emulsion of the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In that case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same spot or different spots in the grain, but different spots are preferable from the viewpoint of facilitating the control of grain formation.
Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, the iodide added during the formation of high silver chloride grains is more likely to exude to the grain surface than bromide, so that the silver iodide-containing phase is likely to be formed in the vicinity of the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different positions in the grain, it is preferable that the silver bromide-containing phase is formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

The silver bromide content or silver iodide content necessary for exhibiting effects such as high sensitivity and high contrast is such that the silver bromide-containing phase or the silver iodide-containing phase is formed inside the grain. However, the silver chloride content may be increased more than necessary, and the rapid processability may be impaired by lowering the silver chloride content more than necessary. Therefore, it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are adjacent to each other in order to concentrate these functions for controlling the photographic effect near the surface in the grain. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume and the silver iodide-containing phase is at any of the positions of 85% to 100% of the grain volume measured from the inside. It is preferable to form a crab. The silver bromide-containing phase is 70% to 95% of the grain volume.
It is more preferable that the silver iodide-containing phase is formed at any position of 90% to 100% of the grain volume.

The introduction of the bromide or iodide ion to contain silver bromide or silver iodide in the silver halide emulsion of the present invention can be carried out by adding a solution of bromide salt or iodide salt alone or by adding a silver salt. A bromide salt or iodide salt solution may be added together with the addition of the solution and the high chloride salt solution. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide salt or iodide salt and the high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ion or iodide ion from the organic molecule described in US Pat. No. 5,389,508. Fine silver bromide grains or fine silver iodide grains can also be used as another bromide or iodide ion source.

The addition of the bromide salt or iodide salt solution is
The particle formation may be concentrated in one period, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained. On the other hand, the bromide salt solution is preferably added to the outside of 50% of the grain volume, more preferably outside of 70%.

The distribution of the bromide or iodide ion concentration in the grain in the depth direction is determined by etching / TOF-SIMS.
(Time of Flight − Secondary Ion Mass Spectrometr
y) method, for example, TRIFT II type TO manufactured by Phi Evans
It can be measured using F-SIMS. The TOF-SIMS method is specifically described in "Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry" edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (issued in 1999). Etching / TOF-SIMS
When the emulsion grains are analyzed by the method, it can be analyzed that even if the addition of the iodide salt solution is completed inside the grains, the iodide ions seep out toward the grain surface. In the emulsion of the present invention, it is preferable that the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration is attenuated toward the inner side in the analysis by the etching / TOF-SIMS method. It is preferable to have a maximum concentration inside. The local concentration of silver bromide can also be measured by an X-ray diffraction method if the silver bromide content is high to some extent.

The equivalent spherical diameter of the silver halide grains contained in the silver halide emulsion of the present invention is not particularly limited, but is preferably 0.4 μm or less for rapid development processing.
More preferably, it is 0.3 μm or less. A particle having a sphere equivalent diameter of 0.4 μm corresponds to a cubic particle having a side length of about 0.32 μm, and a particle having a sphere equivalent diameter of 0.3 μm has a side length of about 0.24 μm.
Corresponds to cubic particles of m. The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains contained in the silver halide emulsion defined in the present invention (that is, specific silver halide grains). However, in the silver halide emulsion defined in the present invention, 50% or more of the total projected area of all grains must be silver halide grains defined in the present invention, and preferably 80% or more. , 90% or more is more preferable.

The silver halide emulsion of the present invention preferably contains iridium. As the iridium compound, a hexacoordinated complex having six ligands and iridium as a central metal is preferable because it can be uniformly incorporated into the silver halide crystal. As one preferable embodiment of iridium used in the present invention, a hexacoordinated complex having Ir as a central metal and having Cl, Br or I as a ligand is preferable, and Ir in which all six ligands are Cl, Br or I is A hexacoordination complex having a central metal is more preferable. In this case, Cl, Br or I may be mixed in the hexacoordinated complex. It is particularly preferable that the hexacoordination complex having Cl, Br or I as a ligand and having Ir as a central metal is contained in the silver bromide-containing phase in order to obtain a hard gradation by exposure to high illuminance.

In the following, all 6 ligands were Cl, Br
Further, specific examples of the hexacoordinated complex of I having Ir as a central metal will be given, but the iridium in the present invention is not limited thereto. [IrCl ₆ ] ^2- [IrCl ₆ ] ^3- [IrBr ₆ ] ^2- [IrBr ₆ ] ^3- [IrI ₆ ] ^3-

As a different preferred embodiment of iridium used in the present invention, a hexacoordination complex having Ir as a central metal and having at least one ligand other than halogen or cyan is preferable, and H ₂ O, OH, O, OCN and thiazole are preferable. Or, a 6-coordination complex having Ir as a central metal having a substituted thiazole as a ligand is preferable, and at least one H ₂ O, OH, O, OCN, thiazole or a substituted thiazole as a ligand and the remaining ligands are Cl,
A hexacoordinated complex having Ir or Ir as a central metal, which is Br or I, is more preferable. Furthermore, one or two 5-methylthiazoles are used as ligands and the remaining ligands are C
Most preferred is a hexacoordinated complex having Ir as a central metal and consisting of 1, Br or I.

In the following, at least one H ₂ O, OH,
Specific examples of the hexacoordinated complex having O, OCN, thiazole or substituted thiazole as a ligand and the rest of the ligands consisting of Cl, Br or I and Ir as the central metal are shown below, but the iridium in the present invention is not limited thereto. .

[Ir (H ₂ O) Cl ₅ ] ^2- [Ir (H ₂ O) ₂ Cl ₄ ] ^- [Ir (H ₂ O) Br ₅ ] ^2- [Ir (H ₂ O) ₂ Br ₄ ] _{^{- [Ir (OH) Cl 5}} ] 3- [Ir (OH) 2 Cl 4] 3- [Ir (OH) Br 5] 3- [Ir (OH) 2 Br 4] 3- [Ir (O) Cl 5 ] ^4- [Ir (O) ₂ Cl ₄ ] ^5- [Ir (O) Br ₅ ] ^4- [Ir (O) ₂ Br ₄ ] ^5- [Ir (OCN) Cl ₅ ] ^3- [Ir (OCN)] Br _5] ^3- [Ir (thiazole) Cl _5] ^2- [Ir ^{_{(thiazole) 2 Cl 4] - [Ir}} ( thiazole) Br _5] ^2- [Ir ^{_{(thiazole) 2 Br 4] - [Ir}} (5- ^{_{methylthiazole) Cl 5] 2- [Ir (}} 5- ^{_{methylthiazole) 2 Cl 4] - [Ir}} (5- ^{_{methylthiazole) Br 5] 2- [Ir (}} 5- methylthiazole) ₂ Br _4] ^-

The metal complexes listed above are anions,
When a salt is formed with a cation, a counter cation which is easily dissolved in water is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion, and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.) before use. You can These iridium complexes are added at 1 x 1 per mole of silver during grain formation.
It is preferable to add 1 × 10 ^-3 mol from 0 ^-10 mol, 1 ×
Most preferably, it is added from 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol.

In the present invention, the above iridium complex is
By adding directly to the reaction solution at the time of silver halide grain formation, or in an aqueous solution of a halide for forming silver halide grains, or in a solution other than that, and then adding to the grain formation reaction solution, the halogen It is preferably incorporated into silver halide grains. Further, it is also preferable to physically ripen fine particles in which an iridium complex has been incorporated into the grains and incorporate them into the silver halide grains. Further, these methods may be combined and contained in the silver halide grains.

When these complexes are incorporated in silver halide grains, they may be made to exist uniformly inside the grains. JP-A-4-208936 and JP-A-2-12524
5, as disclosed in JP-A-3-188437, it is also preferable that the particles are present only in the particle surface layer,
It is also preferable that the complex is present only inside the particles and a layer not containing the complex is added to the surface of the particles. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical aging of fine particles in which a complex is incorporated to modify the surface phase of the particles. Is also preferable. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the above complex is contained, but all 6 ligands have Cl, Br, or I as the central metal 6
The coordination complex is preferably contained in the silver bromide concentration maximum part.

In the present invention, in addition to iridium, other metal ions can be doped inside and / or on the surface of the silver halide grain. The metal ion used is preferably a transition metal ion, of which iron, ruthenium, osmium, lead, cadmium, or zinc is preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion. It is preferable to use a nitrosyl ion, and it is also preferable to use it by coordinating to any of the above-mentioned metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and to use a plurality of types of ligands in one complex molecule. It is also preferable to use. Further, an organic compound can be used as the ligand, and preferred organic compounds include a chain compound having a main chain having 5 or less carbon atoms and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to a metal, and particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds having these compounds as a basic skeleton and substituents introduced therein are also preferable.

The combination of a metal ion and a ligand is preferably an iron ion or a combination of ruthenium ion and a cyanide ion. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably occupies a majority of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide,
It is preferably populated with pyridine, pyrazine or 4,4'-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron or hexacyanoruthenium complex. It is preferable to add 1 × 10 ^-8 mol to 1 × 10 ^-2 mol per mol of silver of the complex having a cyanide ion as a ligand, and 1 × 10 ^-6 mol to 5 × 10 5 mol per 1 mol of silver. It is most preferable to add ^-4 mol. When ruthenium and osmium are the central metals, it is also preferable to use nitrosyl ion, thionitrosyl ion, or water molecule and chloride ion together as ligands.
It is more preferable to form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and it is also preferable to form a hexachloro complex. These complexes are used during the grain formation
It is preferable to add 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol per mol, and more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol.

The oxidation potential of the latent image of the silver halide emulsion of the present invention is preferably nobler than 70 mV, and 100 m
More preferably, it is noble than V. The oxidation potential of the latent image being nobler than 70 mV means that the latent image has relatively strong oxidation resistance. Oxidation potential of latent image is based on Photographic Sensitivity- (Photo
graphic Sensitivity, Oxford
d University Press, Tadaak
i Tani 1995) 103, page 103 and the like. Specifically, the silver halide emulsion coating is subjected to gradation exposure for 0.1 seconds,
Before development, the latent image is bleached by immersing it in a redox bath of various potentials.

The silver halide emulsion of the present invention is usually chemically sensitized. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold-sensitized ones are particularly preferable. By performing gold sensitization, it is possible to further reduce fluctuations in photographic performance when scanning and exposing with laser light or the like.

In order to perform gold sensitization on the silver halide emulsion of the present invention, various inorganic gold compounds, gold (I) complexes having inorganic ligands and gold (I) compounds having organic ligands are used. can do. As the inorganic gold compound, for example, chloroauric acid or a salt thereof, and as the gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate compound such as potassium gold (I) dithiocyanate or gold (I) 3 dithiosulfate is used. Compounds such as sodium dithiosulfate compounds such as sodium can be used.

The silver halide emulsion of the present invention is preferably gold-sensitized with a gold sensitizer having a colloidal gold sulfide or gold complex stability constant log β ₂ of 21 or more and 35 or less. The method for producing colloidal gold sulfide is described in Research Disclosure, 37154, Solid State Ionics, Vol. 79, pp. 60-66, 1995, Compt.Rend.Heb.
t.Seances Acad.Sci.Sect.B Vol.263, p.1328,
It is described in 1966. Various sizes of colloidal gold sulfide can be used, and particles having a particle size of 50 nm or less can also be used. The addition amount may vary widely depending on the case, but it is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 1 as a gold atom per mol of silver halide.
It is 0 ^{-6 to} 5 x 10 ^-4 mol. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound.

Below, the complex stability constant logβ _{2 of} gold is 2
The gold sensitizer of 1 or more and 35 or less will be described. The complex stability constant log β ₂ of gold is measured by a comprehensive
Coordination Chemistry (Compreh
intensive Coordination Chemis
try, Chapter 55, p.864, 1987), Encyclopedia of Electrochemistry of.
The Elements (Encyclopedia of El)
electrochemistry of the Elem
ents, Chapter IV-3, 1975), Journal
Of the Royal Netherlands Chemical Society (Journal of the RoyalN
etherlands Chemical Societ
y, vol. 101, p. 164, 1982), and the measuring methods described in the references thereof, and the measuring temperature is 2
5 ° C, pH adjusted to 6.0 with potassium dihydrogen phosphate / disodium hydrogen phosphate buffer, ionic strength 0.1M
The value of logβ ₂ can be calculated from the value of the gold potential under the condition of (KBr). The value of log β ₂ of thiocyanate ion in this measurement method is 20.5, which is described in the literature (Comprehensive Coordination Chemistry).
ation Chemistry, 1987, 55th
The values described in Chapter, page 864, Table 2)), values close to 20, are obtained.

Gold complex stability constant log β in the present invention
The gold sensitizer in which ₂ is 21 or more and 35 or less is preferably represented by the following general formula (I). General formula ^{(I) {(L 1)} x (Au) y (L 2) z · Q q} p

In the general formula (I), L ¹ and L ² are log
It represents a compound having a β ₂ value of 21 to 35. The compound contained in 22 to 31 is preferable, and the compound contained in 24 to 28 is more preferable.

L ¹ and L ² are, for example, compounds containing at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, hydantoin compounds,
It represents a thioether compound, a mesoionic compound, -SR ', a heterocyclic compound, a phosphine compound, an amino acid derivative, a sugar derivative, and a thiocyano group, which may be the same or different from each other. Here, R'represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a thiocarbamoyl group, or a sulfonyl group. Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, and x and z are 0 to 4
Represents an integer, y and p represent 1 or 2, and q represents a value of 0 to 1 including a decimal. However, neither x nor z is 0.

As the compound represented by the general formula (I), L ¹ and L ² preferably have at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide.
A compound containing one, a hydantoin compound, a thioether compound, a mesoionic compound, -SR ', a heterocyclic compound, or a phosphine compound, and x, y and z
Each represents 1.

More preferably, as the compound represented by formula (I), L ¹ and L ² contain at least one labile sulfur group capable of reacting with silver halide to form silver sulfide. Compound, mesoionic compound, or -S
Represents R ', and x, y, z and p each represent 1.

The gold compound represented by formula (I) will be described in more detail below. In the general formula (I), compounds having an unstable sulfur group capable of reacting with silver halides represented by L ¹ and L ² to produce silver sulfide include thioketones (for example, thioureas, Thioamides or rhodanines), thiophosphates,
Represents thiosulfates.

The compound containing at least one unstable sulfur group capable of reacting with silver halide to produce silver sulfide is preferably thioketones (preferably thioureas, thioamides and the like), thiosulfate. Represents a class.

Next, examples of the hydantoin compound represented by L ¹ and L ² in the general formula (I) include unsubstituted hydantoin and N-methylhydantoin.
The thioether compound contains 1 to 8 thio groups, and they are substituted or unsubstituted linear or branched alkylene groups (for example, ethylene, triethylene, etc.), or chained or cyclic linked with a phenylene group. Thioether (eg bishydroxyethyl thioether,
3,6-dithia-1,8-octanediol, 1,4
8,11-tetrathiacyclotetradecane) and the like, and the mesoionic compound is mesoionic-3.
-Mercapto-1,2,4-triazoles (e.g.
Mesoionic-1,4,5-trimethyl-3-mercapto-1,2,4-triazole etc.) and the like.

Next, in the general formula (I), L ¹ and L ² are-
In the case of representing SR ′, the aliphatic hydrocarbon group represented by R ′ is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n -Butyl, t-butyl, 2-
Pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 1,5-dimethylhexyl,
n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, hydroxyethyl, hydroxypropyl,
2,3-dihydroxypropyl, carboxymethyl, carboxyethyl, sodium sulfoethyl, diethylaminoethyl, diethylaminopropyl, butoxypropyl, ethoxyethoxyethyl, n-hexyloxypropyl, etc.), a substituted or unsubstituted cyclic group having 3 to 18 carbon atoms Alkyl groups (eg cyclopropyl, cyclopentyl,
Cyclohexyl, cyclooctyl, adamantyl, cyclododecyl, etc.), C2-C16 alkenyl groups (eg, allyl, 2-butenyl, 3-pentenyl, etc.), C2-C10 alkynyl groups (eg, propargyl, 3
-Pentynyl, etc.), an aralkyl group having 6 to 16 carbon atoms (eg, benzyl, etc.), and the like, and the aryl group includes a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms and a naphthyl group (eg, unsubstituted phenyl). , Unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, 2-carboxyphenyl and the like), and examples of the heterocyclic group include a substituted or unsubstituted nitrogen-containing hetero 5 Membered ring (for example, imidazolyl, 1,2,4-triazolyl, tetrazolyl,
Oxadiazolyl, thiadiazolyl, benzimidazolyl, purinyl, etc.), a substituted or unsubstituted nitrogen-containing hetero 6-membered ring (eg, pyridyl, piperidyl, 1,3,5-
Triazino, 4,6-dimercapto-1,3,5-triazino, etc.), a furyl group, or a thienyl group, and the like, and examples of the acyl group include acetyl and benzoyl, and examples of the carbamoyl group include dimethylcarbamoyl. And the like. Examples of the thiocarbamoyl group include diethylthiocarbamoyl and the like, and examples of the sulfonyl group include a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, etc.), carbon Examples of the substituted or unsubstituted phenylsulfonyl group of the formulas 6 to 16 (eg, phenylsulfonyl and the like) are included.

Further, as —SR ′ represented by L ¹ and L ² , R ′ is preferably an aryl group or a heterocyclic group, more preferably a heterocyclic group, and further preferably 5 or 6-membered. Is a nitrogen-containing heterocyclic group, most preferably a nitrogen-containing heterocyclic group substituted with a water-soluble group (eg, sulfo, carboxy, hydroxy, amino, etc.).

In the general formula (I), the heterocyclic compound represented by L ¹ and L ² is a substituted or unsubstituted nitrogen-containing hetero 5-membered ring (eg, pyrroles, imidazoles, pyrazoles, 1 , 2,3-triazoles, 1,
2,4-triazoles, tetrazoles, oxazoles, isoxazoles, isothiazoles, oxadiazoles, thiadiazoles, pyrrolidines, pyrrolines, imidazolidines, imidazolines, pyrazolidines, pyrazolines, hydantoins Etc.) and heterocycles containing the 5-membered ring (indoles, isoindoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazole) , Indolines, etc.), and substituted or unsubstituted nitrogen-containing hetero 6-membered rings (eg, pyridines, pyrazines, pyrimidines, pyridazines, triazines, thiadiazines, piperidines, piperazines, morpholines, etc.) ,
And heterocycles containing the 6-membered ring (for example, quinolines, isoquinolines, phthalazines, naphthyridines, quinoxalines, quinazolines, pteridines, phenaziridines, acridines, phenanthrolines,
Phenazines), substituted or unsubstituted furans, substituted or unsubstituted thiophenes, benzothiazolium and the like.

The heterocyclic compound represented by L ¹ and L ² is preferably an unsaturated nitrogen-containing hetero 5- or 6-membered ring, or a heterocycle containing the same, such as pyrroles, Imidazoles, pyrazoles,
1,2,4-triazoles, oxadiazoles, thiadiazoles, imidazolines, indoles, indolizines, indazoles, benzimidazoles,
Purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles, pyridines, pyrazines, pyrimidines, pyridazines, triazines, quinolines, isoquinolines, phthalazines, and the like. Heterocyclic compounds known in the art as antifoggants (eg, indazoles, benzimidazoles, benzotriazoles, tetraazaindenes, etc.) are preferred.

In the general formula (I), the phosphine compound represented by L ¹ and L ² includes an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heterocyclic group (for example, Pyridyl, etc.), a substituted or unsubstituted amino group (eg, dimethylamino, etc.), and / or an alkyloxy group (eg, methyloxy, ethyloxy, etc.) is substituted, and preferably represents 1 to 1 carbon atoms. Examples thereof include phosphines substituted with an alkyl group having 10 or an aryl group having 6 to 12 carbon atoms (eg, triphenylphosphine, triethylphosphine, etc.).

Further, the above-mentioned mesoionic compounds represented by L ¹ and L ² , —SR ′, and the heterocyclic compound include unstable sulfur groups capable of reacting with silver halide to produce silver sulfide. It is preferable that (for example, a thioureido group or the like) is substituted.

Further, the compounds represented by L ¹ and L ² in the above general formula (I) may further have a substituent as much as possible, and the substituent is, for example, a halogen atom (eg, Fluorine atom, chlorine atom, bromine atom etc.), aliphatic hydrocarbon group (eg methyl, ethyl, isopropyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl etc.), alkenyl group (eg allyl, 2- Butenyl, 3-pentenyl etc.), alkynyl group (eg propargyl, 3-pentynyl etc.), aralkyl group (eg benzyl, phenethyl etc.), aryl group (eg phenyl, naphthyl, 4-methylphenyl etc.), heterocyclic group (eg Pyridyl, furyl, imidazolyl, piperidinyl, morpholyl etc.), alkyloxy group (eg methoxy, ethoxy, buto) Shi, 2-ethylhexyl oxy,
Ethoxyethoxy, methoxyethoxy, etc.), an aryloxy group (for example, phenoxy, 2-naphthyloxy, etc.),
Amino group (eg, unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylamino, dibenzylamino, anilino, etc.), acylamino group (eg, acetylamino, benzoylamino, etc.), ureido group (eg, unsubstituted ureido) , N-methylureido, N-phenylureido, etc.), thioureido group (eg, unsubstituted thioureido, N-methylthioureido, N-phenylthioureido, etc.), selenoureido group (eg, unsubstituted selenouride, etc.), phosphine selenide group (eg, Diphenylphosphine selenide, etc.), telluroide group (eg unsubstituted telluroide etc.), urethane group (eg methoxycarbonylamino, phenoxycarbonylamino etc.), sulfonamide group (eg methylsulfonamide, phenyl) Ruhon'amido etc.), a sulfamoyl group (e.g., unsubstituted sulfamoyl group, N, N- dimethylsulfamoyl, N- phenylsulfamoyl, etc.), a carbamoyl group (e.g., unsubstituted carbamoyl,
N, N-diethylcarbamoyl, N-phenylcarbamoyl, etc.), a sulfonyl group (for example, methanesulfonyl, p
-Toluenesulfonyl etc.), sulfinyl group (eg methylsulfinyl, phenylsulfinyl etc.), alkyloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl) , Formyl, pivaloyl etc.), an acyloxy group (eg acetoxy, benzoyloxy etc.), a phosphoramide group (eg N, N-diethylphosphoramide etc.), an alkylthio group (eg methylthio, ethylthio etc.), an arylthio group (eg, Phenylthio, etc.), cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (eg trimethylan) Niobium, etc.), phosphonio group,
Examples thereof include a hydrazino group, a thiazolino group and a silyloxy group (t-butyldimethylsilyloxy, t-butyldiphenylsilyloxy). When there are two or more substituents, they may be the same or different.

Next, Q and q in the general formula (I) will be described. In the general formula (I), the counter anion represented by Q is a halogenium ion (for example, F ⁻ , Cl ⁻ , B
r ⁻ , I ⁻ ), tetrafluoroborate ion (B
F ₄ ^-), hexafluorophosphate ion (P
F ₆ ^-), sulfate ion (SO ₄ ^2-), arylsulfonate ions (e.g., p- toluenesulfonate ion,
Naphthalene-2,5-disulfonate ion etc.), carboxy ion (eg acetate ion, trifluoroacetate ion, oxalate ion, benzoate ion etc.) and the like, and the counter cation represented by Q is an alkali metal ion. (Eg, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, etc.), alkaline earth metal ion (eg, magnesium ion, calcium ion, etc.), substituted or unsubstituted ammonium ion (eg, unsubstituted ammonium ion) , Triethylammonium, tetramethylammonium, etc.), a substituted or unsubstituted pyridinium ion (eg, unsubstituted pyridinium ion, 4-phenylpyridinium ion, etc.), and a proton.
Further, q is the number of Q for making the charge of the compound neutral, and represents a value of 0 to 1, and the value may be a decimal number.

Preferred as the counter anion represented by Q
Is a halogenium ion (eg Cl ^-, Br^-), Tet
Lafluoroborate ion, hexafluorophosphate
Counter cation represented by Q, which is a toion or a sulfate ion
As the alkali metal ion (for example, nato)
Lithium ion, potassium ion, rubidium ion, cell
Sium ion, etc.), substituted or unsubstituted ammonium
Ions (eg, unsubstituted ammonium ions, triethyl
Lumonium, tetramethylammonium, etc.)
Is a proton.

Specific examples of the compound represented by L ¹ or L ² are shown below, but the invention is not limited thereto. In addition, the numerical value in parentheses shows a logβ ₂ value.

[0120]

[Chemical 27]

[0121]

[Chemical 28]

The compound represented by the general formula (I) can be produced by a known method, for example, Inorganic and Nuclear Chemistry Letters (INORG.NUCL.
CHEM. LETTERSVOL. 10, 641 pages, 1
974), Transition Metal Chemistry (T
positionMet. Chem. Pages 1,248,
1976), Actor Crystallographica (Act)
a. Cryst. B32, p. 3321, 1976),
JP-A-8-69075, JP-B-45-8831, JP-A-915371A1, JP-A-6-11788,
JP-A-6-501789, JP-A-4-267249
And JP-A-9-118685 and the like.

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

[0124]

[Chemical 29]

[0125]

[Chemical 30]

[0126]

[Chemical 31]

The gold sensitization in the present invention is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature (preferably 40 ° C. or higher) for a certain period of time. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol per mol of silver halide.

In the present invention, as the gold sensitizer, in addition to the above compounds, a gold compound usually used (eg, chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, Tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichloro gold, etc.) can be used together.

The silver halide emulsion of the present invention can be combined with other chemical sensitizations in addition to gold sensitization. As the chemical sensitization method that can be used in combination, sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization other than gold, or reduction sensitization can be used. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used.

The silver halide emulsion of the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. It can be added.
These compounds include azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles mercaptobenzimidazoles, mercaptothia. Idiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc .; such as oxadrinethione Thioketo compounds; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene) pens Azaindenes; benzenethiosulfonate, can be added benzene sulfinic acid, many compounds known as antifoggants or stabilizers, such as benzenesulfonic acid amide. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A No. 62-215272. In addition, 5-described in EP 0447647
An arylamino-1,2,3,4-thiatriazole compound (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used. The compound is preferable because it has a function of further enhancing the sensitivity to high illuminance in addition to preventing fogging and stabilizing it.

In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A-11-109576 and JP-A-11-327.
Cyclic ketones having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in JP-A No. 094 (particularly represented by the general formula (S1), paragraphs 0036 to 0071 can be incorporated into the specification of the present application), sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011, such as 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2, 5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5
-Dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof, etc.),
General formula (A) of US Pat. No. 5,556,741
Hydroxylamines represented by (US Pat. No. 5,555
No. 6,741 at column 4, line 56 to column 11, line 22 is preferably applied to the present application and incorporated as part of the specification of the present application), JP-A-11-1020.
The water-soluble reducing agents represented by formulas (I) to (III) in JP-A-45-45 are preferably used in the present invention.

Further, the silver halide emulsions of the present invention are represented by the general formulas (BI) and (RI) for the purpose of imparting so-called spectral sensitivity, which is photosensitive in a desired light wavelength region. Other spectral sensitizing dyes can be contained in combination in the same emulsion layer as the compound described above or in a different emulsion layer.
Examples of these spectral sensitizing dyes used for spectral sensitization in the blue, green and red regions include F.I. M. By Harmer He
thermocycliccompounds-Cyani
ne dyes and related compo
unds (John Wiley & Sons
[New York, London] 1964
Year)). Specific examples of the compound and the spectral sensitization method are described in the above-mentioned JP-A-6.
Those described on page 22, right upper column to page 38 of JP-A-2-215272 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dyes described in JP-A-3-123340 are stable, have strong adsorption, It is very preferable from the viewpoint of temperature dependence and the like.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range.

The blue-sensitive silver halide emulsion of the present invention contains 50 to 100 of the total projected area of all blue-sensitive silver halide grains.
% Main plane is {100} plane or {111} plane and thickness is 0.0
1 to 0.30 μm, aspect ratio 2.0 to 100,
Tabular grains having a projected diameter of 0.1 to 10 μm are preferred. The coefficient of variation of projected diameter and thickness (standard deviation of distribution / average projected diameter or average thickness) is preferably 0 to 0.
It is 4. Here, the aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. The larger the aspect ratio, the thinner and flatter the particles.
In the present invention, the tabular grains have an aspect ratio of 1.2.
As described above, the average aspect ratio means the average value of the aspect ratios of all tabular grains in the emulsion. The projected diameter refers to the diameter of a circle having an area equal to the projected area of a grain, and the thickness refers to the distance between two principal planes of tabular grains. The projected diameter of tabular grains refers to the diameter of a circle having an area equal to the projected area when the main plane is placed parallel to the substrate surface and observed from the vertical direction.

The method for forming tabular silver halide emulsion grains having {100} main planes is to add and mix an aqueous silver salt solution and an aqueous halide salt solution into a dispersion medium such as an aqueous gelatin solution while stirring. At this time, at this time, for example, JP-A-6-301129 and JP-A-6-3479.
No. 29, silver iodide, and, for example, JP-A-9-34.
No. 045 discloses a method in which silver bromide is present, strain is caused in a nucleus due to a difference in crystal lattice size from silver chloride, and a screw dislocation is introduced. When a screw dislocation is introduced,
Since the formation of two-dimensional nuclei on that plane is not rate-determining, crystallization proceeds on this plane, and two {1
Introduced into the {00} plane, tabular grains are formed. In addition, imidazoles and 3,5-diaminotriazoles are used in JP-A-6-347928, polyvinyl alcohols are used in JP-A-8-339044, and a {100} plane formation accelerator is added. A method of forming {100} tabular grains is disclosed.

The method for forming tabular silver halide emulsion grains having {111} main planes is, for example, US Pat. Nos. 4,400,463 and 5,185,239.
No. 5,176,991, JP-A-63-2138.
36, U.S. Pat. No. 5,176,992, JP-A-200
No. 0-29156, aminoazaindene,
A method of forming particles in the presence of a crystal habit controlling agent of triaminopyrimidine, hydroxyaminoazine, thiourea, xanthonoid, and pyridinium salt is disclosed.

The steps of preparing a silver halide emulsion in the present invention are, as is generally well known, a silver halide grain forming step by a reaction of a water-soluble silver salt and a water-soluble halide, a desalting step, and a chemical ripening step. It consists of steps.

The silver halide emulsion used in the color photographic light-sensitive material of the present invention contains the silver halide emulsion prepared by the method of the present invention in at least one of the silver halide emulsion layers. As other silver halide used in the color light-sensitive material of the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used, but especially for the purpose of rapid processing. It is preferable to use a high silver chloride emulsion having a silver chloride content of 90 mol% or more, further 95 mol% or more, and particularly 98 mol% or more. Furthermore, it is preferable to have a silver bromide localized phase. Also, the main plane is the {100} plane or the {11} plane.
The use of tabular grains having the 1} plane is preferable in that the [hydrophilic binder amount / silver halide thickness] ratio can be increased and the color development can be accelerated and the process color mixture can be reduced.
Here, the amount of hydrophilic binder means the amount of hydrophilic binder per 1 m ^{2 of the} silver halide emulsion layer (g / m ² ). The term "silver halide emulsion thickness" refers to the thickness (μm) occupied by silver halide emulsion grains in the silver halide emulsion layer in the direction perpendicular to the support.

Next, the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention may be black and white or color, but the silver halide emulsion of the present invention is preferably used in the silver halide color photographic light-sensitive material. The silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material") in which the silver halide emulsion of the present invention is preferably used is a silver halide emulsion layer containing a yellow dye-forming coupler on a support. And a silver halide emulsion layer containing a magenta dye-forming coupler and at least one silver halide emulsion layer containing a cyan dye-forming coupler. At least one layer is characterized by containing the silver halide emulsion of the present invention. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler as a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer thus prepared functions as a cyan coloring layer. The silver halide emulsion contained in each of the yellow color forming layer, the magenta color forming layer and the cyan color forming layer is sensitive to light in wavelength regions different from each other (for example, light in blue region, green region and red region). It is preferable to have

The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer and a coloring layer, which will be described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer and the cyan coloring layer. Good.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention. For example, a transmissive support or a reflective support can be used as the photographic support. Examples of the transmissive support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and further 2,6-naphthalenedicarboxylic acid (NDC).
Polyesters of A) and ethylene glycol (EG), polyesters of NDCA, terephthalic acid and EG, and the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflection type support, a reflection support which is laminated with a plurality of polyethylene layers or polyester layers and which contains a white pigment such as titanium oxide in at least one layer of such a water resistant resin layer (laminate layer) is preferable.

Further preferred reflective supports in the present invention include those having a polyolefin layer having fine pores on a paper base on which a silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no microvoids (eg polypropylene, polyethylene) and is close to the paper substrate. More preferably, it is made of a polyolefin (for example, polypropylene, polyethylene) having micropores on its side. The density of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is 0.40 to
It is preferably 1.0 g / ml, and 0.50 to 0.
70 g / ml is more preferred. The thickness of these multi-layer or one-layer polyolefin layers located between the paper base and the photographic constituent layers is preferably 10 to 100 μm, and 15 to 100 μm.
70 μm is more preferable. The ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably 0.05 to 0.2,
1 to 0.15 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layers of the above paper substrate from the viewpoint of increasing the rigidity of the reflection support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred are polyethylene or polypropylene, with polypropylene being more preferred. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further has a density of 0.
It is preferably 7 to 1.1 g / ml. Regarding the preferred embodiment of the polyolefin layer provided on the paper substrate in the reflective support of the present invention, see JP-A-10-
333277, 10-333278, 11-5.
No. 2513, No. 11-65024, EP088006.
5 and EP 0880066.

Further, it is preferable to contain a fluorescent brightening agent in the water resistant resin layer. Also, a hydrophilic colloid layer containing the fluorescent whitening agent dispersed therein may be separately formed. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used, and more preferably, a benzoxazolylnaphthalene-based or benzoxazolyl-stilbene-based fluorescent whitening agent. The amount used is not particularly limited, but preferably 1 to 10
It is 0 mg / m ² . When mixed with a water resistant resin, the mixing ratio is preferably 0.0005 to 3 mass% with respect to the resin.
And more preferably 0.001 to 0.5 mass%.

The reflective type support may be a transmissive type support or the above-mentioned reflective type support coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular reflective or type II diffuse reflective metal surface.

The support used in the light-sensitive material of the present invention is a support in which a white polyester support or a layer containing a white pigment is provided on the support having a silver halide emulsion layer for display. The body may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of.

In the light-sensitive material of the present invention, for the purpose of improving the sharpness of an image, the hydrophilic colloid layer has a dye decolorizable by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76. (Among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or a dihydric or tetrahydric alcohol (for example, tricarboxylic acid) is added to the water resistant resin layer of the support. It is preferable to contain 12 mass% or more (more preferably 14 mass% or more) of titanium oxide surface-treated with (methylolethane) or the like.

In the light-sensitive material of the present invention, a hydrophilic colloid layer is added in order to prevent irradiation and halation and to improve safety of safelight, etc.
337490A2, pages 27-76,
Dyes that can be decolorized by treatment (including oxonol dyes,
Cyanine dye) is preferably added. Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating color separation include JP-A-5-127324 and 5-1273.
Water-soluble dyes described in No. 25 and No. 5-216185 are preferable.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by treatment with a water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm for ordinary printer exposure).
It is preferable that the optical density value is 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of up to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure). It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed in Japanese Patent Application Laid-Open No. 2-308244
No. 4-13 of the issue. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. Regarding the method of preparing colloidal silver as a light absorber, US Pat. Nos. 2,688,601 and 3,459,
No. 563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The silver halide photographic light-sensitive material of the present invention is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc. Among them, it is preferable to use it as a color photographic paper.
Color photographic paper is a yellow color-forming silver halide emulsion layer,
It is preferable to have at least one magenta color forming silver halide emulsion layer and at least one cyan color forming silver halide emulsion layer. In general, these silver halide emulsion layers are yellow color forming in order from the support. These are a silver halide emulsion layer, a magenta coloring silver halide emulsion layer, and a cyan coloring silver halide emulsion layer.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but when the yellow coupler-containing layer contains silver halide tabular grains, the magenta coupler-containing silver halide It is preferably coated at a position farther from the support than at least one of the emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color due to a sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support as compared with other silver halide emulsion layers. It is preferably provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of the other silver halide emulsion layers, and from the viewpoint of reducing photofading, the cyan coupler-containing silver halide emulsion layer is The bottom layer is preferred. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, JP-A-4-75055 and JP-A-9-1140.
35, 10-246940, US Pat. No. 5,57.
As described in JP-A-6,159, it is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer.

Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied in the present invention, and processing methods and processing additions applied for processing the light-sensitive material. As the agent, JP-A-62-21
5272, JP-A-2-33144, European Patent EP
Those described in 0,355,660A2, particularly those described in European Patent EP0,355,660A2 are preferably used. Furthermore, JP-A-5-34
No. 889, No. 4-359249, No. 4-313753
No. 4, No. 4-270344, No. 5-66527, No. 4
-34548, 4-145433, 2-854.
Issue 1, 1-158431, 2-90145, 3
The silver halide color photographic light-sensitive materials and their processing methods described in JP-A-194539, JP-A-2-93641, European Patent Publication No. 0520457A2 and the like are also preferable.

In particular, in the present invention, the above-mentioned reflection type support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer for silver halide emulsion or antifoggant. , Chemical sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsion dispersion method, color image storability improver (anti-staining agent or anti-fading agent), Regarding the dye (colored layer), the type of gelatin, the layer structure of the photosensitive material and the coating pH of the photosensitive material, those described in each part of the patent shown in Table 3 below are particularly preferably applicable.

[0155]

[Table 3]

Other cyan, magenta and yellow couplers used in the present invention are described in JP-A-62 / 62.
-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, line 3 of JP-A-2-33144, upper right column 1
Line 4 to page 18, upper left column, end line and page 30, upper right column, line 6 to
Page 35, lower right column, line 11 and EP 0355,660A2, page 4, lines 15 to 27, page 5, lines 30 to 28, last line, page 45, lines 29 to 31, line 47, page 23 Line 63
The couplers described on page 50, line 50 are also useful. The present invention also relates to general formulas (II) and (II) of WO-98 / 33760.
I), a compound represented by the general formula (D) of JP-A-10-221825 may be added, which is preferable.

As the cyan dye-forming coupler usable in the present invention (sometimes referred to simply as "cyan coupler"), a pyrrolotriazole-based coupler is preferably used, and a general formula (I) of JP-A-5-313324 or (I
The coupler represented by I), the coupler represented by formula (I) of JP-A-6-347960, and the exemplified couplers described in these patents are particularly preferable. Also,
Phenol-type and naphthol-type cyan couplers are also preferable, and for example, the cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. As a cyan coupler other than the above, European Patent EP048
8248 and EP0491197A1 described above, pyrroloazole type cyan couplers, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, and US Pat. No. 4,873,183.
Nos. 4,916,051 and pyrazoloazole type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position, particularly JP-A-8-171185 and 8-31.
Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in Nos. 1360 and 8-339060 are also preferable.

In addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, 3-hydroxypyridine type cyan couplers (in particular, the couplers listed as specific examples) described in European Patent EP 0333185A2. (42) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, couplers (6) and (9) are particularly preferable) and JP-A-64-322.
Cyclic active methylene-based cyan couplers described in JP-A No. 60 (specifically, coupler example 3 listed as a specific example,
8, 34 are particularly preferred), European Patent EP 0456622.
It is also possible to use the pyrrolopyrazole type cyan couplers described in 6A1 and the pyrroloimidazole type cyan couplers described in European Patent EP0484909.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-28138 is particularly preferable, and paragraphs 0012 to 0059 of the patent are described. Including the exemplified cyan couplers (1) to (47) are directly applied to the present application and are preferably incorporated as part of the specification of the present application.

The magenta dye-forming coupler used in the present invention (sometimes referred to simply as "magenta coupler")
As the 5-
Pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers are used. Among them, secondary or tertiary alkyl groups such as those described in JP-A-61-65245 are used in terms of hue, image stability, color developability and the like. Pyrazolotriazole couplers directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, pyrazoloazole couplers containing sulfonamide group in the molecule as described in JP-A-61-65246, JP-A-61. Pyrazoloazole couplers having alkoxyphenyl sulfonamide ballast groups as described in US Pat.
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 49A and No. 294,785A. Particularly, as the magenta coupler, a pyrazoloazole coupler represented by the general formula (MI) described in JP-A-8-122984 is preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application. Incorporated as part of the specification. In addition to these, the pyrazoloazole couplers having steric hindrance groups at both the 3-position and the 6-position described in European Patent Nos. 854384 and 884640 are also preferably used.

Also, a yellow dye-forming coupler (simply,
(In some cases, referred to as “yellow coupler”), in addition to the compounds listed in the above table, European Patent EP04479
No. 69A1, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, a malondianilide type yellow coupler having a cyclic structure described in European Patent No. EP 0482552A1, European Patent No. 953870A1. Issue No. 953871A1
No., No. 953872A1, No. 953873A1
No. 5,953,874A1, No. 953875A1, etc., and pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide type couplers described in US Pat. No. 5,118,599. An acylacetamide type yellow coupler having a dioxane structure is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The couplers used in the present invention are loadable latex polymers in the presence (or absence) of the high boiling organic solvents described in the above table (eg US Pat.
No. 3,716) or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer to emulsify and disperse in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in US Pat. No. 4,857,449, column 7,
The homopolymers or copolymers described in column 15 and pages 12 to 30 of WO88 / 00723 are mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, WO98 / 33
760, phenidone and hydrazine compounds described in U.S. Pat. No. 4,923,787 and the like, JP-A-5-2496.
37, Japanese Patent Laid-Open No. 10-282815 and German Patent No. 1
White couplers described in 9629142A1 and the like can be used. Further, in particular, when the pH of the developer is raised to accelerate the development, German Patent No. 19618786
A1, European Patent No. 839623A1, European Patent No. 8
It is also preferable to use the redox compounds described in 42975A1, German Patent 1980846A1 and French Patent 2760460A1.

In the present invention, it is preferable to use a compound having a triazine bone nucleus having a high molar extinction coefficient as the ultraviolet absorber, and for example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. For example, JP-A-46-3
No. 335, No. 55-152776, JP-A-5-197.
074, 5-232630, 5-307232.
No. 6, No. 6-211813, No. 8-53427, No. 8
-234364, 8-239368, 9-31
067, 10-15898 and 10-1475.
77, 10-182621, German Patent 1973.
The compounds described in 9797A, EP 711804A, and JP-A-8-501291 can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm or less,
More preferably, it is 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ²
Or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

In the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, a bactericidal / mold-proofing agent as described in JP-A-63-271247 is used. It is preferable to add it. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, adjusting the charge amount, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, betaine surfactants and nonionic surfactants, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. Particularly, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but preferably in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , and preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 ×
It is 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known materials. Examples of the developing system include the automatic printing and developing system described in JP-A-10-333253, and JP-A-2000-1.
No. 0206, a photosensitive material conveying device, JP-A-11-2
A recording system including the image reading device described in JP-A-15312, JP-A-11-88619 and JP-A-10-20.
An exposure system including a color image recording system described in 2950, a digital photo print system including a remote diagnosis system described in JP-A-10-210206, and a photo including an image recording apparatus described in Japanese Patent Application No. 10-159187. A printing system is included.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, before applying image information, a yellow microdot pattern may be pre-exposed and copy regulation may be applied.

The processing of the light-sensitive material of the present invention is described in JP-A-2-
207250, page 26, lower right column, line 1 to page 34, upper right column, line 9, and JP-A-4-97355, page 5, upper left column 1,
The processing materials and processing methods described in line 7 to page 18, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The present invention has rapid processing suitability, and the color development time is 45 seconds at the maximum (preferably 45 seconds to 3 seconds) as described above, but 30 seconds or less (preferably 30 seconds to 3 seconds). Second) is preferable, 20 seconds or less (more preferably 20 seconds to 3 seconds) is more preferable, and 15 seconds to 5 seconds is particularly preferable. Similarly, the bleach-fixing time is at most 45 seconds (preferably 45 seconds to 3 seconds), but is preferably 30 seconds or less (preferably 30 seconds to 3 seconds) and 20 seconds or less (preferably 20 seconds to 3 seconds). Second) is more preferable, and 15 seconds to 5 seconds is particularly preferable. The washing or stabilizing time is preferably 4
It is 0 seconds or less (preferably 40 seconds to 3 seconds), more preferably 30 seconds or less (preferably 30 seconds to 3 seconds), and particularly preferably 20 seconds to 5 seconds. The color developing time means the time from the time when the light-sensitive material enters the color developing solution to the time when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic processor, etc., the time during which the light-sensitive material is immersed in the color developing solution (so-called in-liquid time) and the light-sensitive material leaves the color developing solution, and bleaching in the next processing step occurs. The total of the time during which it is transported in the air toward the fixing bath (so-called aerial time) is called the color development time. Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. The washing or stabilizing time is the time during which the light-sensitive material is in the washing or stabilizing liquid and is in the liquid for the drying step (so-called in-liquid time).
Say.

The drying method according to the present invention may be any conventionally known method for rapid drying of a color photographic light-sensitive material, but for the purpose of the present invention, the color photographic light-sensitive material may be used within 20 seconds, preferably 15 seconds. It is preferable to be able to dry within seconds, most preferably within 5 to 10 seconds.
Either the contact heating method or the hot air blowing method may be used as the drying method, but the combination of the contact heating method and the hot air blowing method allows quicker drying than the case of using either one of them. Which is preferable. A more preferred embodiment of the present invention relating to the drying method is a method in which the photosensitive material is contact-heated by a heat roller and then blown and dried by warm air blown toward the photosensitive material from a perforated plate or nozzle group. In the blow drying section, it is preferable that the mass velocity of the warm air blown per unit area of the heat receiving area of the photosensitive material is 1000 kg / m ² · hr or more. Further, the shape of the air blowing outlet is preferably a shape with little pressure loss, and examples thereof include FIGS. 7 to 15 described in JP-A-9-33998. The light-sensitive material of the present invention has rapid processability and high sensitivity,
Since the pressure fog is small and it is suitable not only for surface exposure but also for high-illuminance scanning exposure, a good image can be obtained in the above-mentioned color development time.

The method of developing the light-sensitive material of the present invention after exposure is as follows: a conventional method of developing with a developer containing an alkali agent and a developing agent, an alkaline solution containing a developing agent in the light-sensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution such as, a heat development method without using a processing solution can be used. In particular, the activator method is a preferable method because the processing solution does not contain a developing agent, so that the processing solution can be easily managed and handled, and that the load at the time of processing the waste solution is small and the environment can be preserved. In the activator method, the developing agent or its precursor incorporated in the light-sensitive material is, for example, JP-A-8-2343.
88, 9-152686, 9-152693
Nos. 9-212814 and 9-160193 are preferred.

Further, a developing method in which the amount of silver coated on the light-sensitive material is reduced and an image amplification process (intensification process) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method as an activator method. Specifically, JP-A-8
The image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed, but in the image amplification processing method using a light-sensitive material having a low silver content,
The desilvering process can be omitted and a simple method such as washing with water or stabilization can be performed. Further, in the method of reading image information from a light-sensitive material with a scanner or the like, it is possible to adopt a processing form which does not require desilvering processing even when a light-sensitive material having a high silver content such as a light-sensitive material for photographing is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known materials and methods can be used. Preferably Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
What was described in No. 234388 can be used.

[0177]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 (Preparation of emulsion B-1) Lime-treated gelatin 3% aqueous solution 10
00 ml was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were added and mixed simultaneously at 66 ° C. while vigorously stirring. From the time of addition of silver nitrate of 80% to the time of 90%, potassium bromide was added with vigorous mixing in an amount of 2 mol% per mol of the finished silver halide. From the time when the addition of silver nitrate was 80% to the time when it was 90%, an aqueous K ₄ [Ru (CN) ₆ ] solution was added in an amount such that the Ru amount was 3 × 10 ^-5 mol per mol of the finished silver halide. 88% from the point when the addition of silver nitrate is 83%
Up to the point of time, an aqueous solution of K ₂ [IrCl ₆ ] was added in such an amount that the Ir amount became 3 × 10 ⁻⁸ mol per mol of the finished silver halide. When the addition of silver nitrate is 90% complete, the aqueous potassium iodide solution is used to prepare the finished silver halide 1.
An amount of 0.2 mol% of I per mol was added with vigorous mixing. 98% from the point when 92% of silver nitrate was added
% Of K ₂ [Ir (5-methylthiazole)
Cl ₅ ] aqueous solution was added in an amount such that the Ir amount was 1 × 10 ⁻⁶ mol per mol of the finished silver halide. 40 ° C
After desalting with 168 g of lime-processed gelatin, pH was adjusted to 5.5 and pCl was adjusted to 1.8. The obtained grains were cubic silver iodobromochloride emulsions having a spherical equivalent diameter of 0.75 μm and a coefficient of variation of 11%. This emulsion was dissolved at 40 ° C., sodium thiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S- 2) using 60
It was aged to be optimum at ℃. After cooling to 40 ° C., the sensitizing dye B-A was added in an amount of 2.4 × 10 4 per mol of silver halide.
^-4 mol, sensitizing dye BB is 1.6 × 10 ^-4 mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole is 2 × 10 ^-4 mol per mol of silver halide, 1- (5-Methylureidophenyl) -5-mercaptotetrazole was added in an amount of 2 × 10 per mol of silver halide.
^-4 mol, 2 x potassium bromide per mol of silver halide
10 ⁻³ mol was added. The emulsion thus obtained is
Emulsion B-1 having a spectral maximum wavelength of 480 nm.

[0178]

[Chemical 32]

(Preparation of emulsion B-2) In preparation of emulsion B-1, sensitizing dye B was used instead of sensitizing dyes B-A and BB.
Emulsion B-2 was prepared which differed only in that -A was added at 4 x 10 ^-4 mol per mol of silver halide. (Preparation of Emulsions B-3 to 5) Exactly the same as the preparation of Emulsion B-2, except that the sensitizing dye species and the addition amount were changed.
The sensitizing dye species and the addition amount are summarized in Table 4.

(Preparation of Emulsion B-6) JP 2000-10
Similar to Emulsion F described in Example 2 of 0345, the main plane was the {111} plane, the thickness was 0.13 μm, the aspect ratio was 6,
A high silver chloride tabular emulsion having a cubic side length of 0.4 μm and an iodine content of 0.4 mol% was prepared. However, the spectral sensitizing dye and the spectral maximum wavelength are as shown in Table 4, and the emulsion is designated as B-6. (Preparation of emulsion G) Lime-treated gelatin 3% aqueous solution 1000
pH was adjusted to 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were added and mixed at 45 ° C. at the same time with vigorous stirring. From the time when the addition of silver nitrate was 80% to the time when it was 90%, an aqueous K ₄ [Ru (CN) ₆ ] solution was added in an amount such that the Ru amount was 3 × 10 ^-5 mol per mol of the finished silver halide. 88% from the point when the addition of silver nitrate is 83%
Up to the point of time, an aqueous solution of K ₂ [IrCl ₆ ] was added in such an amount that the Ir amount became 5 × 10 ⁻⁸ mol per mol of the finished silver halide. 9 from the point when the addition of silver nitrate was 92%
To the point of 5%, an aqueous solution of K ₂ [Ir (5-methylthiazole) Cl ₅ ] was added in an amount of 5 × 10 ⁻⁷ mol of Ir per mol of the finished silver halide. Furthermore,
From the time of addition of silver nitrate of 95% to the time of 98%, K ₂ [Ir (H ₂ O) Cl ₅ ] aqueous solution was added in an amount of 5 × 10 ⁻⁷ mol per 1 mol of the finished silver halide. did. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver chloride emulsions having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 10%. 40 this emulsion
It was dissolved at 0 ° C., sodium thiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S-
It was aged at 60 ° C. using 2) so as to be optimum. 40
After cooling to 0 ° C., the sensitizing dye G-A was 6 × 10 ⁻⁴ mol per mol of silver halide, the 1-phenyl-5-mercaptotetrazole was 2 × 10 ⁻⁴ mol per mol of silver halide,
1- (5-methylureidophenyl) -5-mercaptotetrazole is 8 × 10 ⁻⁴ mol per mol of silver halide, and potassium bromide is 7 × 10 per mol of silver halide.
^-3 mol was added. The emulsion thus obtained was designated as Emulsion G.

[0181]

[Chemical 33]

(Preparation of Emulsion R-1) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were stirred vigorously at 45 ° C.
And mixed at the same time. From the time of addition of silver nitrate of 80% to the time of 100%, potassium bromide was added with vigorous mixing in an amount of 4 mol% per mol of the finished silver halide. From the time when the addition of silver nitrate was 80% to the time when it was 90%, the K ₄ [Ru (CN) ₆ ] aqueous solution had an Ru amount of 3 × 1 per mol of the finished silver halide.
An amount of 0 ^-5 mol was added. From the point of time when the addition of silver nitrate was 83% to the point of 88%, the K ₂ [IrCl ₆ ] aqueous solution was added with an Ir amount of 5 per mol of the finished silver halide.
An amount of × 10 ^-8 mol was added. 90 additions of silver nitrate
%, An aqueous potassium iodide solution was added with vigorous mixing so that the amount of I was 0.1 mol% per mol of the finished silver halide. 92% addition of silver nitrate
From the point of time to the point of 95%, an aqueous solution of K ₂ [Ir (5-methylthiazole) Cl ₅ ] was added in an amount of 5 × 10 ⁻⁷ mol of Ir per mol of the finished silver halide. Further, from the time when the addition of silver nitrate was 95% to the time when 98% was added, the K ₂ [Ir (H ₂ O) Cl ₅ ] aqueous solution was added in an amount of 5 × 10 ^-7 mol per 1 mol of the finished silver halide. Was added. After desalting at 40 ° C, 168g of lime-processed gelatin was added, pH 5.5, pCl
Adjusted to 1.8. The obtained particles have an equivalent spherical diameter of 0.3μ.
It was a cubic silver silver iodobromochloride emulsion having m and a coefficient of variation of 10%.
This emulsion was dissolved at 40 ° C., and sodium thiosulfonate was added in an amount of 2 × 10 ^-5 mol per mol of silver halide.
Sodium thiosulfate pentahydrate was used as a sulfur sensitizer and (S-2) was used as a gold sensitizer, and aging was performed at 60 ° C. so as to be optimum. After the temperature was lowered to 40 ° C., the sensitizing dye RA was added in an amount of 7 × 10 ⁻⁵ mol per mol of silver halide and 1-phenyl-5
2 mol of mercaptotetrazole per mol of silver halide
× 10 ^-4 mol, 1- (5-methylureidophenyl)-
5-mercaptotetrazole is 8 × 10 ⁻⁴ mol per mol of silver halide, compound I is 1 × 10 ⁻³ mol per mol of silver halide, and potassium bromide is 7 × 10 ⁻³ mol per mol of silver halide. Was added. The thus obtained emulsion had a spectral maximum wavelength of 700 nm and was designated as emulsion R-1.

[0183]

[Chemical 34]

[0184]

[Chemical 35]

(Preparation of Emulsion R-2) In preparation of Emulsion R-1, sensitizing dye RB was added in an amount of 7 × 10 ^-5 mol per mol of silver halide instead of sensitizing dye RA. Emulsion R-2, only different, was prepared.

[0186]

[Table 4]

Corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. The photographic constituent layers of No. 1 were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer constitution. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 57 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by mass gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion B-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used as a gelatin hardening agent for each layer. Further, Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² , 60.
0 mg / m ² , 5.0 mg / m ² and 10.0 mg / m ²
Was added.

[0190]

[Chemical 36]

[0191]

[Chemical 37]

Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer.
1.0 × 10 ⁻³ mol and 5.9 × 10 ⁻⁴ mol were added per mol of silver halide, respectively. Further, 1-phenyl-5-mercaptotetrazole was also added to the second layer, the fourth layer, and the sixth layer at 0.2 mg / m ² and 0.2 mg, respectively.
/ M ² and 0.6 mg / m ² . Copolymer latex of methacrylic acid and butyl acrylate in the red-sensitive emulsion layer (mass ratio 1: 1, average molecular weight 200,000)
˜400000) was added at 0.05 g / m ² . Also,
Catechol-3,5-disulfonate disodium was added to the second layer, the fourth layer, and the sixth layer at 6 mg / m ² and 6 m, respectively.
g / m ² and 18 mg / m ² were added. Also,
To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added.

[0193]

[Chemical 38]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support Polyethylene resin laminated paper [White pigment (TiO ₂ ; content 16% by mass, ZnO; content 4% by mass) and fluorescent whitening agent (4,4′-bis (5 -Methylbenzoxazolyl) stilbene, content 0.03% by mass, including bluing dye (ultimate blue)] First layer (blue-sensitive emulsion layer) Emulsion B 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 color image stabilizer (Cpd-1) 0.07 color image stabilizer (Cpd-2) 0.04 color image stabilizer (Cpd-3) 0.07 color image stabilizer (Cpd-8) 02 Solvent (Solv-1) 0.21

[0195]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing inhibitor (Cpd-4) 0.09     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.01     Solvent (Solv-1) 0.06     Solvent (Solv-2) 0.22

[0196]   Third layer (green sensitive emulsion layer)     Emulsion G 0.14     Gelatin 1.36     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.02     Color mixing inhibitor (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.11     Solvent (Solv-4) 0.22     Solvent (Solv-5) 0.20

[0197]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing prevention layer (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.013     Color image stabilizer (Cpd-6) 0.10     Color image stabilizer (Cpd-7) 0.007     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.16

[0198]   Fifth layer (red sensitive emulsion layer)     Emulsion R-1 0.12     Gelatin 1.11.     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-1) 0.05     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.03     Color image stabilizer (Cpd-17) 0.09     Color image stabilizer (Cpd-18) 0.07     Solvent (Solv-5) 0.15     Solvent (Solv-8) 0.05

Sixth Layer (UV Absorbing Layer) Gelatin 0.46 UV Absorbing Agent (UV-B) 0.45 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.25 Seventh Layer (Protective Layer) ) Gelatin 1.00 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01 In the following Examples and Example 2 and thereafter. The compounds used are shown together.

[0200]

[Chemical Formula 39]

[0201]

[Chemical 40]

[0202]

[Chemical 41]

[0203]

[Chemical 42]

[0204]

[Chemical 43]

[0205]

[Chemical 44]

[0206]

[Chemical formula 45]

[0207]

[Chemical formula 46]

[0208]

[Chemical 47]

[0209]

[Chemical 48]

The sample thus obtained was designated as 101.

Laser Scanning Exposure Device The following laser oscillation device was prepared. See Table 5. Blue laser: 488nm, 473nm, 458nm,
440 nm. Green laser: 532 nm (semiconductor laser (oscillation wavelength: 1064 nm) was wavelength-converted by an SHG crystal of LiNbO ₃ having a waveguide-shaped inversion domain structure) and taken out. Red laser: 780nm, 685nm, 650nm,
635 nm. The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror so that the sample could be sequentially scanned and exposed. Fluctuations in the amount of light due to the temperature of the semiconductor laser are suppressed by using a Peltier device to keep the temperature constant. The effective beam diameter is shown in the table. The scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7 × 10 ^−7.
In seconds.

The following experiment was conducted to examine the photographic characteristics of the above-prepared coated sample. 40 ° C (5
5% R. H. ) Leave each BG underneath and leave the environment as it is.
Gradation exposure for sensitometry was given by irradiating the laser beam of R. In addition, each sample is 10 ℃ (55%
R. H. ), And exposed for sensitometry exactly as at 40 ° C. The wavelength of the irradiated laser beam is shown in Table 6. After the exposure, color development processing A shown below was performed.

[0213]

[Table 5]

[0214]

[Table 6]

The processing steps are shown below. [Processing A] A sample of the above light-sensitive material was processed into a roll having a width of 127 mm, and after imagewise exposure using a mini lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., the capacity of the color developing tank was doubled in the following processing steps. A continuous process (running test) was performed until replenishment. The treatment using this running liquid was designated as treatment A. Treatment process Temperature Time Replenishment amount ^* Color development 38.5 ° C. 45 seconds 45 ml Bleach fixing 38.0 ° C. 45 seconds 35 ml Rinse (1) 38.0 ° C. 20 seconds-Rinse (2) 38.0 ° C. 20 seconds -Rinse (3) ^** 38.0 ° C for 20 seconds-Rinse (4) ^** 38.0 ° C for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. The rinsing liquid is taken out from the rinsing device (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was performed from the tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher] 800 ml water 800 ml Dimethylpolysiloxane-based surfactant 0.1g 0.1g (Silicone KF351A, trade name / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8g 8.8g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0g 10.0g 4,5-dihydroxybenzene-1,3-   Sodium disulfonate 0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinylaminostilbene fluorescent 2.5g 5.0g Whitening agent (Hakkor FWA-SF, trade name / Showa Kagaku) Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                     8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-   Amino-4-aminoaniline / 3/2 sulfuric acid monohydrate                                     5.0 g 15.7 g Potassium carbonate 26.3g 26.3g Add water 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                   10.15 12.50

[0217] [Bleach fixer] [Tank solution] [Replenisher] Water 700 ml 600 ml Ethylenediaminetetraacetate Iron (III) ammonium                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g m-carboxybenzenesulfinic acid                                     8.3g 16.5g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium thiosulfate (750 g / l)                           107.0 ml 214.0 ml Ammonium sulfite 16.0 g 32.0 g Ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted with 25 ° C / acetic acid and ammonia)                                   6.0 6.0

[0218] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less)                             1000 ml 1000 ml pH 6.5 6.5

The yellow color density of Sample 101 after the treatment,
The cyan color density was measured and a characteristic curve of laser scanning exposure was obtained. The sensitivity is defined by the reciprocal of the exposure amount that gives a color density 1.0 higher than the minimum color density, and is defined as 10 ° C (55%
R. H. Table 7 shows the sensitivity differences ΔS between B and R with 40 ° C. (55% RH) when the B and R sensitivities of () are 100.

[0220]

[Table 7]

As is clear from the results shown in Table 7, it is clear that the image forming method of the present invention has a remarkably small sensitivity variation due to the exposure temperature. The 440 nm and 650 nm semiconductor lasers are lasers that will become the mainstream in the future and are expected to be easily supplied and inexpensive materials, so that an inexpensive and high-quality image forming system can be provided.

Example 2 The sample of Example 1 was prepared by changing the layer structure as follows to prepare a thin sample. Preparation of Sample First Layer (Blue Sensitive Emulsion Layer) Emulsion B-1 0.14 Gelatin 0.75 Yellow Coupler (ExY-2) 0.34 Color Image Stabilizer (Cpd-1) 0.04 Color Image Stabilizer ( Cpd-2) 0.02 Color image stabilizer (Cpd-3) 0.04 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-1) 0.13

[0223]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing inhibitor (Cpd-19) 0.09     Color image stabilizer (Cpd-5) 0.007     Color image stabilizer (Cpd-7) 0.007     UV absorber (UV-C) 0.05     Solvent (Solv-5) 0.11

[0224]   Third layer (green sensitive emulsion layer)     Emulsion G 0.14     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.05     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-7) 0.008     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.009     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.06     Solvent (Solv-4) 0.11     Solvent (Solv-5) 0.06

[0225]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0226]   Fifth layer (red sensitive emulsion layer)     Emulsion R-1 0.12     Gelatin 0.59     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-7) 0.01     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-15) 0.19     Color image stabilizer (Cpd-18) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0227]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08   Seventh layer (protective layer)     Gelatin 0.70     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

[0228]

[Chemical 49]

The sample prepared as described above was used as sample 20.
It was set to 1.

Using the laser oscillating device of Example 1, laser scanning exposure was performed in the same exposure environment temperature (40 ° C., 10 ° C.).

For each exposed sample, color development processing was carried out according to the development processing B shown below, and an ultra-rapid processing was carried out. The time from immediately after exposure to immersion in the development processing solution was 7 seconds.

[Processing B] 127 m
An image was processed from a negative film of average density to a light-sensitive material sample using an experimental processing device which was processed into a roll of m width, and the processing time and processing temperature were changed to change the mini-lab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. The same exposure was carried out, and continuous processing (running test) was carried out until the capacity of the color developing replenisher used in the following processing steps became 0.5 times the capacity of the color developing tank.

Processing step Temperature Time Replenishment amount ^* Color development 45.0 ° C. 15 seconds 45 mL Bleach-fixing 40.0 ° C. 15 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds-Rinse 2 40.0 ° C. 8 seconds-Rinse 3 ^** 40.0 ° C 8 seconds-rinse 4 38.0 ° C 8 seconds 121mL dry 80.0 ° C 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Attach to (3) and rinse (3)
The rinse liquid is taken out from the pump and sent to a reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse, and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 600mL Optical brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 20.0 g 20.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.50g Potassium chloride 10.0g- 4,5-dihydroxybenzene-   Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate   Ethyl) hydroxylamine 8.5 g 14.5 g 4-amino-3-methyl-N-ethyl-N-   (Β-methanesulfonamidoethyl) aniline   ・ 3/2 Sulfate ・ Monohydrate 10.0g 22.0g Potassium carbonate 26.3g 26.3g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0235] [Bleaching fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / mL)                                   107 mL 214 mL Succinic acid 29.5g 59.0g Ethylene diamine tetraammonium iron (III) acetate                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0236] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C) 6.5 6.5

[0237]

[Chemical 50]

The yellow color density of Sample 201 after the treatment,
The cyan color densities were measured to obtain characteristic curves. The sensitivity was defined exactly as in Example 1, and the sensitivity difference ΔS exactly as in Example 1 was examined.

Similar to the results of Example 1, it was confirmed that in the image forming method of the present invention, the sensitivity variation due to the exposure environment temperature was extremely small.

Example 3 Emulsion B-1 and / or Emulsion R of Sample 201 of Example 2
-1 was replaced with another emulsion. The exposure and development processing was performed in the same manner as the exposure and development processing of Example 2.

Similar to the results of Example 2, it was confirmed that in the image forming method of the present invention, the sensitivity variation due to the exposure environment temperature was extremely small.

[0242]

According to the present invention, it is possible to provide an inexpensive and high-quality digital image forming system which can obtain an image of constant quality even if the exposure environment (temperature) changes in laser scanning digital exposure.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03C 1/76 501 G03C 1/76 501 7/407 7/407

Claims (8)

[Claims] 1. A support having at least a yellow dye-forming agent.
Puller-containing silver halide emulsion layer, magenta dye forming cap
La-containing silver halide emulsion layer, cyan dye forming coupler
Contains silver halide emulsion layer, color mixing prevention layer and protective layer
Image formation using a silver halide color photographic light-sensitive material
In the method described above, the yellow dye-forming coupler-containing
The silver rogenide emulsion layer has a blue color represented by the general formula (BI).
Silver chloride 90 containing at least one sensitizing dye
% Or more of a blue-sensitive silver halide emulsion.
30 nm to 60 with respect to the spectral maximum wavelength of the silver halide emulsion
Exposure using a blue semiconductor laser with a short wavelength of nm
An image forming method characterized by the above. General formula (BI) [Chemical 1] In the formula, Y is necessary to form a benzene ring or a heterocycle
Represents a group of atoms and is fused with another carbocycle or heterocycle.
Or may have a substituent. R¹And R²Is
It represents an alkyl group, an aryl group or a heterocyclic group. V¹,
V², V³And V ^FourRepresents a hydrogen atom or a substituent,
Two adjacent substituents are linked to each other and are saturated or unsaturated
It does not form a condensed ring. L represents a methine group.
M is a counter ion, m is a neutralizing charge in the molecule
Indicates a number of 0 or more necessary for the purpose. 2. A support having at least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer. In the method of forming an image using a silver halide color photographic light-sensitive material, the cyan dye-forming coupler-containing silver halide emulsion layer contains at least one red-sensitizing sensitizing dye represented by the general formula (RI). 40 mol to 80 n with respect to the spectral maximum wavelength of the red-sensitive silver halide emulsion.
An image forming method, which comprises exposing using a red semiconductor laser having a short wavelength of m. General formula (R-I) In the formula, Z ¹ represents a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ each represent a methine group, which may be substituted or may form a 5- or 6-membered ring with another methine group. R ¹ and R ² represent the same or different alkyl groups and may have a substituent, and R ¹ is L ¹ and R ² is L ⁵ and they are linked to each other to form 5 or 6
You may form a member ring. V ¹ , V ² , V ³ , V ⁴ , V ⁵ ,
V ⁶ , V ⁷ and V ⁸ are each a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group, an amino group and an acylamino group. , An alkoxy group, an alkylthio group, an alkylsulfonyl group, a sulfo group, an aryloxy group or an aryl group, and two of V ^{1 to} V ⁸ which are bonded to adjacent carbon atoms form a condensed ring with each other. Good. Y ¹ represents a charge-balancing counterion, and s represents a value necessary to neutralize a charge of 0 or more. 3. A support having at least a yellow dye-forming agent.
Puller-containing silver halide emulsion layer, magenta dye forming cap
La-containing silver halide emulsion layer, cyan dye forming coupler
Contains silver halide emulsion layer, color mixing prevention layer and protective layer
Image formation using a silver halide color photographic light-sensitive material
In the method described above, the yellow dye-forming coupler-containing
The silver rogenide emulsion layer has a blue color represented by the general formula (BI).
Silver chloride 90 containing at least one sensitizing dye
% Or more of a blue-sensitive silver halide emulsion.
30 nm to 60 with respect to the spectral maximum wavelength of the silver halide emulsion
exposure using a blue semiconductor laser with a short wavelength of nm,
In the silver halide emulsion layer containing the cyan dye-forming coupler
Is a small amount of the red-sensitive sensitizing dye represented by the general formula (RI).
At least 90 mol% of silver chloride containing at least one red-sensitive ha
Of a red-sensitive silver halide emulsion containing a silver halide emulsion
Red with a short wavelength of 40 to 80 nm with respect to the spectral maximum wavelength
Image characterized by exposure using a color semiconductor laser
Imaging method. General formula (BI) [Chemical 3] In the formula, Y is necessary to form a benzene ring or a heterocycle
Represents a group of atoms and is fused with another carbocycle or heterocycle.
Or may have a substituent. R¹And R²Is
It represents an alkyl group, an aryl group or a heterocyclic group. V¹,
V², V³And V ^FourRepresents a hydrogen atom or a substituent,
Two adjacent substituents are linked to each other and are saturated or unsaturated
It does not form a condensed ring. L represents a methine group.
M is a counter ion, m is a neutralizing charge in the molecule
Indicates a number of 0 or more necessary for the purpose. General formula (RI) [Chemical 4] Where Z¹Is a nitrogen atom, oxygen atom, sulfur atom or
Z atom²Is an oxygen atom, sulfur atom, or selenium atom
Represents a child. L¹, L², L³, L^Four, L^FiveRepresents the methine group
However, even if it is substituted, it may form a 5- or 6-membered ring with another methine group.
It may be formed. R¹And R²Are the same or different
It represents a good alkyl group and may have a substituent.
R¹Is L¹And R²Is L^Five5 or 6 connected to each other
You may form a member ring. V¹, V², V³, V^Four, V^Five，
V⁶, V⁷, V⁸Are hydrogen atom, halogen atom,
Alkyl group, acyl group, acyloxy group, alkoxycarl
Bonyl group, carbamoyl group, sulfamoyl group, carbo
Xiki, cyano, hydroxy, amino, acyl
Amino group, alkoxy group, alkylthio group, alkyls
Rufonyl group, sulfo group, aryloxy group or aryl
Represents a radical, V¹~ V⁸Bound to adjacent carbon atoms in
Two of them may form a condensed ring with each other. Y¹Is electric
Represents a load-balancing counterion, where s is the neutralization of zero or more charges
Represents the required value for. 4. Blue, green, and red exposure time is 5 μsec or less per pixel, exposure is performed at a resolution of 200 dpi or more, and then a total wetting time is 100 sec or less and a developing solution temperature is 40 ° C. or more. The image forming method according to claim 1, wherein the image forming method is performed. 5. The image forming method according to claim 1, wherein the development processing is performed within 10 seconds after the exposure. 6. A support having at least a yellow dye-forming agent.
Puller-containing silver halide emulsion layer, magenta dye forming cap
La-containing silver halide emulsion layer, cyan dye forming coupler
Contains silver halide emulsion layer, color mixing prevention layer and protective layer
Image formation using a silver halide color photographic light-sensitive material
In the method described above, the yellow dye-forming coupler-containing
The silver rogenide emulsion layer has a blue color represented by the general formula (BI).
Silver chloride 90 containing at least one sensitizing dye
% Or more of a blue-sensitive silver halide emulsion.
The maximum spectral wavelength of silver halide emulsion is blue.
The wavelength is 30 nm to 60 nm, which is a long wavelength.
Characteristic silver halide color photosensitizer for laser exposure
material. General formula (BI) [Chemical 5] In the formula, Y is necessary to form a benzene ring or a heterocycle
Represents a group of atoms and is fused with another carbocycle or heterocycle.
Or may have a substituent. R¹And R²Is
It represents an alkyl group, an aryl group or a heterocyclic group. V¹,
V², V³And V ^FourRepresents a hydrogen atom or a substituent,
Two adjacent substituents are linked to each other and are saturated or unsaturated
It does not form a condensed ring. L represents a methine group.
M is a counter ion, m is a neutralizing charge in the molecule
Indicates a number of 0 or more necessary for the purpose. 7. A support having at least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, a color mixing prevention layer and a protective layer. In the method of forming an image using a silver halide color photographic light-sensitive material, the cyan dye-forming coupler-containing silver halide emulsion layer contains at least one red-sensitizing sensitizing dye represented by the general formula (RI). Red-sensitive silver halide emulsion containing 90 mol% or more of silver chloride, and the spectral maximum wavelength of the red-sensitive silver halide emulsion is 40 nm to 80 nm longer than the exposure wavelength of the red exposure light source. A silver halide color photographic light-sensitive material for laser exposure. General formula (R-I) In the formula, Z ¹ represents a nitrogen atom, an oxygen atom, a sulfur atom or a selenium atom, and Z ² represents an oxygen atom, a sulfur atom or a selenium atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ each represent a methine group, which may be substituted or may form a 5- or 6-membered ring with another methine group. R ¹ and R ² represent the same or different alkyl groups and may have a substituent, and R ¹ is L ¹ and R ² is L ⁵ and they are linked to each other to form 5 or 6
You may form a member ring. V ¹ , V ² , V ³ , V ⁴ , V ⁵ ,
V ⁶ , V ⁷ and V ⁸ are each a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyano group, a hydroxy group, an amino group and an acylamino group. , An alkoxy group, an alkylthio group, an alkylsulfonyl group, a sulfo group, an aryloxy group or an aryl group, and two of V ^{1 to} V ⁸ which are bonded to adjacent carbon atoms form a condensed ring with each other. Good. Y ¹ represents a charge-balancing counterion, and s represents a value necessary to neutralize a charge of 0 or more. 8. A support having at least a yellow dye-forming agent.
Puller-containing silver halide emulsion layer, magenta dye forming cap
La-containing silver halide emulsion layer, cyan dye forming coupler
Contains silver halide emulsion layer, color mixing prevention layer and protective layer
Image formation using a silver halide color photographic light-sensitive material
In the method described above, the yellow dye-forming coupler-containing
The silver rogenide emulsion layer has a blue color represented by the general formula (BI).
Silver chloride 90 containing at least one sensitizing dye
% Or more of a blue-sensitive silver halide emulsion.
The maximum spectral wavelength of silver halide emulsion is blue.
It has a long wavelength of 30 nm to 60 nm with respect to the wavelength.
The silver halide emulsion layer containing the ane dye-forming coupler contains one
At least a red-sensitive sensitizing dye represented by the general formula (R-I)
Red-sensitive halogen containing 90 mol% or more of silver chloride containing one kind
Spectral pole of the red-sensitive silver halide emulsion containing a silver halide emulsion
Large wavelength is 40 nm to 80 with respect to the exposure wavelength of the red exposure light source
For laser exposure characterized by having a long wavelength of nm
Silver halide color photographic light-sensitive material. General formula (BI) [Chemical 7] In the formula, Y is necessary to form a benzene ring or a heterocycle
Represents a group of atoms and is fused with another carbocycle or heterocycle.
Or may have a substituent. R¹And R²Is
It represents an alkyl group, an aryl group or a heterocyclic group. V¹,
V², V³And V ^FourRepresents a hydrogen atom or a substituent,
Two adjacent substituents are linked to each other and are saturated or unsaturated
It does not form a condensed ring. L represents a methine group.
M is a counter ion, m is a neutralizing charge in the molecule
Indicates a number of 0 or more necessary for the purpose. General formula (RI) [Chemical 8] Where Z¹Is a nitrogen atom, oxygen atom, sulfur atom or
Z atom²Is an oxygen atom, sulfur atom, or selenium atom
Represents a child. L¹, L², L³, L^Four, L^FiveRepresents the methine group
However, even if it is substituted, it may form a 5- or 6-membered ring with another methine group.
It may be formed. R¹And R²Are the same or different
It represents a good alkyl group and may have a substituent.
R¹Is L¹And R²Is L^Five5 or 6 connected to each other
You may form a member ring. V¹, V², V³, V^Four, V^Five，
V⁶, V⁷, V⁸Are hydrogen atom, halogen atom,
Alkyl group, acyl group, acyloxy group, alkoxycarl
Bonyl group, carbamoyl group, sulfamoyl group, carbo
Xiki, cyano, hydroxy, amino, acyl
Amino group, alkoxy group, alkylthio group, alkyls
Rufonyl group, sulfo group, aryloxy group or aryl
Represents a radical, V¹~ V⁸Bound to adjacent carbon atoms in
Two of them may form a condensed ring with each other. Y¹Is electric
Represents a load-balancing counterion, where s is the neutralization of zero or more charges
Represents the required value for.