JP2000330247A - Silver halide color photographic sensitive material for photographing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide color photographic sensitive material for photographing superior in a ratio of sensitivity to fog and improved in resistance to harmful gases occurring at the time of combustion exhaust gases. SOLUTION: The silver halide color photographic sensitive material to be used for photographing has a green-sensitive emulsion layer and a nonphotosensitive layer on a support and an image is formed by exposure and color development processing and desilvering. The green sensitive emulsion layer contains flat silver halide grains having pricipal faces (111) and an aspect ratio of >=5 and comprising AgBrI or AgClBrI having a surface AgI content of <=5 mol% and occupying >=50% of the total projection areas of the silver halide, and this photosensitive material has a compound represented by the formula and sulfite ions. In the formula, each of R11-R14 is an H atom or an aryl, alkyl, alkenyl, or alkynyl group; R15 is an alkyl, alkenyl, alkynyl, aryl, or heterocyclic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material for photographing. The present invention particularly relates to a silver halide color photographic light-sensitive material for photographing, which contains tabular silver halide grains in a green-sensitive silver halide emulsion layer.

[0002]

2. Description of the Related Art The use of tabular grains for increasing the light absorption efficiency as a method for improving the sensitivity / granularity ratio of a silver halide photographic emulsion is known from US Pat. No. 4,956,269. The sensitivity is improved by increasing the aspect ratio and increasing the spectral sensitizing dye in such tabular grains. It has been found that fogging is significantly increased by burning combustion gas (for example, exhaust gas from automobiles or the like).

When a reduction sensitization method, which is known as a method for increasing quantum sensitivity, is applied to the above-mentioned particles, the fogging phenomenon caused by exhaust gas from automobiles and the like is further deteriorated, and improvement is strongly desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-sensitivity silver halide color photographic light-sensitive material for photography which has an excellent sensitivity / fog ratio. The present invention simultaneously provides a silver halide color photographic light-sensitive material for photography, which has remarkably improved resistance to harmful gases generated during combustion of automobile exhaust gas and the like.

[0005]

Means for Solving the Problems The inventors of the present invention have maintained the sensitivity of tabular grains which have been subjected to spectral sensitization of green light, while suppressing the increase in fog due to combustion gas generated in the environment. As a result of diligent research, we have found a way to do this.

That is, the objects of the present invention can be achieved by the following silver halide color photographic light-sensitive materials.

(1) At least one green-sensitive silver halide emulsion layer and at least one non-photosensitive layer are formed on a support, and after exposure, an image is formed through a color development step and a subsequent desilvering step. In a silver halide color photographic light-sensitive material for photography, at least one of the green-sensitive silver halide emulsion layers has a (111) plane parallel to the principal plane, an aspect ratio of 5 or more, and a surface silver iodide content. Is 5 mol% or less, and contains tabular silver halide grains composed of silver iodobromide or silver chloroiodobromide comprising a silver halide emulsion occupying 50% or more of the total projected area, and represented by the following general formula (I): A silver halide color photographic light-sensitive material for photography, comprising a compound represented by the formula and a sulfite ion.

Formula (I)

[0009]

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In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an aryl group, a chain or cyclic alkyl group, a chain or cyclic alkenyl group, or an alkynyl group; ₁₅ is a chain or cyclic alkyl group, a chain or cyclic alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group (hereinafter, also referred to as a first embodiment).

(2) The method according to the first aspect, wherein at least one of the cyanine sensitizing dyes represented by the following general formula (II) is contained in an amount of at least 5 × 10 ^-4 mol per mol of silver halide. Silver halide color photographic light-sensitive material for photography.

General formula (II)

[0013]

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In the formula, Z ₁ and Z ₂ each independently represent an atomic group necessary for forming a heterocyclic nucleus together with an oxygen atom. L ₁ and L ₂ each independently represent a methine group or a substituted methine group. X ₁ ^- represents an acid anion group. n ₁ is 1
Or 2 is represented. R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group or allyl group used for the N-substituent of the cyanine dye (hereinafter, also referred to as a second embodiment).

(3) From at least one compound represented by the following general formula (III) and a compound represented by the following general formula (IV-1) and a compound represented by the following general formula (IV-2) A first compound comprising at least one member selected from the group consisting of compounds represented by the following general formulas (AI) to (A-III); The silver halide color photographic light-sensitive material for photography according to the embodiment or the second embodiment.

Formula (III)

[0017]

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In the formula, Het is an adsorptive group to silver halide. However, the group represented by Het is substituted with at least one-(Q) k2- (Hy). Q represents a divalent linking group consisting of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Hy represents a group having a hydrazine structure represented by R ₁ R ₂ N—NR ₃ R ₄ . R ₁ , R ₂ , R ₃ and R ₄
Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; R ₁ and R ₂ ;
R ₃ and R ₄ , R ₁ and R ₃ or R ₂ and R ₄ may combine with each other to form a ring. However, at least one of R ₁ , R ₂ , R ₃ and R ₄ is-(Q) k2 in the general formula (III).
-(Het) k1 is an alkylene group, alkenylene group, alkynylene group, arylene group or divalent heterocyclic residue to be substituted. k1 and k3 are each independently 1,
Represents 2, 3, or 4, and k2 represents 0 or 1.

Formulas (IV-1) and (IV-2)

[0020]

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In the general formula (IV-1), R ₃₁ , R ₃₂ and R ₃₃
And R ₃₄ each independently represent a hydrogen atom or a substituent.
However, when R ₃₁ and R ₃₄ or R ₃₂ and R ₃₃ are each an alkyl group, they do not take substituents having exactly the same carbon number.

In the general formula (IV-2), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom or a substituent. Z is 4
Represents a non-metallic atomic group forming a 6-membered ring.

Formulas (AI) to (A-III)

[0024]

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In the general formula (AI), R _a1 represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R _a2 represents a hydrogen atom or a group represented by R _a1 . R _a3
Represents a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group having 1 to 10 carbon atoms. _Ra1 and _Ra3 or _Ra2 and _Ra3 may be bonded to each other to form a 5- to 7-membered ring.

In the general formula (A-II), X represents a heterocyclic group, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring.

In the general formula (A-III), Y represents -N = C-
In addition, it represents a group of nonmetallic atoms necessary for forming a 5-membered ring.
Y further forms a 6-membered ring together with the -N = C- group.
Represents a necessary group of non-metallic atoms, and represents a carbon atom of a -N = C- group.
The terminal of Y that binds to the child is -N (R _C1)-, -C (R_C2) (R_C3)-, -C
(R_C4) =, 1 selected from the group consisting of -O- and S-
(Bonded to the carbon atom -N = C- on the left side of each group)
Represents R_c1~ R_c4Are each independently a hydrogen atom or substituted
Represents a group (hereinafter, also referred to as a third embodiment).

(4) The silver halide color photographic light-sensitive material for photography according to any one of the first to third aspects, which comprises at least one compound represented by the following general formula (V).

General formula (V)

[0030]

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In the formula (V), R_{twenty one}, R_{twenty two}And R_{twenty three}Are each
Independently hydrogen, alkyl, alkenyl, alkynyl
Represents an aryl group, an aryl group, or a heterocyclic group;_{twenty four}Is water
Element atom, alkyl group, alkenyl group, alkynyl group,
Reel group, or heterocyclic group, or NR_{twenty five}R₂₆The table
Then L_{twenty one}Is -CO- or -SO_Two-, And n is 0 or
Or 1 R_{twenty five}Is hydrogen atom, hydroxy group, amino
Group, alkyl group, alkenyl group, alkynyl group, aromatic
A heterocyclic group or a heterocyclic group;₂₆Is an alkyl group,
Kenyl group, alkynyl group, aromatic group, or heterocyclic group
Represents R_{twenty one}And R _{twenty two}, R_{twenty one}And R_{twenty three}, R_{twenty three}And R_{twenty four}Or
R_{twenty four}And R_{twenty two}May be linked to form a ring.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The silver halide emulsion used in the present invention relates to a silver iodobromide or silver chloroiodobromide tabular grain emulsion.

The tabular grain emulsion has an opposing (111) main surface and side surfaces connecting the main surfaces. Tabular grain emulsions are comprised of silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. Regarding the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 25% or less, and thus the silver iodide content is preferably 20 mol% or less. By reducing the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion can be easily reduced. In particular, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less.
Regardless of the silver iodide content, the coefficient of variation of the silver iodide content distribution between grains is preferably 20% or less, particularly preferably 10% or less.

The tabular grain emulsion preferably has a structure within the grains with respect to silver iodide distribution. In this case, the structure of the silver iodide distribution may be a double structure, a triple structure, a quadruple structure, or even a higher structure.

In the tabular grain emulsion, 50% or more of the total projected area is occupied by grains having an aspect ratio of 5 or more. Here, the projected area and the aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method shadowed with a latex sphere for reference. Tabular grains are generally hexagonal when viewed from a direction perpendicular to the main surface,
Although it has a triangular or circular shape, a value obtained by dividing a diameter (circle equivalent diameter) corresponding to a circle having an area equal to the projected area by the thickness is the aspect ratio. Tabular grain shape is 6
The higher the ratio of the polygons, the better, and the ratio of the lengths of the adjacent sides of the hexagon is preferably 1: 2 or less.

Since the effect of the present invention is more remarkable as the aspect ratio is higher, the tabular grain emulsion accounts for 50% or more of the total projected area by grains having an aspect ratio of preferably 8 or more. More preferably, the aspect ratio is 12 or more. If the aspect ratio is too large, the variation coefficient of the particle size distribution described above tends to increase, so that the aspect ratio is usually preferably 50 or less.

In the present invention, the tabular grain emulsion has a (111) main surface facing and a side surface connecting the main surface.
At least one twin plane exists between the main surfaces. In the tabular grain emulsion used in the present invention, two twin planes are usually observed. The distance between these twin planes is US
As described in US Pat. No. 5,219,720, it can be smaller than 0.012 μm. Further, JP-A-5-2495
As described in No. 85, the value obtained by dividing the distance between the (111) main surfaces by the twin plane spacing can be 15 or more.

In the present invention, it is particularly preferable that 75% or less of all side surfaces connecting the opposing (111) main surfaces of the tabular grain emulsion are composed of (111) surfaces. Here, the fact that 75% or less of all the side surfaces are composed of the (111) plane means that (11)
1) A crystallographic plane other than the plane exists. Usually, the plane can be understood as the (100) plane, but may also include other planes, that is, the (110) plane or a plane with a higher index. In the present invention, the effect is remarkable when 70% or less of all side surfaces are constituted by (111) planes.

Whether or not 70% or less of all side surfaces are composed of (111) planes can be easily determined from electron micrographs of the host tabular grains by a shadowed carbon replica method. Usually, 75% or more of the side surface is (11
1) In the case of a hexagonal tabular grain composed of planes, the six side faces directly connected to the (111) main surface are connected to the (111) main surface at an acute angle and an obtuse angle with each other. On the other hand, when 70% or less of all side surfaces are composed of (111) planes, (1)
11) The six sides directly connected to the main surface are all connected at an obtuse angle to the (111) main surface. By applying shadowing at an angle of 50 ° C. or less, the obtuse angle and the acute angle of the side surface with respect to the main surface can be determined. Preferably, shadowing at an angle of 30 ° or less and 10 ° or more facilitates determination of an obtuse angle and an acute angle.

Furthermore, a method using adsorption of a sensitizing dye is effective as a method for determining the ratio between the (111) plane and the (100) plane. The Chemical Society of Japan, 1984, Volume 6, Page 94
The ratio between the (111) plane and the (100) plane can be quantitatively determined by using the method described in JP-A No. 2-947.
The ratio of the (111) plane on all side surfaces can be calculated and obtained using the ratio and the above-described circle equivalent diameter and thickness of the tabular grains. In this case, it is assumed that the tabular grain is a cylinder using the equivalent circle diameter and thickness. With this assumption, the ratio of the side surface to the total surface area can be determined. The value obtained by dividing the ratio of the (100) plane obtained by the above-described adsorption of the sensitizing dye by the ratio of the above-described side surface and multiplying by 100 is the ratio of the (100) surface in all the side surfaces. By subtracting the value from 100, the ratio of the (111) plane on all side surfaces can be obtained. In the present invention, (111) in all aspects
More preferably, the ratio of the faces is 65% or less.

In the present invention, 7
A method of setting 5% or less to the (111) plane will be described.
Most commonly, the ratio of the (111) face of the side face of the silver iodobromide or silver chloroiodobromide tabular grain emulsion can be determined by pBr at the time of preparing the tabular grain emulsion. Here, pBr is the logarithm of the reciprocal of the Br ^- ion concentration of the system. When the total silver content of the tabular grain emulsion is 100, preferably at least 70 of the total silver content.
% Is set so that the ratio of the (111) plane of the side surface decreases, that is, the ratio of the (100) plane of the side surface increases after the addition of% or more. Most preferably, the pBr is set so that the ratio of the (100) side surface increases after at least 90% or more of the total silver amount is added. 70% of total silver
It is not preferable to set the pBr such that the ratio of the (100) side surface is increased before the addition of the compound, because the aspect ratio of the host tabular grain emulsion is reduced. Further, if the pBr is set so that the ratio of the (100) side surface increases after 98% or more of the total silver amount is added, the (100) surface ratio of the side surface for obtaining the effect of the present invention is achieved. It becomes difficult. Therefore, it is most preferable to set the pBr such that the ratio of the (100) side surface increases after at least 90% or more of the total silver is added until 98% or less of the total silver is added. Then, the effect of the invention is remarkably obtained. However, as another method, it is also possible to increase the ratio by setting the pBr such that the ratio of the (100) side surface increases after the total silver amount is added and then ripening.

The pBr such that the ratio of the (100) side of the side surface increases is defined as the system temperature, pH, type and concentration of protective colloid such as gelatin, presence / absence and type of silver halide solvent,
Its value can vary widely depending on the concentration and the like. Usually, it is preferably pBr 2.0 or more and 5 or less. More preferably, it is pBr2.5 or more and 4.5 or less. However,
As described above, the value of pBr can be easily changed by the presence of, for example, a silver halide solvent. Preferably, no silver halide solvent is used in the present invention.

Examples of the silver halide solvent usable in the present invention include US Pat. Nos. 3,271,157, 3,531,289 and 3,574,628, and JP-A-54-1019. (A) Organic thioethers described in JP-A-53-824 and JP-A-54-158917.
(B) thiourea derivatives described in JP-A Nos. 08-55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-4319, (d) imidazoles described in JP-A-54-100717, e) ammonia, (f) thiocyanate and the like.

Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferred amount is
It is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol.

As a method for changing the plane index of the side surface of the tabular grain emulsion, EP515894A1 or the like can be referred to. Also, polyalkylene oxide compounds described in US Pat. No. 5,252,453 can be used. US4680254, US4680255,
Surface index modifiers described in US Pat. No. 4,680,256 and US Pat. No. 4,684,607 can be used. Ordinary photographic spectral sensitizing dyes can also be used as modifiers having the same plane index as described above.

In the present invention, silver iodobromide or silver chloroiodobromide tabular grain emulsions can be prepared by various methods as long as the above requirements are satisfied. The preparation of a tabular grain emulsion usually comprises basically three steps of nucleation, ripening and growth. US47 in the nucleation process
Use of gelatin having low methionine content described in US Pat. No. 13320 and US Pat.
The nucleation at a high pBr described in No. 4014 and the nucleation in a short time described in JP-A-2-222940 are extremely effective in the nucleation step of the tabular grain emulsion used in the present invention. US5 in the aging process
Performing in the presence of a low-concentration base described in US Pat. No. 254453, or performing at a high pH described in US Pat. No. 5,136,641 may be effective in the ripening step of the tabular grain emulsion used in the present invention. In the growth step, growth is performed at a low temperature described in US Pat. No. 5,248,587, US Pat. No. 4,720,027, and US Pat. No. 4,693,964.
The use of the silver iodide fine particles described in (1) is particularly effective in the step of growing the tabular grain emulsion used in the present invention. Further, it is also preferable to use a silver bromide, silver iodobromide, silver chloroiodobromide fine grain emulsion to be added and ripened for growth. The fine grain emulsion can be supplied by using a stirring device described in JP-A-10-43570.

The emulsion used in the present invention preferably introduces a hole-capturing silver nucleus by intentional reduction sensitization. The intentional reduction sensitization means reduction sensitization performed by adding a reduction sensitizer. The hole-capturing silver nucleus means a small silver nucleus having a small developing activity, and the silver nucleus can prevent recombination loss in a photosensitive process and increase sensitivity. The method of introducing hole-capturing silver nuclei can be achieved by intentionally performing reduction sensitization in the grain formation of the silver halide emulsion.

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

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides, and added during grain growth.

In the present invention, a hole-capturing silver nucleus is preferably formed by adding a reduction sensitizer after 50% of the total silver amount required for grain formation is added. More preferably, a hole-capturing silver nucleus is formed by adding a reduction sensitizer after adding 70% of the total silver amount required for grain formation. It is also possible in the present invention to add a reduction sensitizer after the completion of grain formation to introduce hole-capturing silver nuclei on the grain surface.

When a reduction sensitizer is added during grain formation, a part of the formed silver nuclei can remain inside the grains, but a part of the silver nuclei exudes to form silver nuclei on the grain surface. In the present invention, it is preferable to use the exuded silver nuclei as hole-capturing silver nuclei.

The formation of a hole-capturing silver nucleus is preferably carried out in the presence of a compound of the general formula (V-1) and / or a compound of the general formula (V-2) during intentional reduction sensitization. preferable.

Formulas (V-1) and (V-2)

[0055]

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In the general formulas (V-1) and (V-2), W ₅₁ and W ₅₂ each independently represent a sulfo group or a hydrogen atom. However, at least one of W ₅₁ and W ₅₂ represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as an ammonium salt. Specific examples of preferred compounds include 3,5-
Disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, 2,3-dihydroxy-
6,7-disulfonaphthalene potassium salt and the like. The preferred addition amount is the temperature of the system to be added, pBr, p
H, the type and concentration of a protective colloid such as gelatin, and the presence or absence, type, and concentration of a silver halide solvent may vary.
Generally, from 0.0005 mol to 0.5 mol, more preferably from 0.003 mol to 0.5 mol, per 1 mol of silver halide.
02 moles are used.

The silver iodide content on the surface of the tabular grain emulsion used in the present invention is 5 mol% or less. If the silver iodide content on the grain surface is large, it is difficult to obtain the effects of the present invention.
The silver iodide content on the grain surface specified in the present invention is XP
S (X-ray Photoelectron Spe)
troscopy). XPS used for analysis of silver iodide content near the surface of silver halide grains
For the principle of the method, reference can be made to Aihara et al., "Electron Spectroscopy" (Kyoritsu Library-16, published by Kyoritsu Shuppan, 1978). The standard measurement method of XPS uses Mg-Kα as an excited X-ray, and photoelectrons (usually I-3d5) of iodine (I) and silver (Ag) emitted from silver halide in an appropriate sample form. / 2, Ag-3d5 / 2). To determine the iodine content,
A calibration curve of the intensity ratio of photoelectrons of iodine (I) and silver (Ag) (intensity (I) / intensity (Ag)) was prepared using several types of standard samples having known iodine contents. Can be found. In a silver halide emulsion, XPS must be measured after gelatin adsorbed on the surface of silver halide grains is decomposed and removed by a protease or the like. The tabular grain emulsion having a silver iodide content of 5 mol% or less on the grain surface used in the present invention is one in which the emulsion grains contained in one emulsion have a silver iodide content of 5 mol% or less when analyzed by XPS. Point out. In this case, clearly 2
When more than one emulsion is mixed, centrifugation,
It is necessary to analyze the same type of emulsion after performing an appropriate pretreatment such as a filtration method.

It is a remarkable effect of the present invention that the tabular grain emulsion used in the present invention contains 5 mol% or less of silver iodide on the surface of the grains, and furthermore, the surface of the emulsion has a surface of 3 mol% or less.
More preferably, the grains contain silver iodide in an amount of 1 mol% or more and a surface of 1 to 2.5 mol%. As long as the tabular grain emulsion used in the present invention has a silver iodide content of 5 mol% or less on the surface, the structure is, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide or a higher-order structure having a higher structure. Is also preferred. The boundary of the silver iodide content between the structures may be clear or may be continuously and gradually changing. Normally, the measurement of the silver iodide content using the powder X-ray diffraction method does not show two distinct peaks having different silver iodide contents, and the skirt is shifted toward the high silver iodide content. Such an X-ray diffraction profile is shown.

In the present invention, the silver iodide content of the layer inside the surface is preferably higher than the silver iodide content of the surface, and the silver iodide content of the layer inside the surface is preferably 5%. If it is at least 7 mol%, more preferably at least 7 mol%, the efficiency of the invention will be remarkable.

The photographic emulsion of the present invention is spectrally sensitized to green light sensitivity. Here, the green photosensitivity means that spectral sensitization is performed so that the spectral sensitization sensitivity becomes maximum at 500 nm or more and less than 600 nm.

The tabular grain emulsion used in the present invention is preferably subjected to spectral sensitization with a cyanine dye represented by the following general formula (II).

The cyanine dye represented by formula (II) will be described in detail.

Z ₁ and Z ₂ each independently represent an atom group necessary for forming a heterocyclic nucleus together with an oxygen atom. For example, oxazoline, benzoxazole, naphthoxazole and the like can be mentioned. These heterocyclic nuclei include, for example, lower alkyl groups such as methyl, halogen atoms, phenyl groups, hydroxyl groups, alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, alkoxycarbonyl groups, alkylsulfamoyl groups, and alkylcarbamoyl. Group, acetyl group,
It may be substituted by an acetoxy group, a cyano group, a trichloromethyl group, a trifluoromethyl group, or a nitro group.

L _{1 and} L ₂ each independently represent a methine group or a substituted methine group. Examples of the substituted methine group include a lower alkylene group such as methyl and ethyl, and a methine group substituted by phenyl, substituted phenyl, methoxy, and ethoxy.

R ¹ and R ² are each independently an alkyl group having 1 to 5 carbon atoms; a substituted alkyl group having a carboxy group; for example, β-sulfoethyl, γ-sulfopropyl, δ-sulfobutyl, γ-sulfobutyl, A substituted alkyl group having a sulfo group such as-(3-sulfopropoxy) ethyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, 2-hydroxysulfopropyl, allyl
1) represents a group or a substituted alkyl group commonly used for the N-substituent of a cyanine dye.

[0066] X ₁ ^- represents an acid anion group, for example iodide, bromide, p- toluenesulfonate ion, a perchlorate ion. n ₁ represents 1 or 2, and n ₁ is 1 when it has a betaine structure.

Representative compounds of effective spectral sensitizing dyes used in the present invention are shown below, but the present invention is not limited to these compounds.

[0068]

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[0069]

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[0070]

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These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862 and 4,026,707, British Patent Nos. 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-5
Nos. 2-110618 and 52-109925.

In the present invention, particularly preferably, spectral sensitization of green sensitivity is carried out by adding three or more kinds of cyanine dyes selected from the cyanine dyes represented by the general formula (II). At this time, not all of the three or more cyanine dyes need to be green-sensitive, and as a result of adding the four or more cyanine dyes, they are spectrally sensitized so that the spectral sensitivity is maximized to green light. I just want to. In particular, one or more of the three or more cyanine dyes may be a monomethine cyanine dye.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, this is done after completion of chemical sensitization but before coating, but US Pat. No. 3,628,969.
As described in JP-A-58-113928, addition of a chemical sensitizer and simultaneous addition of a chemical sensitizer and spectral sensitization as described in JP-A-58-113928 can also be used. As described above, it can be carried out prior to chemical sensitization, or it can be added before completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add after the feeling, US Pat.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 3,756.

The addition amount of the sensitizing dye to the tabular grain emulsion used in the present invention is 5 × 10 5 per mol of silver halide.
^-4 mol or more, and when the silver halide grain size is 0.2 to 1.2 μm, about 5 × 10 ^-4 to 4 ×
10 ^-3 mol is more effective.

The sulfite ion contained in the light-sensitive material of the present invention will be described in detail.

The sulfite ion is usually added in the form of an alkali metal salt or an alkaline earth metal salt. Preferably it is sodium sulfite.

The sulfite ion is preferably added at the time of preparing the tabular silver halide emulsion for the green-sensitive layer, and is added before, during or after the chemical sensitization. It can be added before coating the emulsion, or can be added to an adjacent layer or another layer at the time of coating and diffused into the emulsion layer.

The preferable addition amount largely depends on the above-mentioned addition method and the like, but is generally 0.1 to 1 mol per mol of silver halide.
00001 mol to 0.01 mol, more preferably 0.1 mol.
From 0001 mol to 0.001 mol is used.

The compound represented by formula (I) will be described in more detail.

In the general formula (I), the alkyl group, alkenyl group and alkynyl group represented by R ₁₁ and R ₁₂ are:
A substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl,
n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-
Ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl,
Dibutylaminoethyl, n-butoxypropyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl,
Cyclohexyl), an alkenyl group having 2 to 10 carbon atoms (e.g., allyl, 2-butenyl, 3-pentenyl), an alkynyl group having 2 to 10 carbon atoms (e.g., propargyl, 3
-Pentynyl), an aralkyl group having 6 to 12 carbon atoms (e.g., benzyl), and the like. As the aryl group, a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms (e.g., unsubstituted phenyl, 4-methylphenyl) ) And the like.

In the general formula (I), the alkyl group, alkenyl group and alkynyl group represented by R ₁₃ and R ₁₄ are
A substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl,
n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-
Ethylhexyl, 2-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, methoxyethyl, ethoxyethoxyethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl), 2 to 2 carbon atoms 10 alkenyl groups (eg, allyl, 2-butenyl, 3-pentenyl), alkynyl groups having 2 to 10 carbon atoms (eg, propargyl, 3-pentynyl), aralkyl groups having 6 to 12 carbon atoms (eg, benzyl), etc. Examples of the aryl group include a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl, 4-methylphenyl),
And substituted or unsubstituted naphthyl having 10 to 16 carbon atoms (eg, unsubstituted naphthyl).

Further, R ₁₁ or R ₁₂ and R ₁₃ or R ₁₄
May be linked to form a ring.

In the general formula (I), the alkyl group, alkenyl group and alkynyl group represented by R _{15 have} 1 to 1 carbon atoms.
8 substituted or unsubstituted linear or branched alkyl groups (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, diethylaminoethyl),
A substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (eg, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl), 10
(E.g., propargyl, 3-pentynyl), an aralkyl group having 6 to 12 carbon atoms (e.g., benzyl), and the like.
6 substituted or unsubstituted phenyl groups (eg, unsubstituted phenyl, 4-methylphenyl, 4- (2-hydroxyethyl) -phenyl, 4-sulfophenyl, 4-chlorophenyl, 4-trifluoromethylphenyl, 3- Trifluoromethylphenyl, 4-carboxyphenyl, 2,5
-Dimethylphenyl, 4-dimethylaminophenyl, 4
-(3-carboxypropionylamino) -phenyl,
4-methoxyphenyl, 2-methoxyphenyl, 2,5
-Dimethoxyphenyl, 2,4,6-trimethylphenyl), and naphthyl having 10 to 16 carbon atoms (eg, unsubstituted phenyl group, 4-methylnaphthyl). Examples of the heterocyclic group include pyridyl, furyl, imidazolyl. , Piperidyl and morpholyl.

Further, R ₁₁ and R in the above general formula (I)
₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may have a substituent as much as possible. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) and an alkyl group (for example, methyl , Ethyl, isopropyl, n-propyl, t-butyl), alkenyl groups (for example, allyl, 2-
Butenyl), alkynyl group (eg, propargyl), aralkyl group (eg, benzyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl), alkoxy group ( For example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy), an aryloxy group (eg, phenoxy, 2-naphthyloxy), an amino group (eg, unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutyl) Amino, ethylamino, anilino), acylamino group (eg, acetylamino, benzoylamino), ureido group (eg, unsubstituted ureido, N-methylureido), urethane group (eg, methoxycarbonylamino) Phenoxycarbonylamino), a sulfonylamino group (eg, methylsulfonylamino, phenylsulfonylamino), a sulfamoyl group (eg, unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), a carbamoyl group (eg, unsubstituted) Carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl), sulfonyl group (eg, mesyl, tosyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxy Carbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, benzoyl, formyl, pivaloyl), acyloxy groups (eg, acetoxy, benzoy) Oxy), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide), cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, phosphono group, nitro group, ammonium group, phosphonio group Hydrazino group and thiazolino. When there are two or more substituents, they may be the same or different.

In the following, preferred R ₁₁ of the general formula (I),
Examples of R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are shown.

In the general formula (I), R ₁₁ and R ₁₂ each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 10 carbon atoms. Wherein R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or a carbon atom having 6 to 1 carbon atoms.
0 is a substituted or unsubstituted phenyl group, R ₁₅ is a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms, and the compound represented by the general formula (I) has a molecular weight of 3
It is preferably 50 or less.

Further, in the general formula (I), R ₁₁ and R ₁₂
Is a substituted or unsubstituted linear alkyl group having 1 to 3 carbon atoms, R ₁₃ and R ₁₄ are hydrogen atoms, and R ₁₅ is a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, The compound represented by the general formula (I) has a molecular weight of 3
More preferably, it is not more than 00. Further, in the general formula (I), it is most preferable that the total number of carbon atoms of R ₁₁ to R ₁₅ is 11 or less.

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

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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The compound represented by formula (I) can be easily obtained as a commercially available drug or as a compound synthesized from a commercially available drug by a known method. As a method for synthesizing the general formula (I), Journal of Chemical Society (J. Chem. Soc.) 40
8 (1954), U.S. Pat.
3 years), a method described in U.S. Pat. No. 2,772,282 (1953), or a method analogous thereto can be easily synthesized.

The compound represented by the formula (I) is preferably added to an adjacent layer or another layer of the emulsion layer before or at the time of coating the coating solution and diffused into the emulsion layer.
It can also be added before, during or after chemical sensitization during the preparation of the emulsion. The compound represented by the general formula (I) can be added to a light-sensitive layer or a non-light-sensitive layer.

The preferred addition amount largely depends on the above-mentioned addition method and the kind of the compound to be added, but is generally from 5 × 10 ^-6 mol to 0.05 mol, more preferably 1 × 10 ^-6 mol, per mol of light-sensitive silver halide. ^-5 mol to 0.005 mol is used. If the amount is larger than the above amount, adverse effects such as an increase in fog are caused, which is not preferable.

The compound represented by the formula (I) is preferably added after being dissolved in a water-soluble solvent. The pH may be lowered or raised by an acid or a base, or a surfactant may be present. Further, it may be added by dissolving in an organic solvent having a high boiling point as an emulsified dispersion, or may be added as a microcrystal dispersion by a known dispersion method.

The compounds of the formula (I) may be used in combination of two or more kinds. When two or more compounds of the formula (I) are used in combination, these compounds may be added to the same layer or to another layer.

The compound represented by formula (III) will be described in more detail.

First, R, which is preferably used as Hy,
It will be described in detail hydrazine structure represented by _{1 R 2 N-NR 3 R} 4.

R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may be bonded to each other to form a ring,
It does not form an aromatic heterocycle.

However, at least one of R ₁ , R ₂ , R ₃ and R ₄ is-(Q) k2- in the general formula (III).
(Het) k1 is an alkylene group, alkenylene group, alkynylene group, arylene group or divalent heterocyclic residue to be substituted.

R ₁ , R ₂ , R ₃ and R ₄ are, for example, unsubstituted alkyl, alkenyl or alkynyl groups having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms (eg methyl group, ethyl group Propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group, cyclopentyl group, cyclopropyl group, cyclohexyl group), having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. Examples include a substituted alkyl group, an alkenyl group, and an alkynyl group.

Assuming that the substituent is V, the substituent represented by V is not particularly limited. Examples thereof include a carboxy group, a sulfo group, a cyano group, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). Atoms), a hydroxy group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group (eg, methoxy, ethoxy, benzyloxy, phenethyloxy),
Aryloxy group (eg, phenoxy, 4-methylphenoxy, α-naphthoxy), acyloxy group (eg, acetyloxy, propionyloxy), acyl group (eg, acetyl, propionyl, benzoyl, mesyl), carbamoyl group (eg, carbamoyl, N, N -Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl group (for example, phenyl, 4-chlorophenyl, 4- Methylphenyl,
α-naphthyl), a heterocyclic group (eg, 2-pyridyl,
Tetrahydrofurfuryl, morpholino, 2-thienyl), amino group (eg, amino, dimethylamino, anilino, diphenylamino), alkylthio group (eg, methylthio, ethylthio), alkylsulfonyl group (eg, methylsulfonyl, propylsulfonyl), alkyl Sulfinyl group (eg, methylsulfinyl), nitro group, phosphate group, acylamino group (eg, acetylamino), ammonium group (eg, trimethylammonium, tributylammonium), mercapto group, hydrazino group (eg, trimethylhydrazino), ureido group (eg, Ureido, N, N-dimethylureido), imide group, alkenyl group (for example, vinyl group, ethynyl group,
A 1-cyclohexenyl group), an alkynyl group (for example, a benzylidene group), and an alkylidene group (for example, a benzylidene group). The substituent V preferably has 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. V may be further substituted on these substituents.

More specifically, alkyl, alkenyl, and alkynyl groups such as carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 3-sulfopropyl,
4-sulfobutyl, 3-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-cyanoethyl, 2-chloroethyl, 2-bromoethyl, 2-hydroxyethyl, 3
-Hydroxypropyl, hydroxymethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-ethoxycarbonylethyl, methoxycarbonylmethyl, 2-methoxyethyl, 2-ethoxyethyl,
2-phenoxyethyl, 2-acetyloxyethyl, 2
-Propionyloxyethyl, 2-acetylethyl, 3
-Benzoylpropyl, 2-carbamoylethyl, 2-
Morpholinocarbonylethyl, sulfamoylmethyl,
2- (N, N-dimethylsulfamoyl) ethyl, benzyl, 2-naphthylethyl, 2- (2-pyridyl) ethyl, allyl, 3-aminopropyl, 3-ditylaminopropyl, methylthiomethyl, 2-methylsulfonyl Ethyl, methylsulfinylmethyl, 2-acetylaminoethyl, 3-trimethylammoniumethyl, 2-mercaptoethyl, 2-trimethylhydrazinoethyl, methylsulfonylcarbamoylmethyl, (2-methoxy) ethoxymethyl, and the like. Number of atoms 6-1
8, more preferably 6 to 12 aryl groups (for example, phenyl, α-naphthyl, β-naphthyl, and further, for example, the aforementioned substituent V or an alkyl group, an alkenyl group,
Phenyl or naphthyl substituted with an alkynyl group, a heterocyclic group having 4 to 18 carbon atoms, more preferably 4 to 12 carbon atoms (for example, 2-pyridyl, the above-described substituent V or the above-mentioned substituent V substituted with an alkyl, alkenyl, or alkynyl group) 2-pyridyl) is preferred.

Further, R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may be bonded to each other to form a ring. However, it does not form an aromatic hetero ring. These rings may be substituted, for example, by the substituent V described above.

R ₁ , R ₂ , R ₃ and R ₄ are more preferably an unsubstituted alkyl group, alkenyl group, alkynyl group, substituted alkyl group, alkenyl group, alkynyl group, and R ₁ and R ₂ , R ₃ R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ are bonded to each other to form an alkylene group containing no carbon atom other than a carbon atom (eg, an oxygen atom, a sulfur atom, or a nitrogen atom) ｛alkylene group Is the case where｝ which may be substituted (for example, the aforementioned substituent V) is formed.

More preferably, R ₁ , R ₂ , R ₃ and R ₄ are those in which the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group. R ₁ , R ₂ , R
₃ and R ₄ are particularly preferably an unsubstituted alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, butyl), a substituted alkyl group having 1 to 8 carbon atoms {eg, a sulfoalkyl group (eg, 2- Sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl), carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl), hydroxyalkyl group (for example, 2-hydroxyethyl)}, and R ₁ , R ₂ , and R ₃ And R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ are bonded to each other by an alkylene chain to form a 5-, 6- and 7-membered ring.

The hydrazine group represented by R ₁ R ₂ N—NR ₃ R ₄ is substituted by at least one — (Q) k2- (Het) k1. The substitution positions are R ₁ , R ₂ , R ₃ and R ₄
Either may be used.

The hydrazine compound represented by R ₁ R ₂ N—NR ₃ R ₄ can be used in the case where it is advantageous in synthesis and storage.
No problem if isolated as a salt. In such a case, any compound may be used as long as it can form a salt with hydrazines, and the following are preferred salts.

For example, aryl sulfonates (for example, p
-Toluenesulfonate, p-chlorobenzenesulfonate), aryldisulfonates (eg, 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonate, 2,6-naphthalenedisulfonate), thiocyanate Acid, picrate, carboxylate (eg, oxalate, acetate, benzoate, hydrogen oxalate), halogenate (eg, hydrochloride, hydrofluoride, hydrobromide) , Hydroiodide), sulfate, perchlorate, tetrafluoroborate, sulfite, nitrate, phosphate, carbonate, and bicarbonate.

Preferred are hydrogen oxalate, oxalate, 1,5-naphthalenedicarboxylate and hydrochloride.

Further, R ₁ R ₂ NN used in the present invention
The compound represented by R ₃ R ₄ has the following general formula (Hy-
Particularly preferred is a compound selected from 1), (Hy-2) and (Hy-3).

[0114]

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In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ₅ and R ₆ , or R ₇ and R ₈ may be bonded to each other to form a ring.

Z ₁ represents an alkylene group having 4, 5 or 6 carbon atoms. Z ₂ represents an alkylene group having 2 carbon atoms.

Z ₃ represents an alkylene group having 1 or 2 carbon atoms. Z ₄ and Z ₅ represent an alkylene group having 3 carbon atoms. L ₁ and L ₂ represent a methine group.

Further, formulas (Hy-1) and (Hy-2)
And (Hy-3) each have at least one-
(Q) k2- (Het) k1 is substituted.

More preferred are compounds selected from the general formulas (Hy-1) and (Hy-2), and particularly preferred are compounds selected from the general formula (Hy-1).

The general formula (Hy-1) will be described below in detail.

R ₅ and R ₆ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ , and the preferred range is also the same.

It is particularly preferred that the alkyl group and R ₅ and R ₆ be bonded to each other to form an unsubstituted tetramethylene group or pentamethylene group.

Z ₁ represents an alkylene group having 4, 5 or 6 carbon atoms, preferably an alkylene group having 4 or 5 carbon atoms.

However, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group.

The alkylene group may be unsubstituted or substituted. Examples of the substituent include the substituent V described above, and it is preferable that the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group.

Z ₁ is particularly preferably an unsubstituted tetramethylene group or an unsubstituted pentamethylene group.

The hydrazine group represented by the general formula (Hy-1) has at least one-(Q) k2- (Het) k1
Has been replaced. The substitution position may be any of R ₅ , R ₆ and Z ₁ . Preferably, R ₅ and R ₆ .

Hereinafter, the general formula (Hy-2) will be described in detail.

R ₇ and R ₈ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ , and the preferred range is also the same.

Particularly preferred is a case where the alkyl group and R ₇ and R ₈ are bonded to each other to form a trimethylene group.

Z ₁ represents an alkylene group having 2 carbon atoms. Z ₂ represents an alkylene group having 1 or 2 carbon atoms.

Further, these alkylene groups may be unsubstituted or substituted. Examples of the substituent include the substituent V described above.

Z ₂ is more preferably an unsubstituted ethylene group. More preferably, Z ₃ is an unsubstituted methylene group or an ethylene group.

L ₁ and L ₂ represent a substituted and unsubstituted methine group. Examples of the substituent include the aforementioned substituent V, and are preferably an unsubstituted alkyl group (for example, a methyl group or a t-butyl group). More preferably, it is an unsubstituted methine group.

The hydrazine group represented by the general formula (Hy-2) has at least one-(Q) k2- (Het) k1
Has been replaced. The substitution positions are R ₇ , R ₈ , Z ₂ , Z ₃ ,
Any of L ₁ and L ₂ may be used. Preferably they are R ₇ and R ₈ .

The general formula (Hy-3) will be described in detail. Z ₄ and Z ₅ each independently represent an alkylene group having 3 carbon atoms. However, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group.

Further, these alkylene groups may be unsubstituted or substituted. Examples of the substituent include the substituent V described above, and the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene group.

Particularly preferred as Z ₄ and Z ₅ are unsubstituted trimethylene, unsubstituted alkyl group and substituted trimethylene group (for example, 2,2-dimethyltrimethylene).

The hydrazine group represented by the general formula (Hy-3) is substituted with at least one-(Q) k2- (Het) k1. The substitution position may be either Z ₄ or Z ₅ .

Compounds represented by formulas (Hy-1), (Hy-2) and (Hy-3) are represented by R ₁ R ₂ N—NR ₃
It may be isolated as a salt as in the case of the compound represented by R ₄ . Examples of the salt include those similar to the salt represented by R ₁ R ₂ N—NR ₃ R ₄ . Preferably, hydrogen oxalate, oxalate, 1,5-naphthalene, sulfonate and hydrochloride are used.

In the general formula (III), the group represented by Het has any one of the following structures.

5, 6 or 7-membered heterocycle having two or more heteroatoms 5 or 6 or 7-membered nitrogen-containing heterocycle represented by A having a quaternary nitrogen atom Represented by B having a thioxo group 5, 6 or 7
Membered nitrogen-containing heterocycle 5, 6, or 7-membered nitrogen-containing heterocycle represented by C below 5, 6, or 7-membered nitrogen-containing heterocycle represented by D and E below.

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Ra is preferably R ₁ , R ₂ , R
Examples of the alkyl group, alkenyl group, and alkynyl group of ₃ and R ₄ include those described above.

The nitrogen-containing heterocyclic ring containing Za as a ring-constituting atom contains at least one nitrogen atom and also contains a hetero atom other than a nitrogen atom (for example, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom). A 5-, 6- or 7-membered heterocyclic ring, which is preferably an azole ring (for example, imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, thiadiazole, Oxadiazole, benzoselenazole, pyrazole, naphthothiazole, naphthoimidazole, naphthooxazole, azabenzimidazole, purine), pyrimidine ring, triazine ring,
Azaindene rings (for example, triazaindene, tetrazaindene, pentaazaindene) and the like can be mentioned.

However, the group represented by Het is substituted by at least one-(Q) k2- (Hy).

More preferred as Het are the following general formulas (Het-a), (Het-b) and (Het-b).
c) Compounds represented by (Het-d) and (Het-e).

[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ each independently represent a hydrogen atom or a monovalent substituent. R ₂₄ is an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group.

X ₁ represents a hydrogen atom, an alkali metal atom, an ammonium group or a blocking group. Y ₁ is an oxygen atom, a sulfur atom,>NH,> N- (L ₄ ) p ₃ -R ₂₈ ,
L ₃ and L ₄ each represent a divalent linking group; R ₂₅ and R ₂₈ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;

X ₂ has the same meaning as X ₁ . p ₂ and p ₃ are each independently an integer of 0 to 3. Preferably, p ₂ and p ₃ are 1.

Z ₇ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₂₆ represents an alkyl group, an alkenyl group, or an alkynyl group.

R ₂₇ represents a hydrogen atom or an alkyl, alkenyl, or alkynyl group.

However, the general formulas (Het-a) to (Het-a)
-E) includes at least one-(Q) k2-
(Hy) is substituted. However, the general formula (Het-
c), is not to be replaced by X _1, X ₂ of (Het-d).

Of the general formulas (Het-a) to (Het-e), preferably, the general formulas (Het-a) and (Het-e)
c) and (Het-d), and more preferably the general formula (Het-c).

Next, the general formulas (Het-a) to (Het-a)
e) will be described in more detail.

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆
Each independently represents a hydrogen atom or a monovalent substituent. 1
Examples of the valent substituent include the substituents mentioned as preferable examples of R ₁ , R ₂ , R ₃ , R ₄ and V described above.

More preferably, lower alkyl groups (preferably substituted or unsubstituted ones having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-
Butyl, t-butyl, methoxyethyl, hydroxyethyl, hydroxymethyl, vinyl, allyl), carboxy group, alkoxy group (preferably substituted or unsubstituted one having 1 to 5 carbon atoms, for example, methoxy, ethoxy, methoxyethoxy, Hydroxyethoxy), an aralkyl group (preferably substituted or unsubstituted one having 7 to 12 carbon atoms, for example, benzyl, phenethyl, phenylpropyl), an aryl group (preferably substituted or unsubstituted 6 to 12 carbon atoms)
, Such as phenyl, 4-methylphenyl, 4-
Methoxyphenyl), a heterocyclic group (eg, 2-pyridyl), an alkylthio group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, eg, methylthio, ethylthio), an arylthio group (preferably substituted or unsubstituted carbon number) 6-12, for example, phenylthio), aryloxy group (preferably substituted or unsubstituted C6-C6)
12, an alkylamino group having 3 or more carbon atoms (eg, propylamino, butylamino), an arylamino group (eg, anilino), a halogen atom (eg, chlorine atom, bromine atom, fluorine atom) Or the following substituents.

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Here, L ₅ , L ₆ and L ₇ represent a linking group represented by an alkylene group (preferably having 1 to 5 carbon atoms, for example, methylene, propylene, 2-hydroxypropylene).

R ₂₉ and R ₃₀ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group (preferably substituted or unsubstituted carbon atom having 1 to 1 carbon atoms).
0, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, methoxyethyl, hydroxyethyl, allyl, propargyl), an aralkyl group (preferably substituted or unsubstituted carbon Those of numbers 7 to 12, such as benzyl, phenethyl,
Vinylbenzyl), an aryl group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms, for example, phenyl,
-Methylphenyl), or a heterocyclic group (eg, 2-pyridyl).

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by R ₂₄ may be unsubstituted or substituted. Preferably R ₁ , R ₂ , R ₃ , R ₄ and V
And the like.

More preferably, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom), a nitro group, a cyano group, a hydroxy group, an alkoxy group (eg, methoxy),
Aryl groups (eg, phenyl), acylamino groups (eg, propionylamino), alkoxycarbonylamino groups (eg, methoxycarbonylamino), ureido groups,
Amino group, heterocyclic group (eg, 2-pyridyl), acyl group (eg, acetyl), sulfamoyl group, sulfonamide group, thioureido group, carbamoyl group, alkylthio group (eg, methylthio), arylthio group (eg, phenylthio, heterocyclic thio group) (For example, 2-benzothiazolylthio), a carboxylic acid group, a sulfo group, or a salt thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group and amino group each include unsubstituted, N-alkyl-substituted and N-aryl-substituted ones.

[0169] Examples of aryl groups have phenyl group or substituted phenyl group, the above-mentioned R ₁ is as the substituent,
Substituents and the like mentioned as preferred examples of R ₂ , R ₃ , R ₄ and V can be mentioned.

The alkali metal atoms represented by X ₁ and X ₂ are, for example, a sodium atom and a potassium atom,
The ammonium group is, for example, tetramethylammonium or trimethylbenzylammonium. The blocking group is a group that can be cleaved under alkaline conditions.
For example, it represents acetyl, cyanoethyl, or methanesulfonylethyl.

Specific examples of the divalent linking group represented by L ₃ and L ₄ include the following linking groups or a combination thereof.

[0172]

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R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R
₃₇ , R ₃₈ , R ₃₉ and R ₄₀ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group (preferably substituted or unsubstituted one having 1 to 4 carbon atoms, for example, methyl, ethyl, n -Butyl, methoxyethyl, hydroxyethyl, allyl) or an aralkyl group (preferably substituted or unsubstituted one having 7 to 12 carbon atoms, for example, benzyl, phenethyl, phenylpropyl).

R ₂₅ and R ₂₈ are preferably the same as those described above for R ₂₄ .

As a heterocyclic group having Z ₇ as a ring-constituting atom, thiazoliums such as thiazolium, 4-methylthiazolium, benzothiazolium,
-Methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2
1-d] thiazolium}, oxazoliums {eg oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium {, imidazoliums} such as 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium,
1-ethyl-5,6-cyclolobenzimidazolium,
1-allyl-5-trifluoromethyl-6-chloro-benzimidazolium), selenazoliums {e.g., benzoselenazolium, 5-chlorobenzoselenazolium, 5
-Methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [1,2-d] selenazolium
And the like.

Particularly preferred are thiazoliums (for example,
Benzothiazolium, 5-chlorobenzothiazolium,
5-methoxybenzothiazolium, naphtho [1,2-
d] Thiazolium).

R ₂₆ and R ₂₇ are preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl,
Decyl, dodecyl, octadecyl) or a substituted alkyl group as a substituent, for example, a vinyl group, a carboxy group,
Sulfo group, cyano group, halogen atom (for example, fluorine, chlorine, bromine), hydroxy group, alkoxycarbonyl group having 1 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), carbon number 1 to 8 alkoxy groups (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), C6 to C10 monocyclic aryloxy groups (for example, phenoxy, p-tolyloxy), and C1 to C1
3 acyloxy groups (eg, acetyloxy, propionyloxy), C 1-8 acyl groups (eg, acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidi) Carbonyl), a sulfamoyl group (eg, sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl,
Piperidinosulfonyl), an alkyl group having 1 to 18 carbon atoms で substituted with an aryl group having 6 to 10 carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl). However, R ₂₆ is not a hydrogen atom.

More preferably, R ₂₆ is an unsubstituted alkyl group (for example, methyl or ethyl) or alkenyl group (for example, allyl group), and R ₂₇ is a hydrogen atom or an unsubstituted lower alkyl group (for example, methyl or ethyl). It is.

When M ₁ and m ₁ are required to neutralize the ionic charge of the compound represented by the general formula (Het-e), they represent the presence or absence of a cation or an anion. Included in the formula. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be specifically an inorganic or organic anion, such as a halogen anion (eg, fluoride, Chlorine ion, bromine ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion), 2,5-naphthalenedisulfonic acid imide, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, Acetate ion, trifluoromethane Sulfonic acid ions.

Preferred are ammonium ion, iodine ion, bromine ion and p-toluenesulfonic acid ion.

In the general formulas (Het-a) to (Het-e)
Each of the nitrogen-containing heterocycles represented has at least one
-(Q) k2- (Hy) are substituted. Its substitution position
The location is R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R_{twenty four}, R
_{twenty five}, R₂₆, Y₁, L_ThreeAnd Z ₇And so on.

In the general formula (III), Q represents a divalent linking group comprising an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom.

Preferably, an alkylene group having 1 to 8 carbon atoms (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group having 6 to 12 carbon atoms (eg, phenylene, naphthylene), Alkenylene group (eg, ethinylene, propenylene), amide group, ester group, sulfamide group, sulfonic ester group, ureido group, sulfonyl group, sulfinyl group,
Thioether group, ether group, carbonyl group, -N (R
₀ )-(R ₀ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.),
Divalent heterocyclic residue (for example, 6-chloro-1,3,5
-Triazine-2,4-diyl, pyrimidine-2,4-
Diyl, quinoxaline-2,3-diyl) and a divalent linking group having 4 to 20 carbon atoms, which is formed by combining one or more of these. More preferred are ureido, ester and amide groups.

In the general formula (III), k1 and k3
Is preferably 1 or 2. More preferably, k
1, k2 and k3 are all 1.

When k1 or k3 is 2 or more, Hy, He
t may be the same or different.

Among the compounds represented by the general formula (III) of the present invention, more preferred compounds are those represented by the following general formula (III)
-A), (III-B), (III-C), (III-
D) and (III-E).

[0187]

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Further, a particularly preferred compound in the present invention is represented by the following formula (III-F).

[0189]

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In the formula, Q _a has the same meaning as Q in formula (III). Z _b has the same meaning as Z _{1 in} formula (Hy-1).

R ₄₁ represents a monovalent substituent. R ₄₂ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ₄₃ and R ₄₄ each independently represent a hydrogen atom or a monovalent substituent.

N ₁ represents an integer of 0 to 4. n ₂ represents 0 or 1. n ₃ represents an integer of 1-6.

[0193] X ₁ has the same meaning as X ₁ in the general formula (Het-c). Y _1, L _3, p ₂ is Y _1, L of the general formula (Het-d)
₃ and p ₂ are synonymous.

[0194] R ₂₆ has the same meaning as R ₂₆ in formula (Het-e). When n ₁ and n ₃ are 2 or more, R ₄₁ and C
(R ₄₃ ) and (R ₄₄ ) are repeated but need not be identical.

More specifically, Qa is represented by the general formula (II)
The same thing as Q of I) is preferred, and more preferred is
It is a ureido group, an ester group or an amide group.

Z _b is preferably the same as Z _{1 in} formula (Hy-1), more preferably an unsubstituted tetramethylene group or pentamethylene group. R ₄₁ is preferably the same as R ₁₁ .

R ₄₂ is preferably the same as R ₁ , R ₂ , R ₃ and R _4, and is particularly preferably an unsubstituted alkyl group having 1 to 4 carbon atoms (eg, methyl and ethyl). R ₄₃ and R ₄₄ are preferably the same as R ₁₁ , particularly preferably a hydrogen atom.

N ₁ is preferably 0 or 1.
n ₂ is preferably 1. n ₃ is preferably 2
~ 4.

Next, typical examples of the compound used in the present invention will be shown, but it should not be construed that the invention is limited thereto.

[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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In the present invention, the compound represented by the general formula (III)
et. U.S. Pat. No. 3,266,897, Belgian Patent No. 671,402, JP-A-60-138548,
JP-A-59-68732, JP-A-59-123838
No., JP-B-58-9939, and JP-A-59-13795.
No. 1, JP-A-57-202531, JP-A-57-16
No. 4734, JP-A-57-14836, JP-A-57-14836.
No. 116340, U.S. Pat. No. 4,418,140, JP-A-58-95728, JP-A-55-79436,
OLS 2,205,029, OLS 1,962,60
5, JP-A-55-59463, JP-B-48-182.
No. 57, JP-B-53-28084, JP-A-53-48
No. 723, JP-B-59-52414, JP-A-58-2
No. 17928, JP-B-49-8334, U.S. Patent No. 3,598,602, U.S. Patent No. 887,009,
UK Patent 965,047, Belgium Patent 7378
09, U.S. Pat. No. 3,622,340,
-87322, JP-A-57-212142, JP-A-58-158631, JP-A-59-15240, U.S. Pat. No. 3,671,255, JP-B-48-34166.
No., JP-B-48-322112, JP-A-58-221
No. 839, JP-B-48-32367, JP-A-60-1
No. 30731, JP-A-60-122936, JP-A-6-122
No. 0-117240, U.S. Pat. No. 3,228,770,
JP-B-43-13496, JP-B-43-10256
No., JP-B-47-8725, JP-B-47-30206
No., JP-B-47-4417, JP-B-51-25340
No. 1,165,075, U.S. Pat.
No. 2,982, U.S. Pat. No. 1,472,845, JP-B-39-22067, JP-B-39-22068, U.S. Pat. No. 3,148,067, U.S. Pat.
No. 1, U.S. Pat. No. 3,909,268, JP-B-50-4
No. 0665, Japanese Patent Publication No. 39-2829, U.S. Pat.
48,066, JP-B-45-22190, U.S. Pat. No. 1,399,449, British Patent 1,287,284
No. 3,900,321, U.S. Pat.
5,391, U.S. Patent 3,910,792, British Patent 1,064,805, U.S. Patent 3,544,336
No. 4,003,746; British Patent 1,34
No. 4,525, British Patent No. 972,211, Japanese Patent Publication No. 43
-4136, U.S. Patent 3,140,178, French Patent 2,015,456, U.S. Patent 3,114,637
No., Belgian Patent No. 681,359, U.S. Pat. No. 3,22
0,839, British Patent 1,290,868, US Patent 3,137,578, US Patent 3,420,670
No. 2,759,908; U.S. Pat.
2,340, OLS2,501,261, DAS
No. 1,772,424, U.S. Pat. No. 3,157,509
No. 1, French Patent 1,351,234, US Patent 3,63
0,745, French Patent 2,005,204, German Patent 1,447,796, US Patent 3,915,710
No. JP-B-49-8334, British Patent 1,021,1
No. 99, UK Patent 919,061, Japanese Patent Publication No. 46-17
No. 513, U.S. Pat. No. 3,202,512, OLS2.
553,127, JP-A-50-104927, French Patent 1,467,510, U.S. Pat.
No. 6, US Pat. No. 3,503,936, US Pat.
No. 76,638, French patent 2,093,209, British patent 1,246,311, U.S. Pat.
No. 8, US Pat. No. 3,535,115, British Patent 1,1
No. 61,264, U.S. Pat. No. 3,841,878, U.S. Pat. No. 3,615,616, JP-A-48-39039.
No., UK Patent 1,249,077, JP-B-48-34
No. 166, US Pat. No. 3,671,255, British Patent 1
No. 459160, JP-A-50-6323, British Patent 1,402,819, OLS 2,031,314,
Research Disclosure 13651, U.S. Pat. No. 3,910,791, U.S. Pat. No. 3,954,478
No. 3,813,249; British Patent 1,38
7,654, JP-A-57-135945, JP-A-5-135
7-96331, JP-A-57-22234, JP-A-59-26731, OLS 2,217,153, British Patent 1,394,371, British Patent 1,308,7
77, British Patent 1,389,089, British Patent 1,
No. 347,544, German Patent 1,107,508, U.S. Pat. No. 3,386,831, British Patent 1,129,6
No. 23, JP-A-49-14120, JP-B-46-34
675, JP-A-50-43923, U.S. Pat.
42,481; British Patent 1,269,268; U.S. Patent 3,128,185; U.S. Patent 3,295,98.
No. 1, US Pat. No. 3,396,023, US Pat.
No. 95,827, JP-B-48-38418, JP-A-Showa 4
8-47335, JP-A-50-87028, U.S. Pat. No. 3,236,652, U.S. Pat. No. 3,443,951
No., UK Patent 1,065,669, US Patent 3,31
2,552, U.S. Patent 3,310,405, U.S. Patent 3,300,312, British Patent 952,162,
UK Patent 952,162, UK Patent 948,442
No., JP-A-49-120628, JP-B-48-353
No. 72, JP-B-47-5315, JP-B-39-187
06, JP-B-43-4941, JP-A-59-345
No. 30, etc., and can be synthesized with reference to these.

Hy in the general formula (III) of the present invention can be synthesized by various methods. For example, it can be synthesized by a method of alkylating hydrazine. Alkylation methods include substitution alkylation using alkyl halide and alkyl sulfonate, reductive alkylation using carbonyl compound and sodium cyanoborohydride, and hydrogenation after acylation. A reduction method using lithium aluminum and the like are known. For example, SRSandle
r), W. Karo, "Organic Functional Group Preparations (Orga
nic Fanctional Group Preparation) ", Volume 1, 14
Chapter, pages 434-465 (1968), Academic Press (Ac
ademic Press), ELClen
nan) etc.Journal of the American Chemical
Society (Journal of The American Chemical S
etc., Vol. 112, No. 13, page 5080 (1990), etc., and can be synthesized by referring to them.

For the bond formation reaction including the amide bond formation reaction and the ester bond formation reaction of the-(Q) k2- (Hy) moiety, a method known in organic chemistry can be used. That is, a method of linking Het to Hy, a method of linking Het to a Het synthesis raw material and an intermediate, and then synthesizing Het, and conversely, a method of linking the Hy synthesis raw material and an intermediate to the Het portion, and then connecting Hy.
Any method, such as a method of synthesizing, may be used. For the synthesis reactions for these linkages, see, for example, The Chemical Society of Japan, New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds, Vol. IV, Maruzen, Tokyo (1977), Yoshio Ogata, Organic Reaction Theory , Maruzen, Tokyo (1962) LFFieser
and M. Fieser, Advanced Organic Chemistry, Maruzen,
You can refer to books on many organic synthesis reactions, such as Tokyo (1962).

More specifically, Japanese Patent Application Laid-Open No. 7-135341
Can be synthesized by the method shown in Examples 1 and 2 of the above.

The compound represented by the general formula (III) of the present invention is preferably added to a green-sensitive emulsion layer, more preferably during the preparation of an emulsion. The compound represented by formula (III) of the present invention can be added to an emulsion layer other than the green-sensitive emulsion layer.

When it is added during the preparation of an emulsion, it can be added at any time during the process. Examples thereof include a step of forming silver halide grains, a step before the start of a desalting step, a step of desalting, Before the start of chemical ripening, a step of chemical ripening, a step before preparation of a finished emulsion, and the like can be mentioned. Also, it can be added in plural times during these steps.

The compound represented by formula (III) of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. In the case of dissolving in water, a compound whose solubility increases when the pH is increased or decreased may be dissolved by increasing or decreasing the pH, and then added.

The compound represented by the general formula (III) is
It is preferably used for the emulsion layer, but it may be added to the protective layer or the intermediate layer together with the emulsion layer and diffused during coating.

The compound of the formula (III) of the present invention may be added at any time before or after the sensitizing dye, and preferably from 1 × 10 ^{-9 to} 5 × 10 5 per mol of silver halide.
^-2 mol, more preferably 1 × 10 ^-8 to 2 × 10 ^-3 mol, is contained in the silver halide emulsion.

The following formulas (IV-1) and (IV-
The compound represented by 2) will be described in detail.

In the general formula (IV-1), R ₃₁ ,
As the substituent represented by R ₃₂ , R ₃₃ and R ₃₄ , an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 30 carbon atoms)
~ 20. For example, methyl, ethyl, iso-propyl. ), An aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms such as phenylmethyl), an alkenyl group (preferably having 2 to 20 carbon atoms, and more preferably having 2 to 1 carbon atoms).
0. For example, allyl. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10, for example, methoxy and ethoxy), and an aryl group (preferably having 6 to 20 carbon atoms).
30, more preferably 6 to 20), an acylamino group (preferably 2 to 30, more preferably 2 to 20; for example, acetylamino), a sulfonylamino group (preferably 1 to 30 carbon atoms, more preferably 1 to 30 carbon atoms) 20, for example, methanesulfonylamino; a ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, methylureide); an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2) To 20. For example, methoxycarbonylamino.), An aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20; for example, phenyloxycarbonylamino group), an aryloxy group (preferably having 6 to 6 carbon atoms). 3
0, more preferably 6-20. For example, phenyloxy. ), A sulfamoyl group (preferably having 0 to 3 carbon atoms)
0, more preferably 0-20. For example, methylsulfamoyl. ), Carbamoyl group (preferably having 1 to 3 carbon atoms)
0, more preferably 1-20. For example, carbamoyl, methylcarbamoyl. ), Mercapto group, alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. For example, methylthio, carboxymethylthio. ), An arylthio group (preferably having 6 to 30, more preferably 6 to 20; for example, phenylthio), a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms).
0. For example, methanesulfonyl. ), A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, methanesulfinyl), a hydroxy group, a halogen atom (for example, a chlorine atom, a bromine atom, and a fluorine atom), a cyano group, a sulfo group, and a carboxyl group Group, phosphono group, amino group (preferably having 0 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. For example, methylamino. ), An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 30 carbon atoms)
20. ), Acyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, for example, acetyl and benzoyl), and alkoxycarbonyl groups (preferably having 2 carbon atoms).
~ 30, more preferably 2-20. For example, methoxycarbonyl. ), An acyloxy group (preferably having 2 to 3 carbon atoms)
0, more preferably 2 to 20. For example, acetoxy. ),
Examples include a nitro group, a hydroxamic acid group, and a heterocyclic group (eg, pyridyl, furyl, thienyl). Further, these substituents may be further substituted.

Preferred examples of the substituent represented by R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group, an acylamino group, a sulfonylamino group, Ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group, halogen atom, sulfo group,
Carboxyl group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, particularly preferably alkyl group, halogen atom, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group , An aryloxycarbonylamino group.

Of the R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , preferably one or more and three or less are hydrogen atoms, more preferably two or more and three or less are hydrogen atoms. Particularly preferred is the case of three hydrogen atoms.

When R ₃₁ and R ₃₄ are simultaneously an alkyl group,
Substituents having exactly the same number of carbon atoms are not taken. For example, R
₃₁ = t-C ₈ H ₁₇ , R ₃₄ = n-C ₁₅ H ₃₁
At the same time, neither R ₃₁ nor R _{34 is} tC ₈ H ₁₇ .
When the substituents are of the same kind, the difference between the carbon numbers of the substituents of R ₃₁ and R ₃₄ is preferably 5 or more, more preferably 10 or more. R ₃₂ and R ₃₃ is the same as in the case of R ₃₁ and R _34.

Among the compounds represented by the general formula (IV-1), the compound represented by the general formula (IV-1-a) is preferable, and the compound represented by the general formula (IV-1-b) is more preferable. is there.

Formula (IV-1-a)

[0226]

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In the formula, R ₃₁ and R ₃₄ are represented by the formula (IV-
It has the same meaning as those of 1), and the preferred range is also the same.

Formula (IV-1-b)

[0229]

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In the formula, R ₃₁ has the same meaning as that in formula (IV-1), and the preferred range is also the same.

In the general formula (IV-2), R ₄₁ and R ₄₂
And the substituents represented by R ₄₃ include, for example, R ₃₁ , R
_32, the substituent represented by R ₃₃ and R ₃₄ can be exemplified substituent which may have.

Preferred examples of the substituent represented by R ₄₁ include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group, an acylamino group,
Sulfonylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group,
A halogen atom, a sulfo group, a carboxyl group, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, particularly preferably an alkyl group, a halogen atom,
An acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group.

Preferred examples of the substituent represented by R ₄₂ include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, and an alkylthio group. Group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group, hydroxy group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, and particularly preferably Is an alkyl group, an acylamino group,
A sulfonylamino group, a ureido group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group.

Preferred examples of the substituent represented by R ₄₃ include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group, an acylamino group,
Sulfonylamino group, ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylthio group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group,
It is a halogen atom, a sulfo group, a carboxyl group, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, or an aryloxycarbonylamino group, and particularly preferably an alkyl group.

Z represents a nonmetallic atom group necessary for forming a 4- to 6-membered ring. The nonmetallic atom is preferably a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, more preferably a carbon atom or an oxygen atom, and particularly preferably a carbon atom. Further, the preferred number of ring members is 5 or 6, more preferably a 6-membered ring. This is on the ring may have a substituent, and the substituent may be exemplified by those exemplified as the substituents represented by, for example, R _41. The substituent is preferably an alkyl group, an alkenyl group or an alkoxy group, and more preferably an alkyl group or an alkenyl group.
These substituents may further have a substituent.

Of the compounds represented by the general formula (IV-2), preferably a compound represented by the general formula (IV-2-a), more preferably a compound represented by the general formula (IV-2-b) is there.

Formula (IV-2-a)

[0238]

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In the formula, R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as those in formula (IV-2), and the preferred range is also the same. n represents 1 or 2. R ₄₄ and R
₄₅ represents an alkyl group, an alkenyl group, or an alkoxy group, respectively.

Formula (IV-2-b)

[0241]

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In the formula, R ₄₁ , R ₄₂ and R ₄₃ have the same meanings as those in formula (IV-2), and the preferred range is also the same. R _{44 represents} an alkyl group, an alkenyl group, or an alkoxy group.

N is preferably 2. R ₄₄ and R
_The alkyl group and alkenyl group represented by ₄₅ are straight-chain,
It may be branched or cyclic, and is preferably linear or branched. The preferred number of carbon atoms is 1 to 30, more preferably 1 to 20. Examples of the alkyl group include methyl, ethyl and iso-propyl, and examples of the alkenyl group include allyl.

In the alkoxy group represented by R ₄₄ and R ₄₅ , the alkyl portion may be linear, branched or cyclic, and R ₄₄ and R ₄₅ may form a ring like spirochromans. It preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. For example, methoxy and ethoxy can be mentioned.

Among the compounds represented by the general formula (IV-1-b), a compound represented by the following general formula (IV-1-c) is preferable.

Formula (IV-1-c)

[0247]

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As the substituent represented by R ⁵¹ , an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. Such as methyl, ethyl, iso- propyl, -C _{12
H 25, -C 14 H 29,} -C 16 H 33, -C 18 H 37. Particularly preferably, it has 16 to 20 carbon atoms. ), An aralkyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, for example, phenylmethyl), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20, for example, allyl), and aryl. A group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20; for example, phenyl), an acylamino group (preferably having 2 to 30 carbon atoms, and more preferably having 2 to 30 carbon atoms).
20. For example, acetylamino. ), A sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. For example, methylsulfonylamino. ), An aminosulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, methylaminosulfonylamino), and a ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, methylureide) ), An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms,
More preferably, 2 to 20. For example, methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 30, more preferably 7 to 20; for example, phenyloxycarbonylamino), a sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably having 0 to 20 carbon atoms). For example, methylsulfamoyl.), A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom)
~ 20. For example, carbamoyl, methylcarbamoyl. ), An amino group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20; for example, amino and methylamino), and an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, methoxy, Ethoxy),
An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20; for example, phenyloxy); An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1
~ 20. For example, methylthio, carboxymethylthio),
An arylthio group (preferably 1 to 30 carbon atoms, more preferably 1 to 20; for example, phenylthio), a hydrazino group (preferably 1 to 30 carbon atoms, more preferably 1 to 2 carbon atoms)
0. Examples thereof include methyl hydrazino), an azo group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20; for example, phenylazo), a heterocyclic group (eg, pyridyl, furyl, and thienyl). Further, these substituents may be further substituted. When the substituent represented by R ⁵¹ further has an alkyl group or an alkenyl group as a substituent, the substituent may be linear, branched, or cyclic, and is preferably linear or branched. More preferably, it is linear.

Preferred as the substituent represented by R ⁵¹ are an alkyl group, an aryl group, an acylamino group, an ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group and an amino group, more preferably an alkyl group, An aryl group and an amino group, most preferably an alkyl group.

In the following, formulas (IV-1) and (IV-
Specific examples of the compound represented by 2) are shown below, but the invention is not limited thereto.

[0251]

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[0252]

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[0253]

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[0254]

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[0255]

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[0256]

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[0257]

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[0258]

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[0259]

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[0260]

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[0261]

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[0262]

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[0263]

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The compound represented by the general formula (IV-1) is
For example, U.S. Pat. Nos. 2,728,559 and 2,549,118.
No. 2732300, Journal of America Chemical Society 111, 20, 198
9 years, 7932 (Journal of American Chemical Soci
ety, 111, 20, 1989, 7932), Synthesis, 12, 199.
5 years, 1549 pages (Synthesis, 12, 1995, 1549), QJPh
arm, Pharmacol., 17,1944,325, Chem.Pharm, Bull., 14,19
66, 1052, and Chem. Pharm, Bull., 16, 1968, 853.

The compounds represented by the general formula (IV-2) are described, for example, in US Pat.
2, 2411967, 2681371, J. Amer.Che
m.Soc., 65,1943,1276, J.Amer.Chem.Soc., 65,1943,128
1, J. Amer. Chem. Soc., 63, 1941, 1887, J. Amer. Chem. So
c., 107, 24, 1985, 7053, Helv. Chim. Acta., 21, 1938, 939,
Helv. Chim. Acta., 28, 1945, 438, Chem. Ber., 71, 1938, 263
7, J. Org. Chem., 4, 1939, 311, J. Org. Chem., 6, 1941, 22
9, J. Chem. Soc., 1938,1382, Helv. Chim. Acta., 21, 1931,
1234, Tetrahedron Lett., 33, 26, 1992, 3795, J. Chem. So
c. Perkin. Trans. 1, 1981, 1437, Synthesis, 6, 1995, 693 and the like.

The formulas (IV-1) and (IV-) of the present invention
The compound represented by 2) is preferably added to the green-sensitive emulsion layer. In addition to the green-sensitive emulsion layer, it can be added to an adjacent layer or another layer.

The formulas (IV-1) and (IV-) of the present invention
The compound represented by 2) is preferably added as an emulsified dispersion by a known dispersion method. In the case of emulsifying and dispersing, additives commonly used in the photographic industry such as a dye-forming coupler or a high-boiling organic solvent can coexist. It can also be added as a microcrystal dispersion.

The formulas (IV-1) and (IV-) of the present invention
The addition amount of the compound represented by 2) is 5 × 10 ^-4 to 1 mol, more preferably 1 × 10 ^{-3 to} 5 × 10 ^-1 mol, per mol of silver halide in the added emulsion layer.

The formulas (IV-1) and (IV-) of the present invention
Two or more compounds represented by 2) may be used. When two or more kinds are used, they may be added to the same layer or may be added to separate layers.

In the combination of the compounds of the general formulas (III) and (IV-1) or (IV-2), the compounds represented by the general formulas (III-F) and (IV-1-c) Are preferred.

The compounds represented by formulas (AI) to (A-III) will be described in more detail.

The alkyl group in the present invention is a linear, branched or cyclic alkyl group, which may have a substituent.

In the general formula (AI), R _a1 represents an alkyl group (preferably an alkyl group having 1 to 13 carbon atoms, for example, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl) , Decyl, dodecyl, hexadecyl, benzyl), an alkenyl group (preferably an alkenyl group having 2 to 14 carbon atoms, for example, allyl, 2-butenyl, isopropenyl, oleyl, vinyl), an aryl group (preferably having 6 to 14 carbon atoms)
For example, phenyl, naphthyl). R
_a2 represents a hydrogen atom or a group represented by R _a1 . R _a3 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (eg, methyl, i-butyl, cyclohexyl)
Or an alkenyl group (eg, vinyl, i-propenyl)
Represents The total number of carbon atoms contained in which R _a1, R _a2 and a R _a3 is 20 or less, more preferably 12 or less. Examples of the substituent of R _a1 and R _a1 include a hydroxy group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group,
Alkylthio, arylthio, amino, acylamino, sulfonamide, alkylamino, arylamino, carbamoyl, sulfamoyl, sulfo, carboxyl, halogen, cyano, nitro, sulfonyl, acyl , An alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a hydroxyamino group, a heterocyclic group and the like.

R _a1 and R _a3 or R _a2 and R _a3 may be bonded to each other to form a 5- to 7-membered ring.

In the general formula (A-II), X is a heterocyclic group (a group forming a 5- to 7-membered heterocyclic ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom and a phosphorus atom as a ring-constituting atom) And the bonding position of the heterocycle (1
Is a carbon atom, for example, pyridine-2
-Yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, thiazolyl, oxazolyl, 1,
2,4-triazol-3-yl, benzimidazol-2-yl, benzothiazolyl, benzoxazolyl,
Thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-ylmorpholinyl,
Represents phosphinolin-2-yl. R _b1 has the general formula (A
-Represents an alkyl group, an alkenyl group or an aryl group having the same meaning as _{Ra1 in} I).

In the general formula (A-III), Y is -N = C
-A non-metallic atom group necessary to form a 5-membered ring together with (for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl, 3H -Indol-2-yl). Y is a group of nonmetallic atoms necessary for forming a 6-membered ring together with the -N = C- group, and -N
= The terminal of Y bonded to the carbon atom of the C- group is -N (R _c1 )-, -C
One group selected from the group consisting of (R _c2 ) (R _c3 )-, -C (R _c4 ) =, -O- and -S- (a carbon atom of -N = C- on the left side of each group; To combine). R _{c1 to} R _c4 may be the same or different and each represents a hydrogen atom or a substituent (for example, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, Halogen atom). Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl,
1,3,5-triazin-5-yl, 6H-1,2,5
-Thiadiazin-6-yl.

In formula (A-II), R _b1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-IV).

[0278]

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[0279] In formula (A-IV), R _b1 has the same meaning as R _b1 in formula (A-II), X ₁ is the formula (A-II
It is the same as Y in I).

Of the compounds represented by formulas (AI) to (A-III), those having a total carbon number of 20 or less are preferable, and those having 12 or less are more preferable.

Of the compounds represented by the general formulas (AI) to (A-III), those represented by the general formulas (AI) and (A-II) are preferable, and more preferable are those represented by the general formula (AI) A-
I) and (A-IV), and represented by the general formula (A
Those represented by -I) are most preferred.

The compounds represented by the following general formulas (AI) to (A-
Specific examples of the compound represented by III) will be given below, but the invention is not limited thereto.

[0283]

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[0284]

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[0285]

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[0286]

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[0287]

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[0288]

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[0289]

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[0290]

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[0291]

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[0292]

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[0293]

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[0294]

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[0295]

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[0296]

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[0297]

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[0298]

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These compounds used in the present invention include:
J.Org.Chem., 27, 4054 ('62), J.Amer.Chem.Soc., 7
3, 2981 ('51), JP-B-49-10692, or the like, or a method analogous thereto.

In the present invention, the compounds represented by the general formulas (AI) to (A)
The compound represented by -III) may be added by dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof, or may be added by emulsification and dispersion.
In the case of dissolving in water, if the solubility is increased by increasing or decreasing the pH, it may be dissolved by increasing or decreasing the pH, and then added, or a surfactant may be allowed to coexist.

In the present invention, the compounds represented by the general formulas (AI) to (A)
The compound represented by -III) is preferably added at the time of preparing an emulsion. When it is added during the preparation of the emulsion, it can be added at any time during the process, and examples thereof include a silver halide grain forming process, before the start of the desalting process, a desalting process, and a chemical ripening process. Before the start, a step of chemical ripening, a step before preparation of a finished emulsion and the like can be mentioned. Also, it can be added in plural times during these steps. Preferably, it is added before, during or after chemical sensitization. Further, it can be added before coating the coating solution, or can be added to an adjacent layer or another layer at the time of coating and diffused into the emulsion layer. Further, those dispersed and dissolved in an emulsion can be used by mixing with the emulsion.

In the present invention, the compounds represented by the general formulas (AI) to (A)
Two or more of the compounds represented by -III) may be used in combination. When two types are used in combination, it is preferable to select from the compounds represented by formula (AI). When two or more types are used, they may be added to the same layer or may be added to separate layers.

In the present invention, formulas (AI) to (A)
Although the preferred addition amount of the compound represented by -III) largely depends on the above-described addition method and the kind of the compound to be added, 1 × 10 ⁻⁶ per mol of the photosensitive silver halide.
Mol to 5 × 10 ⁻² mol, preferably 1 × 10 ⁻⁵ mol to 5 mol
× 10 ^-3 mol is more preferred.

In the present invention, a compound represented by the general formula (III), a compound selected from the group consisting of compounds represented by the general formulas (IV-1) and (IV-2), and a compound represented by the general formula (A Compounds selected from the group consisting of compounds represented by -I) to (A-III) can be added to the same layer or to different layers, respectively.

Next, the compound represented by formula (V) will be described.

In the formula (V), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₂₄ represents a hydrogen atom , An alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, NR ₂₅ R ₂₆
The stands, L ₂₁ represents -CO- or -SO ₂ - represents, n represents 0 or 1. R ₂₅ is a hydrogen atom, a hydroxyl group,
Amino group, alkyl group, alkenyl group, alkynyl group,
R ₂₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group;

In R ₂₁ , R ₂₂ and R ₂₃ , the alkyl group, alkenyl group and alkynyl group preferably have 1 to 30 carbon atoms, and particularly have 1 to 10 carbon atoms.
A branched or cyclic alkyl group, an alkenyl group having 2 to 10 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group, and aralkyl group include methyl, ethyl, propyl, cyclopropyl, allyl, propargyl, and benzyl. R ₂₁ , R
₂₂ and aryl groups in R ₂₃ is preferably be of 6 to 30 carbon atoms, in particular monocyclic or condensed aryl group having 6 to 12 carbon atoms, such as phenyl, naphthyl and the like. In R ₂₁ , R ₂₂ and R ₂₃ , the heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocycle, for example, pyridyl, imidazolyl, quinolyl, benzimidazolyl,
Pyrimidyl, pyrazolyl, isoquinolyl, thiazolyl,
Thienyl, furyl, benzothiazolyl and the like.

In R ₂₄ , an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group are R ₂₁ , R
₂₂ and R ₂₃ as synonymous. In NR ₂₅ R ₂₆ of R ₂₄ , the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group of R ₂₅ and R _{26 have} the same meaning as R ₂₁ , R ₂₂ and R ₂₃ .

In the formula (V), R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ ,
Each group represented by R ₂₅ and R ₂₆ may be substituted, and examples of the substituent include the following.

A halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, an ammonium group (for example, trimethylammonio), a phosphonio group,
Sulfo group, sulfino group, carboxy group, phosphono group,
Hydroxy group, mercapto group, hydrazino group, alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl), alkenyl group (for example, allyl, 2-
Butenyl, 3-pentenyl), alkynyl group (for example,
Propargyl, 3-pentynyl), aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg, pyridyl, furyl, imidazolyl, piperidyl, morpholino), alkoxy Groups (eg, methoxy,
Ethoxy, butyloxy), aryloxy group (eg, phenoxy, 2-naphthyloxy), alkylthio group (eg, methylthio, ethylthio), arylthio group (eg, phenylthio), amino group (eg, unsubstituted amino group, methylamino , Dimethylamino, ethylamino, alinino), acyl group (eg, acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), carbamoyl group (Eg, unsubstituted carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl), acyloxy group (eg, acetoxy, benzoyloxy), acylamino group ( For example, acetylamino, benzoylamino), an alkoxycarbonylamino group (for example, methoxycarbonylamino), an aryloxycarbonylamino group (for example, phenoxycarbonylamino), a ureido group (for example, unsubstituted ureido, N-methylureido, N -Phenylureido), an alkylsulfonylamino group (eg, methylsulfonylamino),
Arylsulfonylamino group (for example, phenylsulfonylamino), alkylsulfonyloxy group (for example,
Methylsulfonyloxy), arylsulfonyloxy group (eg, phenylsulfonyloxy), alkylsulfonyl group (eg, mesyl), arylsulfonyl group (eg, tosyl), alkoxysulfonyl group (eg, methoxysulfonyl), aryloxysulfonyl group ( For example, phenoxysulfonyl), a sulfamoyl group (eg, unsubstituted sulfamoyl, N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), an alkylsulfinyl group (eg, methylsulfinyl), Arylsulfinyl group (eg, phenylsulfinyl), alkoxysulfinyl group (eg, methoxysulfinyl), aryloxysulfinyl group (eg, phenoxysulfinyl), phosphoric amide (E.g., N, N-diethyl acid amide) and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (V), R ₂₁ and R ₂₂ , R ₂₁
And R ₂₃ , R ₂₃ and R ₂₄ , or R ₂₄ and R ₂₂ may combine to form a ring.

In the general formula (V), when n is 0, R ₂₁ , R ₂₂ and R ₂₃ are preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2
To an alkynyl group, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group, wherein R ₂₄ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2 carbon atoms. To 10, an alkynyl group, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group. More preferably, R ₂₁ , R ₂₂ and R ₂₃ are an alkyl group having 1 to 10 carbon atoms, An alkenyl group, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group, and R ₂₄ is a hydrogen atom.
When n is 1, R ₂₁ , R ₂₂ and R ₂₃ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 2 to 1 carbon atoms.
0 alkenyl group, alkynyl group having 2 to 10 carbon atoms,
An aryl group having 6 to 10 carbon atoms, a nitrogen-containing heterocyclic group, L ₂₁ is —CO—, R ₂₄ is a hydrogen atom,
To 10 alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, 6 to 1 carbon atoms
0 is an aryl group, a nitrogen-containing heterocyclic group, NR ₂₅ R ₂₆ , wherein R ₂₅ is a hydrogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, R ₂₆ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group, which is an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group. , With 6 to 1 carbon atoms
0 is an aryl group or a nitrogen-containing heterocyclic group, more preferably R ₂₁ is an aryl group having 6 to 10 carbon atoms,
R ₂₂ and R ₂₃ are hydrogen atoms, L ₂₁ is —CO—,
R ₂₄ is NR ₂₅ R ₂₆ , where R ₂₅ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group,
Alkynyl group.

The specific compounds represented by formula (V) are shown below, but the invention is not restricted thereto.

[0314]

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[0315]

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[0316]

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[0317]

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[0318]

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The compound represented by formula (V) can be easily obtained as a commercially available drug or a compound synthesized from a commercially available drug by a known method. The method of synthesizing the general formula (V) is described in Journal of American Chemical Society (J. Am. Chem. So
c.), 72, 2762 (1950), Organic Synthesis, 2, 395
Page, New Experimental Chemistry Courses 14-2 and 14-3 (19
77) It can be easily synthesized by the method described in Maruzen or the like or a method analogous thereto.

The compound represented by the formula (V) is preferably added to an adjacent layer or another layer of an emulsion layer before or at the time of coating the coating solution and diffused into the emulsion layer. It can also be added before, during or after chemical sensitization during the preparation of the emulsion.

The preferred addition amount largely depends on the above-mentioned addition method and the kind of compound to be added, but is generally from 5 × 10 ^-6 mol to 0.05 mol, more preferably 1 × 10 ^-6 mol, per mol of light-sensitive silver halide. ^-5 mol to 0.005 mol is used. If the amount is larger than the above amount, adverse effects such as an increase in fog are caused, which is not preferable.

The compound represented by formula (V) is preferably dissolved in a water-soluble solvent and added. The pH may be lowered or raised by an acid or a base, or a surfactant may be present. Further, it may be added by dissolving in an organic solvent having a high boiling point as an emulsified dispersion, or may be added as a microcrystal dispersion by a known dispersion method.

The compounds of the general formula (V) may be used in combination of two or more. When two or more kinds are used in combination, they may be added to the same layer or may be added to separate layers.

In the present invention, tabular grains preferably have dislocation lines. Dislocation lines of tabular grains are, for example, JFHamilt
on, Phot.Sci.Eng., 11, 57 (1967) and T. Shiozawa, J. Soc. Pho
It can be observed by a direct method using a transmission electron microscope at low temperature as described in t. Sci. Japan, 35, 213 (1972). That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the higher the thickness of the particles, the more difficult it is for an electron beam to pass therethrough.
The use of an electron microscope (200 kV or more for particles having a thickness of μm) enables more clear observation. From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably 10 or more per grain on average. More preferably, an average of 20 per particle
More than a book. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more.

A dislocation line can be introduced, for example, in the vicinity of the outer periphery of a tabular grain. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but may not be a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. Conversely, it is also possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

A dislocation line may be formed over a region including the center of two parallel main planes of a tabular grain. When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be approximately (211) crystallographically when viewed from a direction perpendicular to the main plane, but may be in the (110) direction or In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. In some cases, the dislocation lines are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer circumference). is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation line may be limited to an outer periphery, a main plane, or a local position, or may be formed by combining these.
That is, they may be present simultaneously on the outer periphery and on the main plane.

In the present invention, dislocation lines are most preferably formed by adding a sparingly soluble silver halide emulsion to the above-mentioned silver bromide, silver chlorobromide, silver chloroiodobromide or silver iodobromide tabular grain emulsion. Introduce. Here, the sparingly soluble silver halide emulsion means that it is more sparingly soluble than a tabular grain emulsion in a halogen composition, and is preferably a silver iodide fine grain emulsion.

In the present invention, dislocation lines are preferably introduced by rapidly adding a silver iodide fine grain emulsion to the above-described tabular grain emulsion. This step is essentially composed of two steps: a step of rapidly adding a silver iodide fine grain emulsion to a tabular grain emulsion, and a step of growing silver bromide or silver iodobromide to introduce dislocation lines. is there. These two steps may be performed completely separately, or each may be performed at the same time with repetition. It is preferably performed separately. The step of rapidly adding a silver iodide fine grain emulsion to the first tabular grain emulsion will be described.

To rapidly add a silver iodide fine grain emulsion,
Preferably, the silver iodide fine grain emulsion is added within 10 minutes. More preferably, it is added within 7 minutes. These conditions can vary depending on the temperature of the system to be added, pBr, pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type and the concentration, etc., but the shorter is preferable as described above. It is preferable that the addition of an aqueous solution of silver salt such as silver nitrate is not substantially performed during the addition.
The temperature of the system at the time of addition is preferably from 40 ° C to 90 ° C,
A temperature of 50 ° C or higher and 80 ° C or lower is particularly preferred. There is no particular limitation on pBr when the silver iodide fine grain emulsion is added.

The silver iodide fine grain emulsion only needs to be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. Silver iodide has β-form and γ-form in its crystal structure.
And α-isomer or α-isomer-like structure as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before addition as described in US Pat. No. 5,400,479, or may be any of those which have been subjected to a usual washing step. In the present invention, those which have been subjected to the ordinary washing step are preferably used. Used. The silver iodide fine grain emulsion can be easily formed by the method described in the aforementioned US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the grains are formed with a constant pI value during grain formation, is preferred. Where pI is the logarithm of the reciprocal of the I ^- ion concentration of the system. There are no particular restrictions on the temperature, pI, pH, type and concentration of protective colloid such as gelatin, the presence / absence, type and concentration of a silver halide solvent, but the size of the grains is 0.1 μm or less, more preferably 0.1 μm or less. 08 μm
The following are convenient for the present invention. Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when the content is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing the silver iodide fine grains on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of the carbon replica method. This is because the observation error by the carbon replica method becomes large due to the small particle size. Particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined using the same projected area circle diameter. The most effective silver iodide fine grains in the present invention have a grain size of not more than 0.07 μm and not more than 0.02 μm.
As described above, the variation coefficient of the particle size distribution is 18% or less.

The silver iodide fine grain emulsion is preferably subjected to ordinary water washing, concentration adjustment of a protective colloid agent such as pH, pI, gelatin and the like and adjustment of the concentration of contained silver iodide as described in US Pat. Will be pH 5
It is preferably at least 7 and at most 7. The pI value is preferably set to a pI value at which the solubility of silver iodide is at a minimum or a pI value higher than that value. As the protective colloid, ordinary gelatin having an average molecular weight of about 100,000 is preferably used.
Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It is sometimes convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver content in terms of silver atoms per kg of the emulsion is preferably 10 g or more and 100 g or more.
g or less. More preferably, it is 20 g or more and 80 g or less. The amount of gelatin and / or silver is preferably selected to a value suitable for rapidly adding a silver iodide fine grain emulsion.

The addition amount of the silver iodide fine grain emulsion is preferably from 1 mol% to 10 mol% in terms of silver amount relative to the tabular grain emulsion. Most preferably, it is 2 mol% or more and 7 mol% or less. By selecting this addition amount, dislocation lines are preferably introduced, and the effect of the invention becomes remarkable. The silver iodide fine grain emulsion is usually dissolved and added beforehand, but at the time of addition, it is necessary to sufficiently increase the stirring efficiency of the system. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of foam during stirring. Specifically, an antifoaming agent described in Examples of US Pat. No. 5,275,929 is used.

After rapidly adding a silver iodide fine grain emulsion to the tabular grain emulsion, silver bromide or silver iodobromide is grown to introduce dislocation lines. The growth of silver bromide or silver iodobromide may be started before or simultaneously with the addition of the silver iodide fine grain emulsion, but preferably after the addition of the silver iodide fine grain emulsion, the growth of silver bromide or silver iodobromide is started. Start growing. The time from the addition of the silver iodide fine grain emulsion to the start of the growth of silver bromide or silver iodobromide is preferably within 10 minutes and 1 second or more. More preferably, it is 3 seconds or more within 5 minutes. More preferably, it is within one minute. This time interval is preferably as short as possible, but preferably before the start of silver bromide or silver iodobromide growth.

The growth after the addition of the silver iodide fine grain emulsion is preferably silver bromide. In the case of silver iodobromide, the silver iodide content is preferably within 3 mol% with respect to the layer. The amount of silver in the layer grown after the addition of the silver iodide fine grain emulsion is preferably 5 when the total silver content of the finished tabular grain emulsion is 100.
Not less than 50. Most preferably, it is 10 or more and 30 or less. Temperature, pH and pBr for forming this layer
Is not particularly limited, but the temperature is 40 ° C. or more and 90 ° C. or less,
Is usually 2 or more and 9 or less. More preferably 50
C. to 80.degree. C. and a pH of 3 to 7 are used.
With respect to pBr, in the present invention, it is preferable that pBr at the end of the formation of the layer be higher than pBr at the beginning of the formation of the layer. Preferably, the pBr at the beginning of the formation of the layer is 2.9 or less, and the pBr at the end of the formation of the layer is 1.7 or more. More preferably, the pBr at the beginning of the formation of the layer is 2.5 or less, and the pBr at the end of the formation of the layer is 1.9 or more. Most preferably, pBr in the initial stage of the formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less. The dislocation lines in the present invention are preferably introduced by the above method.

The silver halide grains used in the present invention are subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization and noble metal sensitization in any step of the production process of a silver halide emulsion. be able to. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion used in the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose, but the case where at least one type of chemical sensitization nucleus is formed near the surface is preferable.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and is described by TH (James), The Photographic Process, 4th Edition, Macmillan Company. Published, 197
7 years, (THJames, The Theory of the Photographic P
rocess, 4th ed, Macmillan, 1977), pages 67-76, and can also be performed using active gelatin, Research Disclosure Volume 120, 1
April 974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3; 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in US Pat.
Sulfur, selenium at 5-8 and a temperature of 30-80 ° C.
It can be tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li
₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757;
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

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

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

Selenium sensitization is a preferable sensitizing method for the emulsion used in the present invention. In selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium and selenoureas (for example, N,
Selenium compounds such as N-dimethylselenourea, N, N-diethylselenourea), selenoketones, and selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

In the present invention, the thiocyanate is preferably added before the addition of the above-mentioned spectral sensitizing dye and chemical sensitizer. Preferably, it is added after particle formation, more preferably after the end of the desalting step. Preferably, the thiocyanate is added even during chemical sensitization, so that the thiocyanate is added twice or more. As the thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate and the like are used.

Usually, it is added after being dissolved in an aqueous solution or a water-soluble solvent. The addition amount is 1 × per mol of silver halide.
10 ⁻⁵ mol to 1 × 10 ⁻² mol, more preferably 5 × 1
It is from 0 ^-5 mol to 5 × 10 ^-3 mol.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion used in the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. .

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
16, P30 (1966), and enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin may also be used.

The emulsion used in the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The washing temperature can be selected according to the purpose,
It is preferable to select in the range of 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. P at the time of washing
Ag can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

In preparing the emulsion used in the present invention, for example,
During particle formation, desalting, chemical sensitization,
The presence of a salt of the compound is preferred depending on the purpose. particle
In the case of doping, there is modification of the particle surface at the time of particle formation
Or when used as a chemical sensitizer, after chemical formation
It is preferred to add it before completion. Dope the whole grain
And only the core part of the particle, or only the shell part,
Or only in the epitaxal part, or in the base particle
The method of doping only can also be selected. Mg, Ca, Sr, B
a, Al, Sc, Y, LaCr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, Bi or the like can be used. These gold
The genus is ammonium salt, acetate, nitrate, sulfate, phosphoric acid
Particle form such as salt, hydroxide or 6-coordinate complex, 4-coordinate complex
It can be added in the form of a salt that can be dissolved during formation.
You. For example, CdBr_Two, CdCl_Two, Cd (NO_Three)_Two, Pb
(NO_Three)_Two, Pb (CH_ThreeCOO)_Two, K _Three[Fe (CN)₆],
(NH_Four)_Four[Fe (CN)₆], K_ThreeIrCl₆, (NH_Four)_ThreeR
hCl₆, K_FourRu (CN)₆And so on. Coordination compound
Halo, aquo, cyano, cyanate,
Thiocyanate, nitrosyl, thionitrosyl, oki
It can be selected from SO and carbonyl. They are
Only one metal compound may be used, but two or three metal compounds may be used.
More than one species may be used in combination.

The metal compound is preferably added by dissolving a suitable solvent such as water or methanol or acetone in a solvent.
In order to stabilize the solution, an aqueous solution of hydrogen halide (eg, HC
1, HBr, etc.) or alkali halides (eg KC
1, NaCl, KBr, NaBr, etc.). If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. Further, it can be added to a water-soluble silver salt (eg, AgNO ₃ ) or a water-soluble alkali halide (eg, NaCl, KBr, KI) and added continuously during silver halide grain formation. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

The production process of the emulsion used in the present invention is as follows.
It is preferable to use an oxidizing agent for silver therein. However,
It is necessary that the hole-capturing silver nuclei on the grain surface remain to some extent.
You. The oxidizing agent for silver is silver ion that acts on metallic silver
A compound having an action of converting into Especially haloge
By-products during formation of silver halide grains and chemical sensitization
Tiny silver particles that are converted to silver ions
The compound is effective. The silver ions generated here are halo
Forms silver salts that are hardly soluble in water, such as silver gemide, silver sulfide, and silver selenide.
Or form a silver salt easily soluble in water such as silver nitrate.
You may. Oxidizing agents for silver, whether inorganic or
It may be a machine. As inorganic oxidants, ozone,
Hydrogen peroxide and its adducts (eg, NaBO_Two・ H_Two
O_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_FourP_TwoO₇・
2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO _Two・ 2H_TwoO), Peru
Xylate (eg, K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP
_TwoO₈), Peroxy complex compounds (eg, K_Two[Ti
(O_Two) C_TwoO_Four] 3H_TwoO, 4K_TwoSO_Four・ Ti (O_Two) O
H ・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two) (C_TwoH_Four)_Two・ 6
H_TwoO), permanganate (eg, KMnO)_Four),Black
Oxalates (eg, K_TwoCr_TwoO₇), Such as oxyacid salts, iodine
Halogen elements such as bromine and bromine;
Potassium iodate) salts of high valent metals (eg hexa
Potassium ferric cyano) and thiosulfonates
There is.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T). , Chloramine B).

The preferred oxidizing agent used in the present invention is
Ozone, hydrogen peroxide and its adducts, halogen elements,
It is an inorganic oxidizer for thiosulfonates and an organic oxidizer for quinones.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,9
No. 47 and JP-B No. 52-28660 can be used. Japanese Patent Application No. Sho 6
There is a compound described in JP-A-2-47225 (JP-A-63-212932). Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978).
), Item 18716 (November 1979) and Item 308119 (December 1989), and the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer page 649 right column 4 Brightener 24 page 998 right 5 Antifoggant 24-25 page 649 right column 998 right-1000 right and stabilizer 6 light absorber, page 25-26 page 649 right column 1003 Left to 1003 right Filter dye 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardening agent 26 page 651 left column 1004 right to 1005 left 10 Binder 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 650 right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 Static page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left.

The emulsion used in the present invention and techniques such as layer arrangement which can be used for photographic light-sensitive materials using the emulsion, silver halide emulsion, dye-forming coupler, DI
For functional couplers such as R couplers, various additives, etc., and development processing, see EP 056596A1.
(Published October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

[0362] 1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36 to 40, 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34, 7. Emulsion production method: page 62, lines 35 to 40, Silver halide grain size distribution: page 62, 41 to 42
Row, 9. Tabular grains: page 62, lines 43 to 46,10. 10. Internal structure of particle: page 62, lines 47 to 53, Emulsion latent image forming type: page 62, line 54 to page 63, 5
Line, 12. 12. Physical ripening / chemical ripening of emulsion: p. 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14 to 31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49 to 50; Photographic additives: Research Disclosure (R
D) Item 17643 (December 1978), Item 18
716 (November 1979) and Item 307105
(November, 1989), and each item and a description place related thereto are shown below.

Type of Additive RD17643 RD18716 RD307105 1 Chemical sensitizer page 23, page 648, right column, page 866 2 Sensitivity enhancer page 648, right column 3 Spectral sensitizer, page 23-24, page 648, right column 866-868 Color sensitizer ~ page 649 right column 4 whitening agent page 24 page 647 right column page 868 5 antifoggant, page 24-25 page 649 right column 868-870 page stabilizer 6 light absorber, page 25-26 649 Page right column 873 page Filter dye, ~ 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left column to right column 872 8 Dye image stabilizer 25 page 650 left column 872 9 Hardener 26 Page 651 Left column 874 to 875 10 Binder Page 26 651 Left column 873 to 874 11 Plasticizer, lubricant 27 Page 650 Right column 876 Page 12 Coating aid, 26-27 Page 650 Right column 875- Page 876 surfactant 13 static page 27 page 650 right column inhibitors 876-877 inhibitor 14 matting agent pages 878-879.

[0364] 18. Formaldehyde scavenger: 6
Page 4, lines 54-57; 20. Mercapto antifoggant: page 65, lines 1 and 2, Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, lines 7-10, 22. General color couplers: p. 65, lines 11 to 13, 23. 23. Yellow, magenta and cyan couplers: p. 65, lines 14-25; Polymer coupler: page 65, lines 26 to 28, 25. Diffusible dye-forming couplers: p. 65, lines 29 to 31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49 to 53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 35. Back layer: page 67, lines 3 to 8, 36. Overall development processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12 to 30, 38. 39. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12, 41. Developing time: page 68, lines 13 to 15, 42. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32 to 40, 44. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70, lines 34-38, 48. Use for film with lens: page 70, lines 39-41.

Also, a bleaching solution described in EP-A-602600 containing a 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid, a ferric salt such as ferric nitrate, and a persulfate is also used. It can be used preferably. In the use of this bleaching solution, it is preferable to interpose a stopping step and a washing step between the color developing step and the bleaching step,
It is preferable to use an organic acid such as acetic acid, succinic acid, and maleic acid for the stop solution. In addition, this bleaching solution contains p
Organic acids such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid, etc.
It is preferable to contain it in the range of 2 mol / L.

[0366]

Examples of the present invention will be described below. However, it is not limited to this embodiment.

Example 1 In this example, the green photosensitive silver halide emulsion was prepared by increasing the surface area by increasing the aspect ratio of the silver halide tabular grains and increasing the amount of the spectral sensitizing dye added. When the sensitivity is increased by increasing the amount of light absorption, there is a problem that a remarkable fog occurs when the photosensitive material containing the silver halide emulsion is exposed to a gas generated by combustion (for example, exhaust gas of an automobile). At the same time, it is shown that this problem is remarkably solved by the means disclosed in the present invention.

Gelatins 1-4 used as dispersion media in the following emulsion preparations are gelatins having the following attributes.

Gelatin-1: Normal alkali-treated ossein gelatin made from bovine bone. -NH ₂ in the gelatin
No chemical modification of the group.

Gelatin-2: In an aqueous solution of gelatin-1,
A gelatin obtained by adding phthalic anhydride at 50 ° C. and a pH of 9.0 to cause a chemical reaction, removing residual phthalic acid, and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-3: In an aqueous solution of gelatin-1,
Gelatin obtained by adding trimellitic anhydride under conditions of 50 ° C. and pH 9.0 to cause a chemical reaction, and then removing remaining trimellitic acid and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-4: The enzyme was acted on gelatin-1 to reduce the molecular weight to an average molecular weight of 15,000, then the enzyme was inactivated and the gelatin was dried without any chemical modification of the -NH ₂ group.

After the above gelatin-1 to 4 were all deionized, the pH of a 5% aqueous solution at 35 ° C. was 6.
Adjustment was made so as to be zero.

(Preparation of Emulsion A-1) 1.0 g of KBr
1300 mL of an aqueous solution containing 1.1 g of the above gelatin-4
Was kept at 35 ° C. and stirred. (Preparation of 1st liquid) Ag-
38 mL of 1 aqueous solution (containing 4.9 g of AgNO ₃ in 100 mL) and an X-1 aqueous solution (KBr in 100 mL)
And 5.2 mL of an aqueous G-1 solution (containing 8.0 g of the above gelatin-4 in 100 mL) were added by a triple jet method at a constant flow rate over 30 seconds (addition). 1). Then, KBr
6.5 g was added and the temperature was raised to 75 ° C. After heating 1
After a 2-minute aging step, a G-2 aqueous solution (100 mL
Containing 12.7 g of the above gelatin-1) 300
mL and then add 4,5-dihydroxy-1,3
Disodium disulfonate monohydrate (2.1 g) and thiourea dioxide (0.002 g) were sequentially added at intervals of 1 minute.

Next, an Ag-2 aqueous solution (100 mL of A
Gno ₃ which contained 22.1 g) and 157 mL, X-2
Aqueous solution (containing 15.5 g of KBr in 100 mL)
Was added by the double jet method over 28 minutes. At this time, the final flow rate of addition of the Ag-2 aqueous solution is 3.
The flow rate was accelerated so as to be four times, and the aqueous solution of X-2 was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 7.52 (addition 2). Next, an aqueous solution of Ag-3 (containing 32.0 g of AgNO ₃ in 100 mL) 3
29 mL and X-3 aqueous solution (2 mL of KBr in 100 mL)
1.5 g, containing 1.2 g of KI) by the double jet method over 53 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 7.52. This was done to keep (addition 3). Further, 156 mL of an Ag-4 aqueous solution (containing 32.0 g of AgNO ₃ in 100 mL) and X-
Four aqueous solutions (containing 22.4 g of KBr in 100 mL) were added by the double jet method over 17 minutes.
At this time, the Ag-4 aqueous solution was added at a constant flow rate, and X
-3 aqueous solution was added to the pA of the bulk emulsion solution in the reaction vessel.
g was maintained at 7.52 (addition 4).

Thereafter, 0.0025 g of sodium benzenethiosulfonate and 125 mL of a G-3 aqueous solution (containing 12.0 g of the above-mentioned gelatin-1 in 100 mL)
Were added sequentially at one minute intervals. Then KB
of the bulk emulsion solution in the reaction vessel.
After adjusting the Ag to 9.00, the AgI fine grain emulsion (100
12. AgI fine particles having an average particle size of 0.047 μm in g.
03.9 g) and 2 minutes later,
249 mL of the Ag-4 aqueous solution and X-4 aqueous solution were added by the double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 9 minutes, and the X-4 aqueous solution was added only for the first 3.3 minutes so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.00, and the remaining was added. Was added for 5.7 minutes, so that the pAg of the bulk emulsion solution in the reaction vessel finally reached 8.4 (addition 5). Thereafter, desalting is performed by a normal flocculation method, and then water, NaOH, and the above-mentioned gelatin-1 are added while stirring.
It adjusted so that it might become pH6.4 and pAg8.6 at 56 degreeC.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
The average value of the aspect ratio is 3.1 and 60% of the total projected area of the grains has an aspect ratio of 2.5 or more and 4.5 or less;
tabular silver halide grains having an average gI content of 3.94 mol% and a parallel main plane of (111) plane;
The AgI content on the surface of the silver halide grains measured by XPS was 2.1 mol%.

Subsequently, the following sensitizing dye Exs-1, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were successively added and optimally subjected to chemical sensitization. Mercapto compound MER-
Chemical sensitization was terminated by adding a total of 3.6 × 10 ^-4 mol of 1 and MER-2 at a ratio of 4: 1 per mol of silver halide. Emulsion A-1 was optimally chemically sensitized when the amount of Exs-1 added was 4.26 × 10 ^-4 mol per mol of silver halide.

[0379]

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[0380]

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(Preparation of Emulsion A-4) Emulsion A-4 was prepared by changing the preparation conditions of Emulsion A-1 described above as follows.

The amount of the AgI fine grain emulsion added two minutes before (addition 5) is 133.0 g. The addition time of the Ag-4 aqueous solution of (Addition 5) is reduced to 8.37 minutes without changing the flow rate, and the addition time of the X-4 aqueous solution is reduced to 2.67 minutes.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
The average value of the aspect ratio is 3.1 and 60% of the total projected area of the grains has an aspect ratio of 2.5 or more and 4.5 or less;
tabular silver halide grains having an average gI content of 5.94 mol% and a parallel main plane of (111) plane;
The AgI content on the surface of the silver halide grains measured by XPS was 6.7 mol%.

In the emulsion A-4, the sensitizing dye Exs-
1 in an amount of 4.26 × 10 per mol of silver halide
Optimal chemical sensitization at ^-4 mol.

(Preparation of Emulsion B-1) Emulsion B-1 was prepared by changing the preparation conditions of Emulsion A-1 described above as follows.

The gelatin in the G-2 aqueous solution added after a ripening step of 12 minutes after the temperature was raised to 75 ° C. was changed from the above-mentioned gelatin-1 to gelatin-2. The addition of the Ag-2 aqueous solution of (Addition 2)
The addition flow rate was changed so that the addition time was 22.4 minutes while keeping the volume at 57 mL. The flow rate acceleration is such that the final flow rate is 3.4 times the initial flow rate. The addition of the X-2 aqueous solution is performed so that the pAg of the bulk emulsion solution in the reaction vessel is kept at 7.83.

The addition of the Ag-3 aqueous solution of (Addition 3)
The addition time was 42.4 with the addition amount kept at 329 mL.
Change the addition flow rate so that it becomes minutes. The flow rate acceleration is such that the final flow rate is 1.6 times the initial flow rate. Also, X-3
The addition of the aqueous solution depends on the pAg of the bulk emulsion solution in the reaction vessel.
To keep 7.83.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
The average value of the aspect ratio is 5.9 and 60% of the total projected area of the grains has an aspect ratio of 5.0 or more and 8.0 or less;
tabular silver halide grains having an average gI content of 3.94 mol% and a parallel main plane of (111) plane;
The AgI content on the surface of the silver halide grains measured by XPS was 2.4 mol%.

In the emulsion B-1, the sensitizing dye Exs-
1 in an amount of 5.37 × 10 per mol of silver halide
Optimal chemical sensitization at ^-4 mol.

(Preparation of Emulsion B-4) Emulsion B-4 was prepared by changing the above preparation conditions of Emulsion B-1 as follows.

The addition amount of the AgI fine grain emulsion added 2 minutes before (addition 5) is 133.0 g. The addition time of the Ag-4 aqueous solution of (Addition 5) is reduced to 8.37 minutes without changing the flow rate, and the addition time of the X-4 aqueous solution is reduced to 2.67 minutes.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
The average aspect ratio is 5.9, and 60% of the total projected area of the grains has an aspect ratio of 5.0 or more and 8.0 or less,
The average value of the AgI content is 5.94 mol%, the tabular silver halide grains have a parallel main plane of (111) plane, and the AgI of the surface of the silver halide grains measured by XPS is measured.
The content was 7.5 mol%.

In the emulsion B-4, the sensitizing dye Exs-
1 in an amount of 5.37 × 10 per mol of silver halide
Optimal chemical sensitization at ^-4 mol.

(Preparation of Emulsion C-1) Emulsion C-1 was prepared by changing the preparation conditions of Emulsion A-1 described above as follows.

The gelatin in the aqueous G-2 solution added after a ripening step of 12 minutes after the temperature was raised at 75 ° C. was changed from the above-mentioned gelatin-1 to gelatin-3. The addition of the Ag-2 aqueous solution of (Addition 2)
The addition flow rate was changed so that the addition time was 14 minutes while keeping the volume at 57 mL. In the flow rate acceleration, the final flow rate is 3.
4 times. In addition, the addition of the X-2 aqueous solution
The pAg of the bulk emulsion solution in the reaction vessel is maintained at 8.30.

(Addition 3)
The addition flow rate was changed so that the addition time was 27 minutes while keeping the addition liquid amount at 329 mL. The flow rate acceleration is such that the final flow rate is 1.6 times the initial flow rate. The addition of the X-3 aqueous solution is performed so that the pAg of the bulk emulsion solution in the reaction vessel is maintained at 8.30.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
A parallel principal plane having an average aspect ratio of 12.5, 60% of the total projected area of the grains having an aspect ratio of 9.0 to 15.0, an average AgI content of 3.94 mol%, and a parallel principal plane. Consists of tabular silver halide grains having a (111) plane, and Ag on the surface of the silver halide grains measured by XPS.
The I content was 2.6 mol%.

In the emulsion C-1, the sensitizing dye Exs-
1 in an amount of 7.48 × 10 per mol of silver halide.
Optimal chemical sensitization at ^-4 mol.

(Preparation of Emulsion C-2) Emulsion C-2 was prepared by changing the preparation conditions of Emulsion C-1 described above as follows.

The added amount of the AgI fine grain emulsion added 2 minutes before (addition 5) is 93.7 g. The addition time of the Ag-4 aqueous solution of (Addition 5) is reduced to 8.80 minutes without changing the flow rate, and the addition time of the X-4 aqueous solution is reduced to 3.10 minutes.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
Parallel main plane having an average aspect ratio of 12.5, 60% of the total projected area of the grains having an aspect ratio of 9.0 or more and 15.0 or less, and an average value of AgI content of 4.61 mol%. Consists of tabular silver halide grains having a (111) plane, and Ag on the surface of the silver halide grains measured by XPS.
The I content was 4.4 mol%.

The emulsion C-2 used the sensitizing dye Exs-
1 in an amount of 7.48 × 10 per mol of silver halide.
Optimal chemical sensitization at ^-4 mol.

(Preparation of Emulsion C-3) Emulsion C-3 was prepared by changing the preparation conditions of Emulsion C-1 described above as follows.

The amount of the AgI fine grain emulsion added two minutes before (addition 5) was 113.2 g. The addition time of the Ag-4 aqueous solution of (Addition 5) is reduced to 8.58 minutes without changing the flow rate, and the addition time of the X-4 aqueous solution is reduced to 2.88 minutes.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
A parallel principal plane having an average aspect ratio of 12.5, 60% of the total projected area of the grains having an aspect ratio of 9.0 or more and 15.0 or less, and an average AgI content of 5.27 mol%. Consists of tabular silver halide grains having a (111) plane, and Ag on the surface of the silver halide grains measured by XPS.
The I content was 6.1 mol%.

In the emulsion C-3, the sensitizing dye Exs-
1 in an amount of 7.48 × 10 per mol of silver halide.
Optimal chemical sensitization at ^-4 mol.

(Preparation of Emulsion C-4) Emulsion C-4 was prepared by changing the preparation conditions of Emulsion C-1 described above as follows. The addition amount of the AgI fine grain emulsion added 2 minutes before (addition 5) is 133.0 g. The addition time of the Ag-4 aqueous solution of (Addition 5) is reduced to 8.37 minutes without changing the flow rate, and the addition time of the X-4 aqueous solution is reduced to 2.67 minutes.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
Parallel main plane having an average aspect ratio of 12.5, 60% of the total projected area of the grains having an aspect ratio of 9.0 or more and 15.0 or less, and an average value of AgI content of 5.94 mol%. Consists of tabular silver halide grains having a (111) plane, and Ag on the surface of the silver halide grains measured by XPS.
The I content was 8.0 mol%.

In the emulsion C-4, the sensitizing dye Exs-
1 in an amount of 7.48 × 10 per mol of silver halide.
Optimal chemical sensitization at ^-4 mol.

(Preparation of Emulsion C-5) Emulsion C-5 was prepared by changing the preparation conditions of Emulsion C-2 described above as follows.

Immediately before the completion of the chemical sensitization step (immediately before the addition of the water-soluble mercapto compounds MER-1 and MER-2), a step of adding 2.10 × 10 ^{-4 of} sodium sulfite per mol of silver halide was carried out. Add.

The obtained emulsion had a sphere equivalent diameter of 0.99 μm,
The average aspect ratio is 12.5, 60% of the total projected area of the grains has an aspect ratio of 9.0 or more and 15.0 or less, and the average value of AgI content is 4.61 mol. Ag111 on the surface of the silver halide grains, which is composed of tabular silver halide grains of the (111) plane and measured by XPS
The content was 4.4 mol%.

In the emulsion C-5, the sensitizing dye Exs-
1 in an amount of 7.48 × 10 per mol of silver halide.
Optimal chemical sensitization at ^-4 mol.

Emulsions A-1, A-4, B-1, B-
4. When C-1 to C-5 were observed at a liquid nitrogen temperature using a transmission electron microscope of 400 kV, it was found that at least 10 dislocation lines existed in the fringe portion of the tabular grain in any grain. all right.

The emulsions A-1, A-4 and B-
1, B-4, C-1 to C-5 were 4,5-dihydroxy-1,
Reduction sensitization has been achieved by the addition of disodium 3-disulfonate monohydrate and thiourea dioxide.

Further, the emulsions A-1, A-4 and B-
1, B-4, and C-1 to C-5 have wavelengths at which the spectral sensitivity is maximized by adding the sensitizing dye Exs-1 and performing spectral sensitization in the chemical sensitization step in the above emulsion preparation. Is 55
It is a green photosensitive silver halide emulsion having 0 mn.

The above emulsions A-1, A-4, B-1, B-4 and C-1 were coated on a cellulose triacetate film support provided with an undercoat layer under the coating conditions shown in Table 1 below. C-
5 was applied.

[0418]

[Table 1]

By changing the amount of the emulsion to be coated, the amount of sodium sulfite to be added to the silver halide emulsion layer, and the amount of the compound I-2 of the formula (I) to be added to the protective layer, Samples 1-1 to 1-1 were changed. 1-26 was prepared.

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge with a gelatin filter SC-50 (a long-wavelength light transmission filter having a cutoff wavelength of 500 nm) manufactured by Fuji Film Co., Ltd. The photographic performance was evaluated by measuring the density in the above.

The degree of fogging generated by exposing the coated sample to gas generated by combustion (in this embodiment, exhaust gas from a gasoline-powered vehicle) was evaluated by the following method.

As fuel, regular gasoline manufactured by Showa Shell Sekiyu KK was installed, and E manufactured by Nissan Motor Co., Ltd. was used.
-In S14, the motor was stopped in an idling state (motor rotation speed 1000 rpm), and the gas discharged from the exhaust pipe outlet was directly collected at 25 ° C.
1-atm and a relative humidity of 60% were adjusted to be unexposed in the space filled with the adjusted gas.
1-1 to 26 were left for 5 days. Thereafter, the above-described exposure and development processes are performed, and the density of the fog portion is measured with a green filter in the same manner as described above, and the density increase width relative to the density of the fog portion when not exposed to the exhaust gas from the E-S14 is calculated. Were determined and their values were compared relatively.

Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., processing was performed by the method described below (until the cumulative replenishment amount of the liquid became three times the mother liquid tank capacity).

(Processing Method) Process Processing Time Processing Temperature Replenishment Color Developing 2 min 45 sec 38 ° C. 45 mL Bleaching 1 min 00 sec 38 ° C. 20 mL Bleaching solution overflowed into bleach-fix tank Bleach-fix 3 min 15 sec 38 30 ° C water washing (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Water washing (2) 1 minute 00 seconds 35 ° C 30mL Stable 40 seconds 38 ° C 20mL Drying 1 minute 15 seconds 55 ° C * The replenishment amount is 35 mm width / 1.1 m length (corresponding to 24 Ex. 1 line) Next, the composition of the processing liquid is described.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodine 1.5 mg potassium hydroxide-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water and add 1.0 L 1.0 L pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.10.

(Bleaching solution) Common to tank solution and replenishing solution (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 mL water to make 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 6.3 .

(Bleach-fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Aqueous ammonium thiosulfate (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0L 1.0L pH (adjusted with ammonia water and acetic acid) 7.2 7.3.

(Washing solution) Common tank water and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) The mixture was passed through a mixed-bed column packed with to treat the calcium and magnesium ion concentrations at 3 mg / L or less, followed by addition of 20 mg / L of sodium isocyanurate dichloride and 0.15 g / L of sodium sulfate. The pH of this solution is 6.5
〜7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to make 1.0 L pH 8.5.

The results of evaluation by the above method are shown in Table 2 below. The sensitivity was represented by the relative value of the reciprocal of the exposure required to reach the fog density plus the density of 0.2 (the sensitivity of sample 1-1 was taken as 100).

[0431]

[Table 2]

[0432]

[Table 3]

The following matters are clear from the results in Table 2. One is that the sensitivity can be increased by increasing the aspect ratio of the silver halide tabular grains of the green-sensitive silver halide emulsion and increasing the amount of the spectral sensitizing dye added per mole of silver halide. On the other hand, there is a problem that the fogging that occurs when the vehicle is exposed to the exhaust gas of a vehicle is significantly increased. The other is that
Constituent elements of the present invention, that is, the AgI content on the surface of the silver halide grains measured by XPS is 5 mol% or less, and the light-sensitive material contains sulfite ions.
It can be remarkably reduced by including the compound of the general formula (I) in the light-sensitive material.

[0434] Any one of the above constitutional requirements
Even if only one of the components is missing, the above-described effect is significantly reduced, which indicates that the effect of the present invention is specifically exhibited when all of the above-mentioned components are satisfied.

In the above embodiment, the gas generated by the combustion used for the evaluation was the exhaust gas collected from another gasoline-powered vehicle, the gas discharged from the oil hot air heater, or during the combustion. In the case where the gas was collected near the oil stove, the same result as the result of the above example was obtained.

Example 2 Silver halide emulsions DG, Ha, Hb, Ia, Ib, and JR were prepared by the following production methods.

(Production Method of Emulsion D) A phthalated low molecular weight gelatin having a phthalation ratio of 97% and a molecular weight of 15,000, 31.7.
g, 32.2 g of KBr and 42.2 L of an aqueous solution at 35 ° C.
And stirred vigorously. 1583 mL of an aqueous solution containing 316.7 g of AgNO ₃ , 221.5 g of KBr, and 1583 m of an aqueous solution containing 52.7 g of gelatin-4 of Example 1.
L was added over 1 minute by the double jet method. Immediately after the addition was completed, 52.8 g of KBr was added, 2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 29 Br of KBr were added.
2,581 mL of an aqueous solution containing 1.1 g was added over 2 minutes by the double jet method. Immediately after the addition is completed, KBr,
44.8 g were added. Thereafter, the temperature was raised to 40 ° C. and the product was aged. After ripening, 923 g of gelatin-2 of Example 1
And 79.2 g of KBr were added, and AgNO ₃ , 5103
15947 mL of an aqueous solution containing g and an aqueous KBr solution were added over 10 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.90.
After washing with water, gelatin-1 of Example 1 was added thereto to adjust pH, 5.
7, pAg, 8.8, the weight in terms of silver per kg of emulsion, 131.8 g, and the weight of gelatin, 64.1 g, were prepared as a seed emulsion. 46 g of gelatin-2 of Example 1, KBr
1211 mL of an aqueous solution containing 1.7 g was maintained at 75 ° C. and stirred vigorously. After adding 9.9 g of the seed emulsion described above, modified silicone oil (L760, manufactured by Nippon Unicar Co., Ltd.)
0.3 g of 2) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by a double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and an aqueous KBr solution. The flow rate was accelerated as described above and added over 6 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.15. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 105.6 g of AgNO ₃ , 32
8 mL and the aqueous KBr solution were added by a double jet method over a period of 56 minutes by accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 27 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.60. Was. AgNO ₃
And 121.3 mL of an aqueous solution containing 45.6 g of an aqueous solution of KBr were added over 22 minutes by the double jet method. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60. The temperature was raised to 82 ° C., KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 8.80, and then 6.33 g of the aforementioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the end of the addition, 66.4 g of AgNO ₃
206.2 mL of the contained aqueous solution was added over 16 minutes.
During the initial 5 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.80 with an aqueous KBr solution. After washing with water, gelatin-1 of Example 1 was added, and the pH was adjusted to 5.8 at 40 ° C.
The pAg was adjusted to 8.7. After adding the compound ExA-1, the temperature was raised to 60 ° C. Sensitizing dyes Exs-2 and E
After addition of xs-3, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of the chemical sensitization, compound ExA-2 and compound ExA-3 were added. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are selected from the range of 10 ^-1 to 10 ^-8 mol per mol of silver halide.

[0438]

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[0439]

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[0440]

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[0441]

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(Preparation of Emulsion E) Gelatin-4 of Example 1
Aqueous solution containing 0.96 g of KBr and 0.9 g of KBr
The mL was kept at 40 ° C. and stirred vigorously. AgNO ₃ ,
37.5 mL of an aqueous solution containing 1.49 g and 1.0 mL of KBr
37.5 mL of an aqueous solution containing 5 g was 30
Added over seconds. After adding 1.2 g of KBr, 7
The temperature was raised to 5 ° C. and ripened. After ripening, 35 g of gelatin-3 of Example 1 was added to adjust the pH to 7. 6 mg of thiourea dioxide were added. 116 mL of an aqueous solution containing 29 g of AgNO ₃ and an aqueous KBr solution were added by double jet method at an accelerated flow rate such that the final flow rate was three times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.15. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over a period of 30 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D had a silver iodide content of 15.8 m.
ol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.85. 96.5 mL of an aqueous solution containing 24.1 g of AgNO ₃
And an aqueous KBr solution were added over 3 minutes by the double jet method. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.85. Sodium ethylthiosulfonate 2
After adding 6 mg, the temperature was lowered to 55 ° C., an aqueous KBr solution was added, and the pAg of the bulk emulsion solution in the reaction vessel was increased to 9.8.
Adjusted to zero. 8.5 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the addition, AgNO ₃
Was added over 5 minutes. At this time, an aqueous KBr solution was used so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.75. The emulsion was washed with water in almost the same manner as in Emulsion D and chemically sensitized.

(Preparation of Emulsion F) Gelatin-2 of Example 1
Aqueous solution containing 1.02 g of KBr and 0.9 g of KBr
L was kept at 35 ° C. and stirred vigorously. AgNO ₃ , 4.
An aqueous solution containing 47 g, 42 mL, an aqueous solution containing KBr and 3.16 g, 42 mL, were added by a double jet method over 9 seconds. After adding 2.6 g of KBr, the temperature was raised to 63 ° C. to ripen. After ripening, 4 parts of gelatin-3 of Example 1 were added.
1.2 g and 18.5 g of NaCl were added. After adjusting the pH to 7.2, dimethylamine borane, 8 mg, was added. 203 mL of aqueous solution containing 26 g of AgNO ₃
And an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.65. Ag
440.6 mL of an aqueous solution containing 110.2 g of NO ₃ and K
The Br aqueous solution was added over a period of 24 minutes by double jet method with the flow rate accelerated so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was simultaneously added at an accelerated flow rate such that the silver iodide content became 2.3 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was 8.50. Kept. After addition of 10.7 mL of a 1N aqueous solution of potassium thiocyanate, AgNO ₃ , 2
153.5 mL of an aqueous solution containing 4.1 g and an aqueous KBr solution were added by a double jet method over 2 minutes and 30 seconds. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.05. The aqueous KBr solution was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.25. AgI mentioned above
6.4 g of the fine grain emulsion was added in terms of KI weight. Immediately after the addition, 404 m of an aqueous solution containing 57 g of AgNO ₃
L was added over 45 minutes. At this time, an aqueous KBr solution was used so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.65. The emulsion was washed with water in almost the same manner as in Emulsion D and chemically sensitized.

(Preparation of Emulsion G) In the preparation of Emulsion F, the amount of AgNO ₃ added during nucleation was changed to 2.3 times. Then, 404 mL of an aqueous solution containing 57 g of the final AgNO ₃
Was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 6.85 with an aqueous KBr solution. Other than that, it was prepared almost in the same manner as Emulsion F.

(Preparation of Emulsion Ha) Emulsion C- of Example 1
In the preparation of Compound 3 prior to chemical sensitization, compound ExA
-1 is added, and the sensitizing dye added at the beginning of chemical sensitization is Exs-1 and Exs-
4 and Exs-5. Other than that, it was prepared almost in the same manner as Emulsion C-3. The amount of each sensitizing dye used was Exs-
1 was 5.50 × 10 ^-4 mol, Exs-4 was 1.30 × 1
0 ^-4 mol, Exs-5 is 4.65 × 10 ^-5 mol.

[0446]

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(Preparation of Emulsion Hb) Emulsion C- of Example 1
In the preparation of compound 1, prior to chemical sensitization, compound ExA
-1 was added, and the sensitizing dye added at the beginning of the chemical sensitization was changed to the combination of Exs-1, Exs-4 and Exs-5 described above. Other than that, it was prepared in substantially the same manner as in the emulsion C-1. The amount of each sensitizing dye used is the same as that of the emulsion Ha.

(Production Method of Emulsion Ia) An aqueous solution 12 containing 0.75 g of gelatin-4 of Example 1 and 0.9 g of KBr
00 mL was kept at 39 ° C., the pH was adjusted to 1.8 and stirred vigorously. An aqueous solution containing 1.85 g of AgNO ₃ and 1.
An aqueous KBr solution containing 5 mol% of KI was added over 16 seconds by a double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After the ripening, 20 g of gelatin-2 of Example 1 was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. A
288 mL of an aqueous solution containing gNO ₃ and 27.4 g and KBr
The aqueous solution was added by the double jet method over 53 minutes.
At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was increased to 9.4.
It was kept at zero. After adding 2.5 g of KBr, AgNO
_{3. An} aqueous solution containing 87.7 g and an aqueous KBr solution were added over 63 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the above AgI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 10.5 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.50. AgN
132 mL of an aqueous solution containing 41.8 g of O ₃ and an aqueous KBr solution were added over 25 minutes by the double jet method. The pAg of the bulk emulsion solution in the reaction vessel at the end of the addition is 8.1.
The addition of the aqueous KBr solution was adjusted to be 5. The pH was adjusted to 7.3 and 1 mg of thiourea dioxide was added.
Add KBr and add pAg of bulk emulsion solution in reaction vessel
Was adjusted to 9.50, and the above AgI fine grain emulsion was adjusted to K
8.78 g in terms of I weight was added. Immediately after the addition, 609 mL of an aqueous solution containing 63.3 g of AgNO _{3 was} added to 10
Added over minutes. During the initial 6 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50 with an aqueous KBr solution. After washing with water, gelatin-1 of Example 1 was added and
The pH was adjusted to 6.5, pAg, and 8.2 at 0 ° C. Emulsion H
Chemical sensitization was performed in almost the same manner as in -a. The amount of the sensitizing dye used was such that Exs-1 was 1.0 per mole of silver halide.
8 × 10 ⁻³ mol, Exs-4 is 2.56 × 10 ⁻⁴ mol,
Exs-5 is 9.16 × 10 ^-5 mol.

(Preparation of Emulsion Ib) In the preparation of Emulsion Ia, the amount of the AgI fine grain emulsion added immediately before the addition of 609 mL of the final aqueous solution containing AgNO ₃ was changed to K.
The amount of AgNO ₃ contained in 609 mL of the aqueous solution containing AgNO ₃ was 6.73 g in terms of I weight, and the amount of AgNO ₃ was 6
Changed to 6.4 g. Other than that, it was prepared almost in the same manner as the emulsion Ia.

(Preparation of Emulsion J) Gelatin-4 of Example 1
0.70 g, KBr, 0.9 g, KI, 0.175
g, modified silicone oil 0.2 used in the preparation of Emulsion D
g of an aqueous solution containing 1200 g was maintained at 33 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. 1.8 g of AgNO ₃
And an aqueous KBr solution containing 3.2 mol% of KI were added by a double jet method over 9 seconds. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 62 ° C. and ripened. After ripening, 2 parts of gelatin-3 of Example 1 were added.
7.8 g were added. After adjusting the pH to 6.3, KB
r, 2.9 g were added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes by the double jet method. At this time, the aqueous solution of gelatin-4, the aqueous solution of AgNO _{3, and the} aqueous solution of KI of Example 1 were mixed in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570, immediately before the addition, to prepare. The AgI fine grain emulsion having a grain size of 0.008 μm was added at the same time so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.
It was kept at 15. After adding 2.6 g of KBr, AgN
An aqueous solution containing 87.7 g of O ₃ and an aqueous KBr solution were added by a double jet method over a period of 49 minutes while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing just before the addition was accelerated simultaneously so that the silver iodide content became 7.9 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was increased to 9.3.
It was kept at zero. After adding 1 mg of thiourea dioxide, A
Gno _3, an aqueous solution containing 41.8 g 132 mL of KBr
The aqueous solution was added by the double jet method over 20 minutes.
The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 7.90.
After the temperature was raised to 78 ° C. and the pH was adjusted to 9.1, KBr was added to increase the pAg of the bulk emulsion solution in the reaction vessel to 8.7.
It was set to 0. The AgI fine grain emulsion used in the preparation of Emulsion D was added in an amount of 5.73 g in terms of KI weight. Immediately after the addition, 321 mL of an aqueous solution containing 66.4 g of AgNO _{3 was} added to 4 parts of the solution.
Added over minutes. During the first two minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.70 with an aqueous KBr solution. It was washed with water and chemically sensitized almost in the same manner as the emulsion Ha.
The amount of the sensitizing dye used was 1.25 × 10 ⁻³ mol for Exs-1, 2.85 × 10 ⁻⁴ mol for Exs- ⁴ , and 3.29 for Exs-5 per mol of silver halide. × 10 ^-5
Is a mole.

(Preparation of Emulsion K) Gelatin-1 of Example 1
And an aqueous solution containing 17.8 g, KBr, 6.2 g, KI and 0.46 g was kept at 45 ° C. and stirred vigorously. AgN
An aqueous solution containing 11.85 g of O ₃ and an aqueous solution containing 3.8 g of KBr were added by a double jet method over 45 seconds. After the temperature was raised to 63 ° C, gelatin-1 of Example 1 was added to 24.
1 g was added and the mixture was aged. After aging, AgNO ₃ , 13
An aqueous solution containing 3.4 g and an aqueous KBr solution were added by a double jet method over 20 minutes so that the final flow rate was 2.6 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60. Ten minutes after the start of the addition, 0.1 mg of K ₂ IrCl ₆ was added. NaCl 7
g of an aqueous solution containing 45.6 g of AgNO ₃ and K
The aqueous Br solution was added by the double jet method over 12 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 6.90. Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of the addition. KB
After adding 14.4 g of r, A used in the preparation of emulsion D
6.3 g of the gI fine grain emulsion was added in terms of KI weight. Immediately after the addition was completed, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 11 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was
Was maintained at 6.90. Washed with water in substantially the same manner as for emulsion Ha,
Chemical sensitization. The amount of the sensitizing dye used was such that Exs-1 was 5.79 × 10 ⁻⁴ mol per mol of silver halide,
1.32 × 10 ⁻⁴ mol of Exs- ⁴ and 1.30 mol of Exs-5.
52 × 10 ^-5 mol.

(Preparation of Emulsion L) Emulsion K was prepared in substantially the same manner except that the temperature during nucleation was changed to 35 ° C. The amount of the sensitizing dye used was 1 silver halide.
9.66 × 10 ⁻⁴ mol of Exs-1 per mol, Ex
2.20 × 10 ^-4 mol for s-4, 2.54 for Exs-5
× 10 ^-5 mol.

(Preparation of Emulsion M) Gelatin-4 of Example 1
Aqueous solution 1200 containing 0.75 g of KBr and 0.9 g of KBr
The mL was kept at 39 ° C., the pH was adjusted to 1.8 and stirred vigorously. An aqueous solution containing 0.34 g of AgNO ₃ and 1.5 mo
1% KBr aqueous solution containing 1% KI by double jet method
Added over 6 seconds. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After completion of the ripening, 20 g of gelatin-2 of Example 1 was added. pH 5.
After adjusting to 9, KBr, 2.9 g was added. After adding 3 mg of thiourea dioxide, AgNO ₃ , 28.8 was added.
288 mL of an aqueous solution containing g and a KBr aqueous solution were added by a double jet method over 58 minutes. At this time, the silver iodide content of the AgI fine grain emulsion having a grain size of 0.03 μm was 4.1.
mol%, and the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.40. KBr,
After the addition of 2.5 g, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method at a rate accelerated to a final flow rate 1.2 times the initial flow rate over a period of 69 minutes. At this time, the above AgI fine grain emulsion was simultaneously added at an accelerated flow rate so that the silver iodide content became 10.5 mol%, and the p emulsion of the bulk emulsion solution in the reaction vessel was added.
Ag was kept at 9.50. 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 27 minutes by the double jet method. KBr so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition becomes 8.15.
The addition of the aqueous solution was adjusted. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.50.
The above AgI fine grain emulsion was added in an amount of 5.73 g in terms of KI weight. Immediately after completion of the addition, 609 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 11 minutes. During the initial 6 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50 with an aqueous KBr solution. After washing with water, gelatin was added and the pH was adjusted to 6.5, pAg, and 8.2 at 40 ° C. Thereafter, the compound ExA-1 was added, and the temperature was raised to 56 ° C. The sensitizing dyes Exs-1 and Exs-6 were added, and then potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added and ripened for optimal chemical sensitization. Compound E at the end of chemical sensitization
xA-2 and compound ExA-3 were added. The amount of the sensitizing dye used was Exs per mol of silver halide.
-1 is 3.69 × 10 ^-4 mol, Exs-6 is 8.19 ×
10 ^-4 mol.

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(Preparation of Emulsion N) Gelatin-2 of Example 1
Solution containing 0.38 g of KBr and 0.9 g of KBr
L was maintained at 60 ° C., the pH was adjusted to 2, and the mixture was stirred vigorously.
An aqueous solution containing 1.03 g of AgNO ₃ and 0.8% of KBr
An aqueous solution containing 8 g and 0.09 g of KI was added by a double jet method over 30 seconds. After completion of the ripening, 12.8 g of gelatin-3 of Example 1 was added. After adjusting the pH to 5.9, KBr, 2.99 g, NaCl, 6.2 g
Was added. An aqueous solution containing 27.3 g of AgNO ₃ 60.
7 mL and an aqueous KBr solution were added by the double jet method over 39 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.05. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were accelerated by a double jet method so that the final flow rate was 2.1 times the initial flow rate, and 46
Added over minutes. At this time, the AgI fine grain emulsion used in the preparation of Emulsion D was simultaneously added at an accelerated flow rate such that the silver iodide content became 6.5 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.05. Kept. After adding 1.5 mg of thiourea dioxide, AgNO ₃ , 41.
132 mL of an aqueous solution containing 8 g and an aqueous KBr solution were added over 16 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition became 7.70. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.80. The above AgI fine grain emulsion was 6.2 in terms of KI weight.
g was added. Immediately after completion of the addition, AgNO ₃ , 88.5
g of an aqueous solution containing 300 g was added over 10 minutes.
The aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 7.40.
After washing with water, the gelatin-1 of Example 1 was added and adjusted to pH 6.5, pAg and 8.2 at 40 ° C. Compound ExA
After adding -1, the temperature was raised to 58 ° C. Sensitizing dye Exs
-7, Exs-8 and Exs-9 after addition of K ₂
IrCl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of chemical sensitization, compound ExA-
2 and compound ExA-3 were added.

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(Preparation of Emulsion O) In the preparation of Emulsion N,
The amount of AgNO ₃ added during nucleation is 1.96 g,
The amount of Br was changed to 1.67 g, the amount of KI was changed to 0.172 g, and the temperature at the time of chemical sensitization was changed from 58 ° C to 6 ° C.
The temperature was changed to 1 ° C. Other than that, it was prepared in substantially the same manner as in emulsion N.

(Preparation of Em-P) Gelatin of Example 1
4, an aqueous solution 1200 containing 4.9 g of KBr and 5.3 g of KBr
The mL was kept at 40 ° C. and stirred vigorously. AgNO ₃ , 8.
27 mL of an aqueous solution containing 75 g and 36 mL of an aqueous solution containing 6.45 g of KBr were added over 1 minute by the double jet method. After the temperature was raised to 75 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃ was added over 2 minutes. NH ₄ N
After sequentially adding O ₃ , 26 g, 1N, NaOH and 56 mL, the mixture was aged. After aging, the pH was adjusted to 4.8. 438 mL of an aqueous solution containing 141 g of AgNO ₃ and K
458 mL of an aqueous solution containing 102.6 g of Br was added by a double jet method so that the final flow rate was four times the initial flow rate. After cooling to 55 ° C., 240 mL of an aqueous solution containing 7.1 g of AgNO ₃ and an aqueous solution containing 6.46 g of KI were added over 5 minutes by a double jet method. 7.1 KBr
g of sodium benzenethiosulfonate,
mg and K ₂ IrCl _6, was 0.05mg added. AgNO
₃ , 177 mL of an aqueous solution containing 57.2 g and KBr, 4
223 mL of an aqueous solution containing 0.2 g was added by the double jet method over 8 minutes. The emulsion was washed with water in almost the same manner as in Emulsion N and chemically sensitized.

(Preparation of Emulsions Q and R) Emulsions K and L were prepared almost in the same manner. However, chemical sensitization is emulsion O
Was performed in substantially the same manner.

Table 3 summarizes the characteristic values of the silver halide emulsion. The surface iodine content can be determined by XPS as follows. The sample was cooled to −115 ° C. in a vacuum of 1 × 10 torr transfer, irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA, and measured for Ag3d5 / 2, Br3d, and I3d5 / 2 electrons. The integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio. The emulsions D to G, Ha, Hb, and I-
Dislocation lines as described in JP-A-3-237450 were observed in silver halide grains a, Ib, and J to R using a high-pressure electron microscope.

Table 3 below shows the properties of the emulsion used in this example.

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[Table 4]

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[Table 5]

1) Support The support used in this example was prepared by the following method.

100 parts by weight of polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 326 (manufactured by Ciba-Geigy) and 2 parts by weight, and then melted at 300 ° C.
It was extruded from the die, stretched 3.3 times at 140 ° C., stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to form a 90 μm-thick PEN (polyethylene). A naphthalate) film was obtained. Note that this P
The EN film has a blue dye, a magenta dye, and a yellow dye (public technique: I-1, I-4, I-6, I-24, I-26, and I-2 described in Japanese Patent Publication No. 94-6023).
7, II-5) was added in an appropriate amount. Furthermore, diameter 20cm
And a heat history of 110 ° C. for 48 hours was given to obtain a support that is less likely to have a curl.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment on both surfaces thereof, and then each surface was coated with 0.1 g / m ² of gelatin and sodium α-. Sulfodi-2-
Ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g
/ M ² , (CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH
₂ 0.012 g / m ² , an undercoat solution of polyamide-epichlorohydrin polycondensate 0.02 g / m ² was applied (10c
c / m ² , using a bar coater) and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 N
HCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
It was coated with m ² and resorcin.

3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ²⁾ / G, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu
/ G, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² to diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill),
_{C 2 H 5 C (CH 2} OCONH-C 6 H 3 as a curing agent (C
0.3 g / m ² of H ₃ ) NCO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of an abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as a matting agent / M
² was added. Drying was carried out at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). X- write saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.3 ×
10 ⁴ A / m and the squareness ratio were 65%.

3-3) Adjustment of Sliding Layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH
(OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg /
m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b,
9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1 /
In 1), the mixture was melted at 105 ° C., and poured into and dispersed in propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone (average particle size: 0.01 μm). As a matting agent, silica particles (0.3 μm) and aluminum oxide (0.15 μm) coated with 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by weight) as an abrasive are each 15 mg / m 2.
² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a kinetic friction coefficient of 0.12 between the emulsion surface and the sliding layer described later. Excellent characteristics.

4) Coating of Photosensitive Layer (Sample 101) Next, on the side opposite to the back layer obtained above, layers having the following compositions were applied in a multi-layered manner.
01 was created.

(Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: Gelatin hardener (specific compounds are described below with numerical values following symbols and chemical formulas after).

The number corresponding to each component indicates the coating amount in g / m ² , and the coating amount in terms of silver is shown for silver halide.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion T Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-20 0.001 HBS-1 0.004 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.011 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.014 solid disperse dye ExF-3 0.020.

Third layer (intermediate layer) Silver iodobromide emulsion S 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion R silver 0.065 silver iodobromide emulsion Q silver 0.258 ExC-1 0.109 ExC-3 0.044 ExC-40 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver iodobromide emulsion P silver 0.21 silver iodobromide emulsion O silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-30 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion N silver 1.47 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY- 5 0.008 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12.

Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84.

Eighth Layer (Layer Which Gives Layered Effect to Red Sensitive Layer) Silver iodobromide emulsion M 0.560 Cpd-3 0.020 Cpd-4 0.030 ExM-2 0.096 ExM-3 0. 028 ExY-1 0.031 ExG-1 0.006 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.39 silver iodobromide emulsion K silver 0.28 silver iodobromide emulsion J silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 Cpd-3 0.010 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion Ia Silver 0.45 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 ExG-1 0.005 Cpd-3 0.006 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44.

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Ia Silver 0.30 Silver Iodobromide Emulsion Ha Silver 0.69 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 ExG-1 0.005 Cpd-3 0.004 Cpd-4 0.007 HBS- 1 0.18 polyethyl acrylate latex 0.099 gelatin 1.11.

12th Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.010 Cpd-1 0.16 Oil-soluble Dye ExF-5 0.010 Solid Dispersion Dye ExF-6 0.020 HBS-1 0.082 Gelatin 1 .057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion G silver 0.18 silver iodobromide emulsion E silver 0.20 silver iodobromide emulsion F silver 0.07 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-10 .24 gelatin 1.41.

Fourteenth Layer (High Sensitive Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd- 2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91.

Fifteenth Layer (First Protective Layer) Silver Iodobromide Emulsion S Silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-180 0.0009 F-19 0.005 F-20 0.005 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-30 .05 S-1 0.20 gelatin 0.75.

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-5, B-4 to B -6,
F-1 to F-18 and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, ruthenium salts, and rhodium salts. Further, 8.5 × 10 ^-3 g per mol of silver halide to the coating solution of the eighth layer, a 7.9 × 10 ^-3 grams of calcium in the 11th layer was added with an aqueous solution of calcium nitrate to form Sample .

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 mL and 3 mL of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were placed in a 700 mL pot mill, and the dye ExF -2 and 5.0 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, BO made by Chuo Koki
A mold vibration ball mill was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

In the same manner, a solid dispersion of ExF-4 was obtained. The average particle size of the fine dye particles is 0.24 μm, respectively.
It was 0.45 μm and 0.52 μm. ExF-2 is a microprecipipi described in Example 1 of EP-A-549,489A.
station) and dispersed by a dispersion method. The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method.

To 2800 g of an ExF-6 wet cake containing 18% of water, 376 g of 4.0 kg of water and a 3% solution of W-2 were added and stirred to obtain a slurry having a concentration of 32% of ExF-6. Next, 1700 mL of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and crushed for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min through the slurry. did.

The compounds used for forming each of the above layers are as shown below.

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(Preparation of Sample 102) A sample 102 was prepared by making the following changes to the sample 101.

1) In the tenth layer, silver iodobromide emulsion Ia was replaced with emulsion Ib having an equal silver amount. 2) In the eleventh layer, silver iodobromide emulsion Ia was replaced with emulsion Ib having the same silver amount, and silver iodobromide emulsion Ha was replaced with emulsion Hb having the same silver amount.

3) In the coating solutions of the photosensitive silver halide emulsion layers from the eighth layer to the eleventh layer, sodium sulfite was contained at 2.10 × 10 ^-4 mol per mol of silver halide.

4) The coating solution of the formula (I)
Compound I-2 was added. The amount added is the same for all photosensitive halos.
5.0 × with respect to 1 mol of silver halide in silver halide emulsion layer
10 ^-FiveIt was adjusted so as to be applied in molar.

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge and a gelatin filter SC-39 (a long-wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by FUJIFILM Corporation. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is an invention association disclosed technique 94-49.
No. 92 is mounted.

The processing steps and the composition of the processing solution are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20mL 11.5L Bleaching 50 seconds 38.0 ° C 5mL 5L Fixing (1) 50 seconds 38.0 ° C-5L Fixing (2) 50 seconds 38.0 ° C 8mL 5L Water washing 30 seconds 38.0 ° C 17mL 3L stable (1) 20 seconds 38.0 ° C-3L stable (2) 20 seconds 38.0 ° C 15mL 3L Drying 1 minute 30 seconds 60.0 ° C * Replenishment amount is 35mm width of photosensitive material Per 1.1 m (equivalent to 24 Ex. 1 line).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.
2.5mL, 2.0mL, 2.0m / m
L. The crossover time was 6
Seconds, and this time is included in the processing time of the previous step.

The opening area of the above processor was 10
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² .

[0521] The composition of the treatment liquid is shown below.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with aqueous ammonia] 4.6 4.0.

(Fixing (1) Tank Liquid) A 5/95 (ratio by volume) mixed solution (pH 6.8) of the above bleaching tank liquid and the following fixing tank liquid.

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3
mg / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L.
L was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Disodium ethylenediaminetetraacetate 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

The photographic performance was evaluated by measuring the density of the processed sample with a green filter. The degree of fogging generated by exposing the samples 201 and 202 to gas generated by combustion was evaluated in the same manner as in Example 1. The results obtained are shown in Table 4 below. The sensitivity was expressed as a relative value of the reciprocal of the exposure necessary for the magenta density to reach the fog density plus the density of 0.2.
(The sensitivity of Sample 201 was set to 100.)

[0529]

[Table 6]

As is clear from Table 4, the silver iodobromide emulsion grains of the tenth and eleventh layers, which are medium- and high-sensitivity green-sensitive emulsion layers, have an AgI content of 5 mol% or less. The sample 202 containing a sulfite ion and a compound represented by the formula (I) in the light-sensitive material has a silver iodobromide emulsion grain surface of the 10th and 11th layers whose AgI content is 5 mol%. Sample 20 which does not contain a sulfite ion and a compound represented by the formula (I) in the photosensitive material
On the other hand, the fog generated when exposed to the exhaust gas of an automobile is remarkably small while maintaining almost the same photographic sensitivity as that of No. 1, which is preferable.

(Example 3) (Preparation of Samples 301 to 323) Samples 301 to 323 were prepared in the same manner as in Sample 2 of Example 2 except that the compounds defined in the present invention were added or replaced as shown in Table 5.
323 were created.

(When added at the time of preparing an emulsion)
Compounds (III-1) and (III-19) of II)
Are emulsions Hb, Ib, J, and K of the green-sensitive layer of Sample 202.
Emulsions were prepared in the same manner except that they were added after the completion of chemical ripening. These (III-1) and (III-1)
A sample was similarly prepared using the emulsion to which the compound of 9) was added.

The compounds represented by the general formulas (AI) to (A-II)
The sample of I) and the sample added during the preparation of the emulsion were also prepared.
Compounds AI-14, AI-11 and A-II- in Table 5
6 and A-III-5, and all green-sensitive emulsions H-
b, Ib, J, K and L are represented by the following comparative compound Ex-
Samples were prepared in the same manner using the emulsion prepared by adding Compound No. 1 before spectral sensitization.

[0534]

[Table 7]

[0535]

[Table 8]

The amount of addition was shown in parentheses in Table 5 as the number of moles per mole of silver halide in the emulsion. In each case, the addition was performed as an aqueous solution.

[0537]

Embedded image

(When diffusing from another layer at the time of coating) The compounds of the general formulas (I), (AI) to (A-III), and (V) are added to the fifteenth protective layer. It was diffused and contained in the green-sensitive emulsion layer.

The values in parentheses in Table 5 indicate the amount of addition in terms of moles per mole of silver halide in all photosensitive emulsions. The addition was performed as an aqueous solution or a methanol solution.

(When added as an emulsified dispersion at the time of preparing a coating solution) The compound of the general formula (IV-1) or (IV-2) was used as the compound Cpd-
3 was added to the compounds shown in Table 5 in a 1-fold molar amount, and a sample was prepared. These compounds were emulsified and dispersed together with a dye-forming coupler or a high-boiling organic solvent in the same layer in the presence of a surfactant and added during the preparation of a coating solution.

The sensitivity and the increase in fog concentration due to the exhaust gas from a gasoline-powered vehicle were tested and evaluated in the same manner as in Example 2. The results are shown in Table 5.

The following is clear from the results in Table 5. The green-sensitive emulsion layer contains the compound of the formula (III), and the green-sensitive emulsion layer contains the compound of the formula (IV-1) or (IV-2), which is a constituent feature of the third embodiment of the present invention. To the green-sensitive emulsion layer, the formula (AI) or (A-
By containing the compound of III), the effect of suppressing the increase in fog generated by the exhaust gas was further improved by combining with the constituent features of the first aspect or the second aspect, and the increase in fog could be remarkably reduced. . This additional effect cannot be obtained even if any one of-is missing, and is specifically exhibited when all the constituents of-are satisfied.

The inclusion of the compound of the formula (V) in the light-sensitive material, which is a constituent element of the fourth embodiment of the present invention, has a greater effect when combined with the constituent elements of the first or second embodiment. Could be obtained. It can be seen that the greatest effect can be obtained by combining with the constituent features of the third aspect.

(Example 4) Compound 3-2 of formula (I) in Samples 312 and 318 of Example 3 was
A sample was prepared and evaluated in the same manner as in Example 3, except that a dispersion was prepared by the dispersion method described in JP-2011974 and contained as a microcrystalline dispersion. As a result, a great effect was obtained as in Example 3. .

[0545]

According to the present invention, there is provided a silver halide color photographic light-sensitive material for photography, which has high sensitivity and remarkably improved resistance to an increase in fog against harmful gases generated during combustion of automobile exhaust gas and the like. can do.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/00 510 G03C 7/00 510 (72) Inventor Mamoru Sakurazawa 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Inside (72) Inventor Hiroshi Takeuchi 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd. (72) Inventor Tadashi Inaba 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd. (72) Inventor Masayoshi Yoshikawa 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H016 BB02 BB04 BC01 BD00 BD01 BD02 BM04 2H023 BA02 BA04 CA07 CA13 CC01 CC02 CC09 CD00

Claims (4)

[Claims] 1. A method comprising: a support having at least one green-sensitive silver halide emulsion layer and at least one non-light-sensitive layer;
After exposure, a silver halide color photographic light-sensitive material for photography, which forms an image through a color development step and a subsequent desilvering step, has at least one of the green-sensitive silver halide emulsion layers having a parallel principal plane of (111). ) Tabular silver halide grains of silver iodobromide or silver chloroiodobromide having a surface and an aspect ratio of 5 or more and a surface silver iodide content of 5 mol% or less are 50% or more of the total projected area. A silver halide color photographic light-sensitive material for photography, comprising a silver halide emulsion occupying the following formula, and a compound represented by the following general formula (I) and a sulfite ion. General formula (I) Wherein represents R _11, R _12, R ₁₃ and R ₁₄ are each independently a hydrogen atom, an aryl group, a linear or cyclic alkyl group, a linear or cyclic alkenyl or alkynyl group,, R ₁₅ is a chain A cyclic or cyclic alkyl group, a chain or cyclic alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. 2. The method according to claim 1, wherein at least one cyanine sensitizing dye represented by the following formula (II) is contained in an amount of 5 × 10 ^-4 mol or more per mol of silver halide.
2. A silver halide color photographic light-sensitive material for photography according to item 1. Formula (II) In the formula, Z ₁ and Z ₂ each independently represent an atom group necessary for forming a heterocyclic nucleus together with an oxygen atom. L ₁ and L ₂ each independently represent a methine group or a substituted methine group. X ₁ ^- represents an acid anion group. n ₁ represents 1 or 2. R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group or allyl group used for the N-substituent of the cyanine dye. 3. A compound represented by the following general formula (III):
And at least one kind represented by the following general formula (IV-1)
And a compound represented by the following general formula (IV-2)
At least one selected from the group consisting of:
From compounds represented by general formulas (AI) to (A-III)
Containing at least one member selected from the group consisting of
The halogenation for photography according to claim 1 or 2,
Silver color photographic light-sensitive material. General formula (III)In the formula, Het is an adsorptive group to silver halide. However,
The group represented by Het includes at least one-(Q) k2
-(Hy) is substituted. Q is a carbon atom, a nitrogen atom,
A source containing at least one of a sulfur atom and an oxygen atom
Represents a divalent linking group consisting of an atom or an atomic group. Hy is
R₁R_TwoN-NR_ThreeR_FourHas a hydrazine structure represented by
Represents a group. R₁, R_Two, R_ThreeAnd R_FourAre independent
Alkyl, alkenyl, alkynyl, aryl
Or a heterocyclic group;₁And R_Two, R_ThreeAnd R_Four, R₁When
R_ThreeOr R_TwoAnd R_FourMay combine with each other to form a ring
No. Where R₁, R_Two, R_ThreeAnd R_FourAt least one of
Is-(Q) k2- (Het) k1 in the general formula (III).
Is an alkylene group, alkenylene group,
Quinylene group, arylene group or divalent heterocyclic residue
is there. k1 and k3 each independently represent 1, 2, 3 or 4
And k2 represents 0 or 1. Formulas (IV-1) and (IV-2)In the general formula (IV-1), R₃₁, R₃₂, R₃₃And R₃₄Is
Each independently represents a hydrogen atom or a substituent. Where R₃₁
And R₃₄Or R₃₂And R₃₃Is the place of each alkyl group
In this case, substituents having exactly the same number of carbon atoms are not taken. The general formula (IV
-2), R₄₁, R₄₂And R₄₃Are each independently a hydrogen atom
Or a substituent. Z is a non-metal forming a 4- to 6-membered ring
Represents an atomic group. Formulas (AI) to (A-III)In the general formula (AI), R_a1Is a substituted or unsubstituted alkyl
R, alkenyl, or aryl;_a2Is water
Elemental atom or R_a1Represents a group represented by R_a3Is a hydrogen atom
Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
Or an alkenyl group. R_a1And R_a3Or R_a2And R
_a3May combine with each other to form a 5- to 7-membered ring. one
In the general formula (A-II), X represents a heterocyclic group;_b1Is
Represents an alkyl group, an alkenyl group or an aryl group. X
And R_b1May combine with each other to form a 5- to 7-membered ring.
No. In the general formula (A-III), Y is a 5-member with -N = C-
Represents a group of non-metallic atoms necessary to form a ring. Y is more
Necessary to form a 6-membered ring together with the -N = C- group.
Represents a group of metal atoms and is bonded to a carbon atom of a -N = C- group
The terminal of Y is -N (R _C1)-, -C (R_C2) (R_C3)-, -C (R_C4) =,
One group selected from the group consisting of —O— and S— (each
Bond on the left side of the group with a carbon atom of -N = C-)
You. R_c1~ R_c4Each independently represents a hydrogen atom or a substituent
You. 4. A compound represented by the following general formula (V):
Claim 1 or Claim 2 characterized by containing at least one.
3. The silver halide color photography for photography according to any one of 3.
True photosensitive material. General formula (V)In the formula (V), R_{twenty one}, R_{twenty two}And R_{twenty three}Are independently hydrogen sources
, Alkyl, alkenyl, alkynyl, aryl
A heterocyclic group or a heterocyclic group;_{twenty four}Is a hydrogen atom, al
Kill, alkenyl, alkynyl, aryl,
Or a heterocyclic group, or NR_{twenty five}R₂₆And L_{twenty one}Is -C
O- or -SO_TwoRepresents-and n represents 0 or 1.
R_{twenty five}Is hydrogen atom, hydroxy group, amino group, alkyl
Group, alkenyl group, alkynyl group, aromatic group, or
Represents a telocyclic group, R₂₆Represents an alkyl group, an alkenyl group,
Represents a rukinyl group, an aromatic group, or a heterocyclic group. R_{twenty one}
And R _{twenty two}, R_{twenty one}And R_{twenty three}, R_{twenty three}And R_{twenty four}Or R_{twenty four}And R
_{twenty two}May be linked to form a ring.