JP2001330930A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having high sensitivity, low fog and improved latent image stability. SOLUTION: In the silver halide color photographic sensitive material with photographic constituent layers comprising at least two red-sensitive layers, at least two green-sensitive layers, at least two blue-sensitive layers and at least two non-photosensitive layers on at least one side of the base, the blue- sensitive layers contain at least one yellow coupler selected from the group comprising yellow couplers of formulae (Y-1), (Y-2) and (Y-3) and silver halide grains subjected to reduction sensitization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic material.

[0002]

2. Description of the Related Art In recent years, performance requirements for silver halide color photographic light-sensitive materials have become more and more severe, and photographic properties such as sensitivity, fog, graininess, and storability have been required to be higher. Has occurred. In particular, recently, with the spread of compact zoom cameras and cameras with lenses, which are generally single-use cameras, higher sensitivity is required for photographic materials, and photographic equipment is being carried to various places. Therefore, it is expected that the vehicle will be placed under severe conditions (for example, being left in a car in summer). For this reason, in the photographic material, high performance has been particularly required for the storage stability of the blue-sensitive emulsion layer before exposure and the stability of the latent image from exposure to development.

Therefore, Japanese Patent Application Laid-Open No. Hei 7-306491, European Patent No. 0902321 and Japanese Patent Application Laid-Open No. 54-119917 disclose the sensitivity when two kinds of spectral sensitizing dyes are combined.
The effect on fog is disclosed. On the other hand, regarding reduction sensitization, the Journal of Photographic
Science (Journal of Photogra
phy Science), Vol. 25, pp. 19-27 (1977) and Photographic Science
And Engineering (Photographic)
Science and Engineering)
Vol. 23, pp. 113-117 (1979), etc., report that reduction sensitization nuclei appropriately applied contribute to sensitization. Japanese Patent Application Laid-Open No. 9-236881 discloses a technique for improving the stability of a latent image by performing reduction sensitization.

However, the above-mentioned prior art is insufficient to provide the performance of a silver halide color photographic light-sensitive material required in today's market, and further improvement has been desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic material having high sensitivity, low fog and improved latent image stability.

[0006]

The above objects of the present invention have been attained by the following items 1 to 8.

[0007] 1. A silver halide color photographic material having at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer on one side of a support, wherein the blue-sensitive layer is General formulas (Y-1) and (Y-2)
And silver halide grains containing at least one yellow coupler selected from the group consisting of (Y-3) and reduction sensitized silver halide grains. Photosensitive material.

[0008] 2. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer, and a non-light-sensitive layer on one side of a support. The photosensitive layer has the general formula (Y
-1) a spectral sensitizing dye containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3), and represented by the formula (S-1) 2
A silver halide color photographic light-sensitive material characterized by containing at least one species.

3. 3. The silver halide color photographic light-sensitive material as described in (2) above, wherein the spectral sensitizing dye represented by the general formula (S-1) is represented by the general formula (S-2).

[0010] 4. 4. The silver halide color photographic light-sensitive material as described in 3 above, which contains reduction-sensitized silver halide grains.

5. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer, and a non-light-sensitive layer on one side of a support. The photosensitive layer has the general formula (Y
-1) containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3), and containing the silver halide emulsion 1 described above. Silver color photographic light-sensitive material.

6. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer, and a non-light-sensitive layer on one side of a support. The photosensitive layer has the general formula (Y
-1), containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3), and represented by the general formula (A-1) or (A-2). A silver halide color photographic light-sensitive material comprising at least one compound represented by the formula:

7. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer, and a non-light-sensitive layer on one side of a support. The photosensitive layer has the general formula (Y
-1) containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3) and the compound represented by the formula (I), and selenium-sensitized. Silver halide color photographic light-sensitive material, characterized by containing silver halide grains.

8. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least two red-sensitive layers, a green-sensitive layer, a blue-sensitive layer, and a non-light-sensitive layer on one side of a support. The photosensitive layer is represented by at least one yellow coupler selected from the group consisting of the general formulas (Y-1), (Y-2) and (Y-3), and the general formula (II) A silver halide grain containing a compound, and during the preparation of the silver halide grain, the compound represented by the general formula (II) is added between the addition of a sensitizing dye and the addition of a chalcogen sensitizer. A silver halide color photographic light-sensitive material characterized by being added to a silver halide color photographic light-sensitive material.

Hereinafter, the present invention will be described in detail. The yellow couplers represented by formulas (Y-1), (Y-2) and (Y-3) according to the present invention will be described.

In the general formula (Y-1), examples of the substituent represented by R ₁ include an alkyl group (for example,
Methyl group, ethyl group, isopropyl group, t-butyl group,
Hexyl group, dodecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, adamantyl group, etc.), aryl group (eg, phenyl group, pt-
Octylphenyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group, etc.), alkoxy group (eg, methoxy group, etc.), aryloxy group (eg, 2,4-di-t-amylphenoxy group) Etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group), an aryloxy group (e.g., an m-pentadecylphenoxycarbonyl group, etc.), a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), an alkylsulfonyl group (e.g., Methanesulfonyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (eg, dodecanesulfonylamino group, etc.), nitro group, cyano group, amino group (eg, dimethylamino group, Anilino group, etc.), alkylthio group (eg, methylthio group, etc.) And a hydroxyl group.

The substituent represented by R ₁ may be further substituted. In the above description, an alkoxy group is preferably used as R ₁ , and a methoxy group is particularly preferable.

In the general formula (Y-1), the alkyl group having 7 to 20 carbon atoms represented by R ₂ may be branched or unbranched. As the branched alkyl group,
The typical specific examples are shown below, but the present invention is not limited thereto.

[0019]

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R ₂ may have a substituent. In this case, examples of the substituent include the same groups as the substituents represented by R ₁ in formula (Y-1).

In the general formulas (Y-1), (Y-2) and (Y-3), R ₃ represents a hydrogen atom or a halogen atom. Among them, a halogen atom is preferably used. Preferably used is a chlorine atom.

In the general formulas (Y-1) and (Y-2), m represents an integer of 1 to 5. m is preferably 1, and particularly preferably, the substitution position of R ₁ is the same as that of the general formula (Y
-1) and para position of the acyl group in (Y-2).

In the general formulas (Y-1), (Y-2) and (Y-3), Z ₁ is> NR ₄ (R ₄ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or Represents a heterocyclic group) or —O—, and Z ₂ represents> N—R ₅
(R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or> C (R ₆ )
(R ₇ ) (R ₆ and R ₇ represent a hydrogen atom or a substituent)
Represents

The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₄ and R ₅ are exemplified as the substituent represented by R ₁ in the above general formula (Y-1). And the same groups as the alkyl group, cycloalkyl group, aryl group and heterocyclic group.

The alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R ₄ and R ₅ may have a substituent. In this case, examples of the substituent include those represented by the aforementioned general formula (Y The same groups as the substituents represented by R ₁ in -1) can be mentioned.

As the substituents represented by R ₆ and R ₇ , for example, the same groups as the substituents represented by R ₁ in formula (Y-1) can be mentioned.

The substituents represented by R ₆ and R ₇ may be further substituted. In the general formula (Y-2),
The alkyl group, cycloalkyl group or aryl group represented by R ₈ is the same as the alkyl group, cycloalkyl group and aryl group represented by the examples of the substituent represented by R ₁ in formula (Y-1). Similar groups can be mentioned.

The alkyl group, cycloalkyl group or aryl group represented by R ₈ may have a substituent. In this case, examples of the substituent include those represented by formula (Y-1)
And the same groups as the substituents represented by R ₁ in the above.

In the general formula (Y-2), the alkyl group or the cycloalkyl group represented by R ₉ is represented as an example of the substituent represented by R ₁ in the general formula (Y-1). Examples include the same groups as the alkyl group and the cycloalkyl group.

The alkyl group or cycloalkyl group represented by R ₉ may have a substituent. In this case, examples of the substituent include those represented by R ₁ in formula (Y-1).
And the same groups as the substituents represented by.

In the general formula (Y-2), R ₈ and R ₉
Has a carbon number of 7 to 20. The general formula (Y-3)
In the above, the non-diffusible alkyl group represented by R ₁₀ preferably includes an alkyl group having 8 to 21 carbon atoms, which may be linear or branched, octyl group, 2-ethylhexyl Group, decyl group, 2,4-diethylheptyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group and the like.

The non-diffusible alkyl group represented by R ₁₀ may further have a substituent. In this case, examples of the substituent include those represented by R ₁ in the general formula (Y-1). Although the same groups as the substituents represented can be mentioned, in the present invention, the diffusion-resistant alkyl group preferably has a total carbon number of 7 to 30 including the substituent,
More preferably, the total number of carbon atoms is 8 to 21.

The yellow couplers represented by formulas (Y-1), (Y-2) and (Y-3) are bonded at any of the substituents to form a bis, tris, tetrakis or polymer. May be formed.

The following formulas (Y-1) and (Y-
Representative specific examples of the yellow couplers represented by 2) and (Y-3) are shown below, but the present invention is not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The yellow couplers represented by formulas (Y-1), (Y-2) and (Y-3) can each be synthesized by referring to conventionally known methods. Further, in the present invention, the general formulas (Y-1), (Y-2) and (Y-3)
May be used in combination of two or more, and may be used in combination with other yellow couplers.

The content of the yellow couplers represented by formulas (Y-1), (Y-2) and (Y-3) is as follows:
It is preferably 0.1 to 3.0 g / m ^{2, and} more preferably 0.5 to 1.5 g / m ² .

The yellow couplers represented by formulas (Y-1), (Y-2) and (Y-3) are used together with a high boiling organic solvent. The content of the high boiling point organic solvent is preferably 1 g or less per 1 g of the yellow coupler represented by formulas (Y-1), (Y-2) and (Y-3).

Next, the silver halide grains and the silver halide emulsion containing the same according to the present invention will be described.

The production of the silver halide emulsion according to the present invention comprises:
A conventionally known method can be applied.
No. 43, No. 61-14630, No. 61-112142
No. 62-157024, No. 62-18556,
63-92942, 63-151618, 6
Nos. 3-163451, 63-220238, 63
-31244, RD38957, Sections I and III,
It can be manufactured by selecting appropriate conditions with reference to the XV section of RD40145 and the like.

When a silver halide color photographic light-sensitive material is prepared using the silver halide emulsion according to the present invention, the silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. RD389 in each step
Various additives such as those described in Sections IV and V of 57, XV of RD40145 and the like can be used.

Known photographic additives (for example, spectral sensitizers, supersensitizers, antifoggants, stabilizers, etc.) which can be used in the present invention are also the same as those described in RD38957, sections II to X and RD4.
The compounds of paragraphs I to XIII of 0145 can be used.

In the preparation of the silver halide grains subjected to reduction sensitization and the silver halide emulsion containing the same according to the present invention, a reducing agent is used. Specific examples of the reducing agent include, for example, thiourea dioxide, ascorbic acid and its derivatives, stannous salts, borane compounds, hydrazine derivatives,
Formamidine sulfinic acid, silane compounds, amines and polyamines, sulfites and the like are used, and thiourea dioxide, ascorbic acid and its derivatives, stannous salts and the like are preferably used.

[0057] In the preparation of silver halide grains of the present invention, when using a reducing agent, the content per 1 mol of silver halide is preferably 10 ^-2 to 10 ^-8 mol, more preferably 10 ^{- 3} to 10 ^-7 mol.

In the preparation of the silver halide grains according to the present invention, when reduction sensitization is carried out by using a protective colloid aqueous solution in which silver halide grains are grown under a low pAg condition of pAg 7.0 or less, After adding a silver salt to the aqueous protective colloid solution to obtain an appropriate pAg, it is preferable to ripen or grow the silver halide grains. The silver salt is preferably a water-soluble silver salt, and particularly preferably an aqueous solution of silver nitrate. The pAg at the time of aging is suitably 7.0 or less, and preferably 2.0 to 5.0. (Where the pAg value is Ag
⁺ Shows the common logarithm of the reciprocal of the concentration. In the preparation of the silver halide grains according to the present invention, when reduction sensitization is carried out by using a protective colloid aqueous solution in which silver halide grains are grown under a high pH condition of pH 7.0 or more, After an alkaline compound is added to the aqueous protective colloid solution to obtain an appropriate pH, the silver halide grains are ripened or grown. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, ammonia and the like can be used, but it is preferable that the compound is other than the ammonium compound.

In the preparation of the silver halide grains according to the present invention, the reduction sensitization in the silver halide emulsion is performed by adjusting the aqueous solution of the protective colloid in which the silver halide grains are grown to pH.
It was most effectively achieved by using a high pH condition of 7.0 or more.

The method for adding the reducing agent, the silver salt for reduction ripening, and the alkaline compound may be rush addition or may be added over a certain period of time. In this case, uniform addition may be performed, or function addition may be performed. Further, the required amount may be added several times.
Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed with the soluble halide solution and added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

In the preparation of silver halide grains according to the present invention, reduction sensitization is preferably carried out at pH 7.0 or higher in an aqueous protective colloid solution in which silver halide grains are grown. The pH is more preferably 7.5 or more and 11.0 or less,
The value is most preferably 8.0 or more and 10.0 or less.

In the present invention, an oxidizing agent can be used for deactivating the reducing agent described above or for other purposes.

Hydrogen peroxide (water) and its adduct: H
₂ O ₂ , NaBO ₂ , H ₂ O ₂ -3H ₂ O, 2NaCO ₃ -3
_{H 2 O 2, Na 4 P} 2 O 7 -2H 2 O 2, 2Na 2 SO 4 -H 2 O
Such as ₂ -2H ₂ O. Peroxy acid salts: K ₂ S ₂ O ₃ , K ₂ C ₂
O ₃ , K ₄ P ₂ O ₃ , K ₂ [Ti (O ₂ ) C ₂ O ₄ ] -3H
Examples include ₂ O, peracetic acid, ozone, I ₂ , and thiosulfonic acid compounds.

In the present invention, the above-mentioned oxidizing agent can be used for purposes other than deactivation of the reducing agent. The addition amount of the oxidizing agent, the type of the reducing agent, reduction sensitization conditions, timing of addition of oxidizing agent, is influenced in its amount by the addition conditions of the oxidizing agent, the reducing agent per mole ^10-3 to using Molar is preferred.

The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It may be added prior to the addition of the reducing agent. As an adding method of the oxidizing agent,
In the art, a method in which an additive is generally added to a silver halide emulsion can be applied. For example, it can be previously dissolved in an appropriate organic solvent represented by alcohols, or added as an aqueous solution.

After the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the oxidizing agent, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The addition amount of these reducing substances is preferably from 10 ^-3 to 1 mol per mol of the oxidizing agent used.

Next, the silver halide emulsion 1 according to claim 5 will be described. The silver halide emulsion 1 of the present invention according to claim 5 contains tabular silver halide grains. In the present invention, tabular grains are crystallographically classified as twins.

A twin is a silver halide crystal having one or more twin planes in one grain, and the twins are classified according to a report by Klein and Moiser, a photographer Correspond. Dents (Photographish)
e Korespondenz), 99, 100
Page 100, Vol. 100, p. 57.

The tabular grains according to the present invention have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows.

First, a silver halide photographic emulsion is coated on a support so that the contained tabular grains are oriented substantially parallel to the main plane to prepare a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The distance between the twin planes in the tabular grain of the present invention is determined by observing the section using a transmission electron microscope as described above. The distance between the two twin planes having the shortest distance among the even twin planes parallel to the main plane is obtained for each particle, and the average is obtained by averaging.

In the present invention, the distance between twin planes is a factor affecting the supersaturation state during nucleation, for example, gelatin concentration, gelatin type, temperature, iodine ion concentration, pBr, pBr.
It can be controlled by appropriately selecting a combination of various factors such as H, ion supply speed, and stirring rotation speed. In general, the distance between twin planes can be reduced as nucleation is performed in a highly supersaturated state.

The details of the supersaturation factor are described in, for example, JP-A-63-92924 and JP-A-1-213637.

The average distance between twin planes is 0.01 to 0.05.
μm is preferable, and 0.013 to 0.02 is more preferable.
5 μm.

The thickness of a tabular grain can be obtained by observing a section using a transmission electron microscope as described above, similarly obtaining the thickness of each grain, and performing averaging. The thickness of the tabular grains is preferably from 0.05 to 1.5 μm, more preferably from 0.07 to 0.50 μm.

The tabular grains according to the present invention have a variation coefficient (to be described later) of all silver halide grains of 20% or less, and an aspect ratio (grain size / grain size) of 50% or more of the total projected area of the silver halide grains. Tabular grains having a grain thickness of 5 or more, preferably 60% or more of the total projected area are tabular grains having an aspect ratio of 7 or more, and more preferably 70% of the total projected area.
The above are tabular grains having an aspect ratio of 9 or more.

The grain size of the tabular grains is represented by a circle equivalent diameter of the projected area of the silver halide grains (diameter of a circle having the same projected area as the silver halide grains), and is 0.1 to 5.0.
μm is preferred, and more preferably 0.5 to 3.0 μm.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 70,000, and measuring the particle diameter on the print or the area at the time of projection (measurement particles). The number shall be 1000 or more indiscriminately).

Here, the average particle diameter r is defined as the particle diameter ri at which the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle diameter ri becomes maximum (3 significant digits, minimum Digits are rounded off to the nearest 5).

The silver halide emulsion 1 according to the present invention is preferably a monodispersed silver halide emulsion. Here, the monodispersed silver halide emulsion means ± 20% around the average grain size r.
% Of the total silver halide grain mass is preferably 60% or more of the total silver halide grain mass.
It is more preferably at least 70%, further preferably at least 80%.

The highly monodispersed emulsion according to the present invention has a distribution of not more than 20% when defined by (standard deviation / average particle size) × 100 = coefficient of variation of particle size (%), More preferably, it is 16% or less. here,
The average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

The tabular grains according to the present invention have dislocation lines in both the central region and the peripheral region of the main plane. The central region of the main plane of the tabular grains referred to herein has a radius of 80% of the radius of a circle having the same area as the main plane of the tabular grains, and the thickness of the tabular grains in the circular portion when the center is shared. Is a region that has On the other hand, the outer peripheral region of a tabular grain refers to a region having an area corresponding to an annular region outside the central region, existing around the tabular grain, and having a thickness of the tabular grain.

The number of dislocation lines present in one particle is measured as follows. A series of particle photographs with different inclination angles with respect to the incident electrons are taken for each particle to confirm the existence of dislocation lines. At this time, if the number of dislocation lines can be counted, the number of dislocation lines is counted. For example, when dislocation lines exist densely or dislocation lines intersect each other,
If the number of dislocation lines per particle cannot be counted, it is counted that there are many dislocation lines.

Many of the dislocation lines existing in the central region of the main plane of the tabular grains according to the present invention form a so-called dislocation network, and the number thereof may not be clearly counted.

On the other hand, the dislocation lines existing in the outer peripheral region of the tabular grains according to the present invention are observed as lines extending radially from the center of the grains toward the sides, but often meander.

The tabular grains according to the present invention have a number ratio of 30.
% Or more have dislocation lines in both the central region and the outer peripheral region of the main plane, and the number of dislocation lines in the outer peripheral region is 20 or more per particle. ) Has dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 1
Preferably at least 30 particles per particle, 70%
More preferably, the tabular grains having the above (number ratio) have dislocation lines in both the central region and the outer peripheral region of the main plane, and the number of dislocation lines in the outer peripheral region is 40 or more per grain.

As a method for introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jet, a fine grain emulsion containing silver iodide , A method of adding only a solution containing iodide ions,
Dislocations that originate dislocation lines can be formed at desired positions using a known method such as a method using an iodide ion releasing agent as described in No. 1. Among these methods, a method of adding a fine grain emulsion containing silver iodide and a method of using an iodide ion releasing agent are particularly preferable.

In the present invention, Research D
publication magazine no. 308119, p. 1001
It is preferable to use a DIR coupler described in Section VII-F or the like in combination. Specifically, it is preferable to use the following compound in the blue-sensitive layer.

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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When a color light-sensitive material is constituted by using the silver halide emulsion according to the present invention, the silver halide emulsion comprises:
Use those that have been subjected to physical ripening, chemical ripening and spectral sensitization.

The additive used in such a step is R
D17643, page 23, section III to page 24, section VI-M, RD1
8716, pages 648 to 649 and RD308119, 9
It is described in page 96, section III-A to page 1000, section VI-M.

Known photographic additives that can be used in the present invention are also RD17643, page 25, VIII-A to page 27.
Section XIII, RD18716, pages 650 to 651, RD30
8119, page 1003, paragraphs VIII-A to 1012, XXI-E
Those described in the section can be used.

Various couplers can be used in the color light-sensitive material. Specific examples thereof are RD17643, 25
Page VII-C to G, RD308119, page 1001 VII-
It is described in sections C to G.

The additive used in the present invention is RD3081
19, page 1007, section XIV.

In the present invention, the aforementioned RD 17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

The light-sensitive material includes RD308119, 1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The photosensitive material is RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

The silver halide emulsion according to the present invention can be used for various color light-sensitive materials represented by general or movie color negative films, slide or television color reversal films, color papers, color positive films and color reversal papers. Can be preferably applied.

Next, the compounds represented by the general formulas (S-1) and (S-
The spectral sensitizing dye represented by 2) will be described.

As each substituent such as a benzene ring and a naphthalene ring formed by Z _{1 and} Z ₂ , a lower alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, i -Propyl group, t-pentyl group, methylthioethyl group, methoxyethyl group, etc.), halogen atom (fluorine, chlorine, bromine atom, etc.), vinyl group, styryl group, aryl group (for example, phenyl group, p-tolyl group, p-bromophenyl group, trifluoromethyl group, alkoxy group (methoxy group, ethoxy group, i-propyl group, etc.), aryloxy group (phenoxy group, p-tolyloxy group, etc.), alkylthio group (for example, methylthio group , An ethylthio group, a benzylthio group, etc.), an arylthio group (for example, phenylthio group, p-bromophenylthio group, p-
Methoxyphenylthio group, etc.), carbonyloxy group (eg, acetyloxy group, propanoyloxy group, benzoyloxy group, etc.), amino group (eg, amino group, dimethylamino group, anilino group, etc.), heterocyclic group (pyridyl group) Group, pyrrolyl group, furyl group, thienyl group, imidazolyl group, thiazolyl group, pyrimidinyl group, etc., acyl group (eg, acetyl group, benzoyl group, etc.), cyano group, carbamoyl group (eg, carbamoyl group, N, N- Dimethylcarbamoyl group, morpholinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N-phenylsulfamoyl group, morpholinosulfonyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, o-hydroxy) Benzoylamino group), alkyl sulfo Arylamino group or an arylsulfonylamino group (e.g., methanesulfonylamino group,
Benzenesulfonylamino group, etc., alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, trifluoroethoxycarbonyl group, etc.), hydroxyl group, carboxyl group, alkylsulfonyl group, and arylsulfonyl group (eg, methanesulfonyl group, ethane Sulfonyl group, benzenesulfonyl group, etc.),
It is arbitrarily selected from a trifluoromethylsulfinyl group and the like, and can be substituted at any position.

Examples of the aliphatic group represented by R ₁ and R ₂ include a branched or straight-chain alkyl group having 1 to 10 carbon atoms (methyl, ethyl, propyl, butyl, pentyl,
i-pentyl group, 2-ethylhexyl group, octyl group,
Decyl group), an alkenyl group having 3 to 10 carbon atoms (2
-Propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group and the like, and an aralkyl group having 7 to 10 carbon atoms (for example, , Benzyl group, phenethyl group, etc.)
Is mentioned.

The above-mentioned groups further have 1 to 5 carbon atoms.
A lower alkyl group, a halogen atom, a vinyl group, an aryl group, a trifluoromethyl group, an alkoxy group, an aryloxy group, a cyano group, a sulfonyl group, an alkoxycarbonyl group (for example, ethoxycarbonyl group, butoxycarbonyl group, etc.), amino Group, aryl group, heterocyclic group, acyl group, ureido group (eg, ureido group, 3-methylureide group, 3-phenylureide etc.), thioureido group (eg, thioureido group, 3-methylthioureido group, etc.), alkylthio Groups, arylthio groups, heterocyclic thio groups (eg, 2-thienylthio group, 3-thienylthio group, etc.), carbonyloxy groups, acylamino groups, groups such as thioamide groups (eg, thioacetamide groups, thiobenzoylamino groups, etc.), Or a sulfo group, a carboxyl group,
Phosphono group, sulfato group, hydroxyl group, mercapto group, sulfino group, carbamoyl group (eg, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), sulfonamide group (eg, methanesulfonamide group, butanesulfonamide group, etc.), sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.) ), Acylaminosulfonyl groups (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl groups (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), Sulfinyl aminocarbonyl group (e.g., methanesulfinyl aminocarbonyl group, such as ethanesulfinyl aminocarbonyl group), may be substituted with a hydrophilic group such as a sulfoamino group.

Specific examples of the aliphatic group in which these hydrophilic groups are substituted include a carboxymethyl group, a carboxyethyl group, a carboxybutyl group, a carboxypentyl group and a carboxypentyl group.
-Sulfate butyl group, 3-sulfopropyl group, 2-
Hydroxy-3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 3-sulfopentyl, 3
-Sulfinobutyl group, 3-phosphonopropyl group, hydroxyethyl group, N-methanesulfonylcarbamoylmethyl group, N-acetylaminosulfonylmethyl group, sulfoaminopropyl group, 2-carboxy-2-propenyl group, o-sulfo Each group includes a benzyl group, a p-sulfophenethyl group, a p-carboxybenzyl group and the like.

(X ₁ ) _n1 is included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye. Therefore, n1 can take an appropriate value of 0 or more as needed.

Specific examples of typical cations include proton, organic ammonium ion (each ion such as triethylammonium, triethanolammonium and pyridinium), and inorganic cation (each cation such as lithium, sodium, potassium, calcium and magnesium). Specific examples of the acid anion include, for example, a halogen ion (each ion such as chlorine, bromine and iodine), an acid ion (p-toluenesulfonic acid, perchloric acid, boron tetrafluoride, sulfuric acid, methyl sulfate) , Ethyl sulfate, methanesulfonic acid, trifluoromethanesulfonic acid, etc.).

Specific examples of the spectral sensitizing dyes represented by formulas (S-1) and (S-2) (hereinafter also referred to as blue-sensitive sensitizing dyes of the present invention) are shown below. Is not limited to these.

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The above general formula (S-1) and general formula (S-2)
The sensitizing dye represented by may be a known compound, for example,
U.S. Pat. Nos. 3,149,105 and 2,238,2
No. 31, British Patent No. 742,112 or "The Cyanine Soybeans and Related Compounds" by FM Hama (Interscience Publishing, NY, 1964), p. 55 et seq. , Those not described can be synthesized by referring to a similar method.

The above general formulas (S-1) and (S-2)
The addition amount of the sensitizing dye represented by the formula (1) and the sensitizing dye according to the present invention is 1 × 10 ^-5 to 1 / mol per silver halide.
× 10 ^-2 mol, more preferably 5 mol
It is from × 10 ^{-5 to} 5 × 10 ^-3 mol. In addition, the general formula (S-
When the dye represented by the general formula (S-2) is used in combination with the dye represented by the general formula (S-1),
The ratio of the added amount of the dye represented by 2) is 1:50 in molar ratio.
５０50: 1 is preferred, more preferably 1:20.
To 20: 1, particularly preferably 1:10 to 10: 1.

When the sensitizing dyes represented by formulas (S-1) and (S-2) are added, they may be added simultaneously to the silver halide emulsion or separately. or,
Two or more dyes represented by formula (S-1) or two or more dyes represented by formula (S-2) may be used in combination.

In the present invention, formulas (S-1) and (S
The method of adding the sensitizing dye represented by each of -2) can be a commonly known method. For example, a method of dissolving in an appropriate solvent (methanol, ethanol, propanol, fluorinated alcohol, 1-methoxyethanol, water or an acid or alkali aqueous solution having an appropriate pH value) and adding it to the emulsion in the form of a solution, US Patent No.3,4
No. 69,987, etc., a method of dissolving in a volatile organic solvent and dispersing this solution in a hydrophilic colloid, and adding a dispersion to the emulsion, as described in JP-B-46-24185, etc. And a method of dissolving a water-insoluble dye or dispersing it in a water-soluble solvent, and adding this dispersion to an emulsion.

In the present invention, the compound represented by the general formula (S-
It is preferable that the sensitizing dyes represented by 1) and (S-2) are added to the silver halide emulsion in a solid state. In order to add the dyes represented by formulas (S-1) and (S-2) in a solid state to a silver halide emulsion, a method of adding them in a granular state or a method of adding them in a powder state And a method of dispersing in an appropriate liquid and adding as a dispersion.

In the present invention, general formula (S-1):
A method is preferred in which the sensitizing dye represented by (S-2) is dispersed in water in a state substantially free of an organic solvent, and is added to the emulsion as a dispersion. In order to disperse the sensitizing dye in water substantially without an organic solvent, various dispersion methods are effectively used. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser, or the like is used. Among them, a high-speed stirrer is preferably used in the present invention.

The above-mentioned organic solvent is a solvent containing a carbon atom and liquid at room temperature. Conventionally, especially as a solvent for the sensitizing dye, a water-miscible organic solvent, for example, alcohols, ketones,
Nitriles, alkoxy alcohols and the like have been used. Specifically, methanol, ethanol, propyl alcohol, i-propyl alcohol, ethylene glycol,
Propylene glycol, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol,
-Ethoxyethanol and the like.

In the present invention, “contains substantially no organic solvent” refers to a state in which the above-mentioned organic solvent is 10% or less, preferably 5% or less, particularly preferably 3% or less by mass with respect to water.

As a high-speed stirring type disperser, for example, FIG.
As shown in FIG. 1A, there is a tank comprising a tank 1, a dissolver 2, a vertical shaft 3, and a dispersion 4. FIG. 1B shows the impeller 5 and the wings 6 and 7 that constitute the dissolver 2.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on a vertical axis or a multi-axis dissolver having a plurality of vertical axes. In addition to the dissolver alone, a high-speed stirring type disperser having an anchor blade is more preferable. As a specific working example, after water is put into a temperature-adjustable tank, a certain amount of the sensitizing dye powder is put, and the mixture is stirred for a certain period of time under a temperature control with a high-speed stirrer, crushed, Spread.

The pH and the temperature at the time of mechanically dispersing the sensitizing dye are not particularly limited. However, at low temperatures, the dispersion does not reach the desired particle size even after long-time dispersion, and re-aggregation or decomposition occurs at high temperatures. As a result, there is a problem that desired photographic performance cannot be obtained, and a problem that the viscosity of the solution system is lowered when the temperature is increased, so that the efficiency of pulverizing and dispersing solids is greatly reduced. Therefore, the dispersion temperature is preferably 15 to 50 ° C. Further, the stirring rotation speed at the time of dispersion requires a long time to obtain a desired particle size at a low rotation speed, and at too high a rotation speed, bubbles are involved and the dispersion efficiency is reduced. Dispersing is preferred.

The dispersion used in the present invention refers to a suspension of a sensitizing dye, and preferably has a sensitizing dye having a mass ratio of 0.2 to 5.0% in the suspension. Used.

The dispersion of the sensitizing dye prepared according to the present invention may be added directly to the silver halide emulsion or may be appropriately diluted before addition. Is used.

In dispersing the sensitizing dye in water, a surfactant may be used. The surfactant referred to here includes an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant.

The general formulas (S-1) and (S-
The dye represented by 2) may be simultaneously dispersed in water,
They may be dispersed separately.

The general formulas (S-1) and (S-
The addition time of the dye represented by 2) may be any time as long as it is during the period from the formation of silver halide grains to immediately before coating, but from the end of silver halide grain formation to the end of chemical sensitization. It is preferably added during a period. It is particularly preferable that the compound is added during a period from completion of silver halide grain formation to before addition of a chemical sensitizer.

The compound represented by formula (A-1) according to the present invention will be described. In the general formula (A-1), R _A11 and R _A12 each represent a substituent, and R _A13 to R _A11
A16 represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, a halogen atom, and a cyano group.
And the substituents described on page 1564. R _A11 and R _A12 may be the same or different, R _A11 to R
_A16 may combine with each other to form a cyclic compound. R _{A11 to} R _A16 may be linear or branched.

R _A11 and R _A12 are preferably an alkyl group,
It is an aryl group or an alkenyl group, and R _{A13 to} R _A16 are preferably a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or a halogen atom.

The compound represented by the general formula (A-1) may be contained in any layer of the silver halide color photographic light-sensitive material of the present invention. It is preferable to include the dye-forming coupler in the same layer as the dye-forming coupler, since the effects described in the present invention can be remarkably obtained.

The compound represented by formula (A-1) may be used in an amount of 0.01 to 100 times by mass the dye-forming coupler represented by formula (Y-1). In view of the physical properties of the silver halide color photographic light-sensitive material, it is preferably used in the range of 0.05 to 5 times. The compound represented by the general formula (A-1) is preferably used by emulsifying and dispersing. Further, the compound represented by the general formula (Y
It is preferably dispersed in the same dispersion as the dye-forming coupler represented by -1).

Specific examples of the compound represented by formula (A-1) according to the present invention are shown below, but the compound represented by formula (A-1) according to the present invention is not limited to these. Not done.

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Next, the compound represented by formula (A-2) according to the present invention will be described. In Formula (A-2), R _{A21 to} R _A25 each represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, a halogen atom, a cyano group, and a hydroxyl group, which are described in Physics and Chemical Dictionary (published by Iwanami Shoten, 3rd edition), pages 1562-1564. And substituents. R _A21 to R _A25 may be the same or different from each other, R _A21 to R _A25 may be bonded to form a cyclic compound with each other. R _{A21 to} R _A25 may be linear or branched. At least one of R _{A21 to} R _A25 is preferably a substituent. R _A21 -R
_A25 is preferably a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or a halogen atom.

The compound represented by formula (A-2) may be contained in any layer in the silver halide color photographic light-sensitive material of the present invention, but is represented by formula (Y-1). It is preferable to include it in the same layer as the dye-forming coupler because the effects of the present invention can be remarkably obtained.

The compound represented by formula (A-2) may be used in an amount of 0.01 to 100 times by mass the dye-forming coupler represented by formula (Y-1). In view of the physical properties of the silver halide color photographic light-sensitive material, it is preferably used in the range of 0.05 to 5 times. The compound represented by the general formula (A-2) is preferably used by emulsifying and dispersing. Further, the compound represented by the general formula (Y
It is preferred that the dye-forming coupler represented by -1) is used after being dispersed in the same dispersion liquid.

Hereinafter, the compounds represented by the general formula (A-
Specific examples of the compound represented by 2) are shown below, but the compound represented by formula (A-2) used in the present invention is not limited thereto.

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The compound represented by the general formula (I) according to the present invention described in claim 7 will be described.

In the general formula (I), the aliphatic group represented by R ₁ and R ₂ is a linear or branched alkyl or alkenyl having 1 to 30, preferably 1 to 20 carbon atoms.
Each group such as alkynyl or cycloalkyl is exemplified.
Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-
Butyl, 2-ethylhexyl, allyl, 2-butenyl,
Each group includes 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclododecyl and the like. Examples of the aromatic group represented by R ₁ and R ₂ include those having 6 to 20 carbon atoms, and specific examples include phenyl, naphthyl, and anthranyl. The heterocyclic group represented by R ₁ and R ₂ may be a single ring or a condensed ring, and is a 5- to 6-membered heterocyclic group having at least one of O, S and N atoms and an amine oxide group in the ring. Is mentioned.

Specifically, for example, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan,
Examples include thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole, and groups derived from these benzerogues. R ₁ and R ₂ form a ring,
A 4- to 7-membered ring can be mentioned. It is preferably a 5- to 7-membered ring.

Preferred groups for R ₁ and R ₂ are a heterocyclic group and an aromatic group, more preferably a heteroaromatic group. The aliphatic group, aromatic group or heterocyclic group represented by R ₁ and R ₂ may be further substituted with a substituent, and the substituent may be a halogen atom (eg, a chlorine atom, a bromine atom, etc.). An alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group, a trifluoromethyl group, a t-butyl group, etc.), a cycloalkyl group (eg, a cyclopentyl group,
Cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (eg, methoxy group) Ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 4-methoxyphenoxy group, etc.), cyano group, acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (E.g., methylthio, ethylthio, butylthio, etc.), arylthio (e.g., phenylthio,
p-methylphenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group, 3,3-dimethylureido group, 1,3- Dimethylureido group, etc.), sulfamoylamino group (eg, dimethylsulfamoylamino group, diethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl Group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, p-chlorophenoxycarbonyl Base ), A sulfonyl group (for example,
Methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (eg, methylamino group, ethylamino group, dimethylamino group, etc.), hydroxyl Group, nitro group, nitroso group, amine oxide group (for example, pyridine oxide group), imide group (for example, phthalimide group), disulfide group (for example, benzene disulfide group, benzothiazolyl-2-disulfide group, etc.), hetero Ring group (for example, pyridyl group, benzimidazolyl group, benzthiazolyl group,
Benzoxazolyl group, etc.). Substituents containing an electron withdrawing group are particularly preferred. R ₁ and R ₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. m is an integer of 2 to 6, preferably 2
~ 3.

Hereinafter, the compounds represented by the general formula (I) used in the present invention will be described.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

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As the selenium sensitizer according to the present invention, a selenium compound disclosed in a conventionally known patent can be used. That is, the emulsion is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include, for example, JP-B-44-15748 and JP-B-43-13.
No. 489, JP-A-4-25832 and JP-A-4-10924.
It is preferable to use the compound described in No. 0. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, 2
-Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium. No.

Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. One skilled in the art would speak of an unstable selenium compound as a sensitizer for photographic emulsions, as long as selenium is unstable, the structure of the compound is not critical and the organic moiety of the selenium sensitizer molecule Is generally understood to have no role other than to carry selenium and make it present in the emulsion in an unstable form, and unstable selenium compounds having such a broad concept are advantageously used.

Non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-3449.
Compounds described in Nos. 2 and 52-34491 are used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof.

In the present invention, a tellurium sensitizer can also be used. Specific examples of preferable compounds are shown below as the selenium sensitizer and the tellurium sensitizer according to the present invention, but are not limited thereto.

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These selenium sensitizers and tellurium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent.
No. 8, No. 4-140742, No. 5-1381, No. 5-1385 or No. 5-1388 and can be added at the time of chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer and the tellurium sensitizer used are not limited to one kind, and two or more of the above-described selenium sensitizer and tellurium sensitizer can be used in combination. An unstable selenium compound and a non-unstable selenium compound may be used in combination. Further, at least one of each of the selenium sensitizer and the tellurium sensitizer may be used in combination. The addition amount of the selenium sensitizer and tellurium sensitizer used in the present invention depends on the activity of the selenium sensitizer and tellurium sensitizer used, the type and size of silver halide, the ripening temperature and time, and the like. Different,
It is preferably at least 1 × 10 ⁻⁸ mol per mol of silver halide, and more preferably from 1 × 10 ⁻⁷ mol to 3 × 10 ⁻⁸ mol.
^-5 moles. The temperature of chemical ripening when using a selenium sensitizer and a tellurium sensitizer is preferably 45 ° C. or higher.
More preferably, it is 50 ° C. or more and 80 ° C. or less. pAg
And the pH are arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9. Selenium sensitization and tellurium sensitization are more effective when performed in the presence of a silver halide solvent.

The compound represented by formula (II) according to the invention described in claim 8 will be described.

In the general formula (II), examples of the alkyl group represented by R ₃ include a methyl group, an ethyl group,
Examples include propyl group, i-propyl group, butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group and dodecyl group. These alkyl groups further include a halogen atom (for example, chlorine, bromine, fluorine, etc.) and an alkoxy group (for example,
Methoxy group, ethoxy group, 1,1-dimethylethoxy group, hexyloxy group, dodecyloxy, etc.), aryloxy group (eg, phenoxy group, naphthyloxy, etc.), aryl group (eg, phenyl group) , Naphthyl, etc.), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a 2-ethylhexylcarbonyl group, etc.), an aryloxycarbonyl group (for example, a phenoxycarbonyl group, a naphthyloxycarbonyl group) Alkenyl group (e.g., vinyl group, allyl group, etc.), heterocyclic group (e.g., 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group,
Each group such as piperazyl group, selenazolyl group, sulfolanyl group, piperidinyl group, tetrazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, pyrimidyl group, pyrazolyl group, and furyl ), Alkynyl groups (for example, propargyl groups), amino groups (for example, amino groups, N, N-dimethylamino groups, anilino groups, etc.), hydroxyl groups, cyano groups, sulfo groups, carboxy groups, and sulfonamides It may be substituted by a group (for example, methanesulfonylamino group, ethanesulfonylamino group, butylsulfonylamino group, octylsulfonylamino group, phenylsulfonylamino, etc.).

Examples of the alkenyl group represented by R ₃ include a vinyl group and allyl, and examples of the alkynyl group include propargyl, and examples of the aryl group include a phenyl group and naphthyl. Further, as the heterocyclic group, for example, a pyridyl group (for example,
2-pyridyl, 3-pyridyl, 4-pyridyl, etc.), thiazolyl, oxazolyl, imidazolyl, furyl, chenyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, selenazolyl, sulfolanyl Group, piperidinyl group, pyrazolyl group,
And a tetrazolyl group.

The alkenyl group, alkynyl group, aryl group and heterocyclic group can all be substituted by the same groups as the alkyl groups represented by R ₃ and the substituents of the alkyl groups.

Hereinafter, specific examples of the compound represented by formula (II) will be shown, but the present invention is not limited thereto.

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In the present invention, the compound represented by the general formula (II) is added between the addition of a sensitizing dye and the addition of a chalcogen sensitizer. Spectral sensitizers and supersensitizers can be used,
For example, items II to X of RD38957 and I to XIII of RD40145 can be used.

The chalcogen sensitizer according to the present invention refers to a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer well known in the art. The chalcogen sensitizer is added to a solution containing silver halide grains at the time of chemical sensitization, and causes a decomposition reaction on the surface of the silver halide grains.In the case of a sulfur sensitizer, a sulfur element is added to the selenium sensitizer. In the case, selenium element is released, and in the case of tellurium sensitizer, tellurium element is released.

A typical example of the chalcogen sensitizer in the present invention is a sulfur sensitizer. Specifically, 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3
Thiourea derivatives such as-(2-thiazolyl) thiourea,
Preference is given to rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, thiosulfates, elemental sulfur and the like.
In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable. In addition, U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955 No. and other specifications, West German application published (O
LS) 1,422,869, JP-A-56-24937.
And the sulfur sensitizers described in JP-A-55-45016 and the like can be used. The selenium sensitizer according to the present invention described in claim 7 can also be used as a chalcogen sensitizer.

The amount of the chalcogen sensitizer added in the present invention varies over a considerable range depending on various conditions such as pH, temperature, and the size of silver halide grains. 1 × 10 ^-1 to 1 × 10 ^-7 per
Molar is preferred.

The silver halide color photographic light-sensitive material of the present invention can be produced by the method described in RD17643, pages 28 to 29, section XIX, RD
18716,651 and RD308119,1010
Developing can be carried out by a usual method described in section XIX on page 1011.

The silver halide color photographic light-sensitive material of the present invention is provided with a red, green and blue light-sensitive silver halide emulsion layer,
Each layer can contain a coupler. It is preferable that the coloring dye formed from the coupler contained in each of these layers has a spectral absorption maximum separated by at least 20 nm. As the coupler, it is preferable to use a cyan coupler, a magenta coupler, and a yellow coupler. As a combination of each emulsion layer and a coupler, a combination of a yellow coupler and a blue photosensitive layer, a combination of a magenta coupler and a green photosensitive layer, a combination of a cyan coupler and a red photosensitive layer are used, but are not limited to these combinations. , And other combinations.

In the present invention, a DIR compound can be used. Specific examples of DIR compounds that can be used include, for example, D-1 to D-34 described in JP-A-4-114153, and these compounds can be preferably used in the present invention.

DIR that can be used in the present invention
Specific examples of the compounds other than those described above include, for example, U.S. Pat. Nos. 4,234,678, 3,227,554, 3,647,291, 3,958,993,
No. 4,419,886, No. 3,933,500
JP-A-57-56837 and JP-A-51-13239, U.S. Pat. Nos. 2,072,363 and 2,072.
0,266, Research Disclosure 1981
And those described in December 21,228.

Further, specific examples of the coupler usable in the present invention are described in RD308119 and RD17643.

As the support of the silver halide color photographic light-sensitive material of the present invention, RD17643, p. 28, RD
18716 647-648 and RD 308119
The supports described in XIX can be used.

The silver halide color photographic light-sensitive material of the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in RD308119 VII-K.

The silver halide color photographic light-sensitive material of the present invention can have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in RD308119 VII-K.

To develop the silver halide color light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The Theory of The Photog
rafic ProcessForth Edition
n) Pages 291 to 334 and Journal of the
American Chemical Society (Journa1
of the American Chemical
Society, 73, 3,100 (195
The developer known per se described in 1) can be used, and RD17643 28-2 described above can be used.
Page 9, RD18716 page 615 and RD308119
Development can be carried out by the usual method described in XIX.

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EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, “%” represents “% by mass” unless otherwise specified.

Example 1 (Preparation of emulsion Em-1) [Nucleation and ripening step] The following gelatin aqueous solution-1 in a reaction vessel was kept at 30 ° C, and a mixing and stirring apparatus described in JP-A-62-160128 was used. While stirring vigorously using, the following aqueous silver nitrate solution-1 and aqueous halide solution-1 solution were added at a constant flow rate for 1 minute using the double jet method to form nuclei.

(Aqueous Gelatin Solution-1) Alkali-treated inert gelatin (average molecular weight 100,000) 32.4 g Potassium bromide 9.9 g H ₂ O 13.0 l (Silver nitrate aqueous solution-1) Silver nitrate 50.43 g H ₂ O 225. 9 ml (halide solution -1) potassium bromide 35.33g H ₂ O 224.7ml the addition finished, immediately following aqueous gelatin solution -2 addition, the temperature was raised to 60 ° C. over a period of 30 minutes, the pH 5 .
It was adjusted to 0 and kept in that state for 20 minutes.

(Aqueous Gelatin Solution-2) Alkali-treated inert gelatin (average molecular weight 100,000) 17.5 g Potassium bromide 3.18 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 ( CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by mass methanol solution 0.20 ml H ₂ O 673.5 ml [Particle growth step-1] After the ripening step is completed, the double jet method is used. Silver nitrate aqueous solution-2 and halide aqueous solution-
2 was added with increasing flow rate. After the addition was completed, an aqueous solution of gelatin-3 was added, and subsequently, an aqueous solution of silver nitrate-3 and an aqueous solution of halide-3 were added at an increased flow rate. During this time, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 6 mV using a 1 mol / l potassium bromide solution.

[0190] (aqueous silver nitrate solution -2) nitrate 639.8g H ₂ O 2866.2ml (halide solution -2) Potassium bromide 448.3g H ₂ O 2850.7ml (aqueous gelatin solution -3) alkali-processed inert gelatin (average 175.9 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by mass methanol solution 0 .67ml H ₂ O 4260.1ml (aqueous silver nitrate solution -3) nitrate 989.8g H ₂ O 1437.2ml (halide solution -3) potassium bromide 679.6g iodide 19.35g H ₂ O 1412.0ml [particles Growth step-2] 1 m after completion of the particle growth step-1
ol / l aqueous nitric acid solution, the pH was adjusted to 5.0, then the silver potential in the reaction vessel was adjusted to -19 mV using a 3.5 mol / l aqueous potassium bromide solution. 4 and the halide aqueous solution-4 were added while accelerating the flow rate.

(Aqueous solution of silver nitrate-4) 720.0 g of silver nitrate 1045.6 ml of H ₂ O (aqueous solution of halide-4) 499.3 g of potassium bromide 7.0 g of potassium iodide 1027.1 ml of H ₂ O The grain growth step-1 2, the addition rates of the aqueous silver nitrate solution and the aqueous halide solution were adjusted so that no new silver halide grains were formed, and that the grain size distribution did not deteriorate due to Ostwald ripening between the growing silver halide grains. Optimal control.

After completion of the growth, desalting and washing are performed.
Add gelatin and disperse well.
8. The pAg was adjusted to 8.1. When the obtained emulsion was examined by a replica method, it was found to be a silver halide emulsion composed of hexagonal tabular grains having an average grain size of 1.4 μm, a grain size distribution of 22% and an average aspect ratio of 7. Further, when observed using a transmission electron microscope, almost no particles having dislocation lines were present in Em-1.

(Preparation of Emulsion Em-2) Em-2 was prepared in the same manner as Em-1 except for the following. Em-
2 was examined by a replica method, and the average particle size was 1.4 μm.
It was a silver halide emulsion composed of hexagonal tabular grains having a grain size distribution of 22% and an average aspect ratio of 7. Further, when the state of dislocation lines formed in the silver halide grains was examined using a transmission electron microscope, Em-2 contained 90% or more (number) of grains having 5 or more dislocation lines per grain. did.
Many dislocation lines were formed in the fringe portions of the tabular grains.

[Particle growing step-2 '] Particle growing step-1
After completion, the following aqueous solution-A1 was added, and the pH was adjusted to 9.3 with a 1 mol / l aqueous potassium hydroxide solution to adjust the pH to 4.
The iodine ions were released while aging for a minute. Then 1
pH was adjusted to 5.0 using a mol / l nitric acid aqueous solution,
Next, the silver potential in the reaction vessel was adjusted to -19 mV using a 3.5 mol / l aqueous solution of potassium bromide, and subsequently, an aqueous silver nitrate solution-4 and an aqueous halide solution-4 were added at an accelerated flow rate.

(Aqueous solution-A1) 112.6 g of sodium p-iodoacetamidobenzenesulfonate 1000 ml of H ₂ O (aqueous silver nitrate-4) 720.0 g of silver nitrate 1045.6 ml of H ₂ O (aqueous halide solution-4) Potassium bromide 494. except 4g potassium iodide 14.1g H ₂ O 1027.1ml (preparation of emulsion Em-3) following description was prepared Em-3 in the same manner as Em-2. When Em-3 was examined by a replica method, the average particle size was 1.4 μm, and the particle size distribution was 22 μm.
%, And a silver halide emulsion comprising hexagonal tabular grains having an average aspect ratio of 7.

[Grain Growth Step-1 '] After the ripening step,
Subsequently, silver nitrate aqueous solution-2 and halide aqueous solution-2 were added while accelerating the flow rate using a double jet method. After the addition was completed, an aqueous solution of gelatin-3 was added, and (I-4 solution) was added. Subsequently, an aqueous solution of silver nitrate-3 and an aqueous solution of halide-3 were added at an increased flow rate. After the addition is completed (J
-4 liquid). During this time, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was 1
It was controlled at 6 mV using a mol / l potassium bromide solution.

(I-4 solution) 100 ml of an aqueous solution containing 1 × 10 ⁻⁵ mol of thiourea dioxide per mol of silver halide (J-4 solution) 2.5 × of sodium ethylthiosulfonate per mol of silver halide 100 ml of an aqueous solution containing 10 ^-4 mol 100 ml (Preparation of coating emulsion A) After a part of the emulsion Em-1 was dissolved by heating, a sensitizing dye shown in Table 1 was added, and sodium thiosulfate pentahydrate, triphenylphosphine selec Add an appropriate amount of a mixture of nide, chloroauric acid and potassium thiocyanate,
Aged so that the sensitivity was 1/100 second optimal. At the end of ripening, the stabilizer ST-1 was added, the temperature was lowered, and the mixture was cooled and solidified to obtain Emulsion A.

(Preparation of Coated Emulsions BP) Emulsions BP were obtained by changing the preparation conditions from Emulsion A as shown in Table 1.

[0199]

[Table 1]

(Preparation of a silver halide color photographic light-sensitive material) On a triacetylcellulose film support provided with an undercoat layer, layers having the following compositions are sequentially formed from the support side to form a multilayer color photographic light-sensitive material. Material 101 was produced. The addition amount is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.05 CC-1 0.03 OIL-1 0.10 Gelatin 1.80 Second Layer (Low Sensitivity red-sensitive layer) Silver iodobromide emulsion b 0.36 Silver iodobromide emulsion c 0.12 SD-1 2.2 × 10 ^-5 SD-2 3.0 × 10 ^-5 SD-3 1.0 × 10 ^-4 SD-4 1.0 × 10 ^-4 SD-5 2.0 × 10 ^-4 C-1 0.34 CC-1 0.025 OIL-2 0.22 AS-2 0.001 Gelatin 0. 80 Third layer (medium-speed red-sensitive layer) Silver iodobromide emulsion a 0.39 Silver iodobromide emulsion b 0.39 Silver iodobromide emulsion d 0.53 SD-1 1.7 × 10 ^-4 SD- ^{4 2.5 × 10 -4 SD-5} 3.0 × 10 -4 C-1 0.19 C-2 0.53 CC-1 0.08 DI-1 0.086 DI-4 0.011 OIL-2 0.53 AS-2 0.005 Gelatin 2.30 Fourth layer (high-sensitivity red-sensitive layer) Silver iodobromide emulsion c 0.07 Silver iodobromide emulsion d 1.34 SD-11 0.5 × 10 ^-5 SD-2 6.5 × 10 ^-5 SD-4 2.8 × 10 ^-4 SD-5 2.5 × 10 ^-5 C-1 0.040 C-2 0.126 CC- 1 0.03 DI-1 0.02 DI-4 0.01 OIL-2 0.22 AS-2 0.005 Gelatin 1.10 Fifth layer (intermediate layer) F-1 0.01 Y-10. 09 OIL-1 0.40 AS-1 0.30 Gelatin 1.00 Sixth layer (low-sensitivity green-sensitive layer) Silver iodobromide emulsion b 0.25 Silver iodobromide emulsion c 0.13 SD-6 ^{0 × 10 -5 SD-7 5.5} × 10 -4 M-1 0.28 CM-1 0.040 DI-3 0.007 OIL-1 0.24 AS- 0.005 Gelatin 0.75 7th layer (Medium Sensitivity Green-sensitive layer) Silver iodobromide emulsion e 1.09 SD-6 3.5 × 10 -5 SD-7 1.7 × 10 -4 SD-8 2 0.0 × 10 ^-4 SD-9 1.5 × 10 ^-4 SD-10 2.5 × 10 ^-5 M-1 0.33 CM-1 0.07 CM-2 0.03 DI-2 0.06 OIL-1 0.50 AS-2 0.02 Gelatin 1.10 8th layer (highly sensitive green-sensitive layer) Silver iodobromide emulsion c 0.06 Silver iodobromide emulsion f 1.20 SD-6 3.0 × 10 ^-5 SD-8 3.0 × 10 ^-4 SD-9 3.0 × 10 ^-5 SD-10 3.5 × 10 ^-5 M-1 0.090 CM-2 0.010 DI-30 0.003 OIL-1 0.30 AS-2 0.010 Gelatin 1.00 Ninth layer (yellow filter layer) Yellow colloidal silver 0.10 OIL-1 0.20 A -1 0.20 X-1 0.06 Gelatin 0.85 10th layer (low-sensitivity blue-sensitive layer) Silver iodobromide emulsion g 0.23 Silver iodobromide emulsion h 0.29 Silver iodobromide emulsion i0 .13 SD-11 2.5 × 10 ^-4 SD-12 5.5 × 10 ^-4 SD-13 1.5 × 10 ^-5 Y-1 0.96 OIL-1 0.29 AS-2 0.005 X-1 0.08 Gelatin 1.80 Eleventh layer (highly sensitive blue-sensitive layer) Silver iodobromide emulsion j 0.60 Silver iodobromide emulsion h 0.26 SD-11 5.0 × 10 ^-5 SD- 12 1.0 × 10 ^-4 SD-13 5.0 × 10 ^-5 Y-1 0.31 DI-1 0.06 OIL-1 0.08 AS-2 0.005 X-1 0.07 Gelatin 0 .80 12th layer (first protective layer) Silver iodobromide emulsion k 0.30 UV-1 0.10 UV-2 0.06 Liquid paraffin 0.50 X-1 .15 gelatin 1.50 13th layer (second protective layer) PM-1 0.15 PM-2 0.05 WAX-1 0.02 gelatin 0.56 The characteristics of the silver iodobromide emulsion used above were as follows. (The average particle size is one side length of a cube having the same volume).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide emulsion a 0.56 2.4 5.5 b 0.38 8.0 Octahedral twin c 0.27 2.0 1.0 d 0.70 2.4 6.4 e 0.65 8.0 6.5 f 0.85 2.9 6.4 g 0.74 3.5 6.2 h 0.44 4.2 6.1 i 0.30 1.9 5.5 j 1.00 8.0 2.0 k 0.03 2.0 1.0 The above-mentioned sensitizing dye was added to each of the above emulsions, and after ripening, Triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added, and a product subjected to chemical sensitization according to a conventional method so as to optimize fog and sensitivity was used.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1, two kinds of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000, inhibitors AF-3, AF-4, AF-5,
Hardener H-1 and preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

[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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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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The yellow couplers (Y-1) used in the tenth and eleventh layers in the light-sensitive material construction of Sample 101 were changed to the couplers shown in Table 1 in equimolar amounts. Samples 102 to 116 were prepared in the same manner as Sample 101 except that the emulsions shown were changed.

<< Sensitivity Immediately After Coating >> Each sample was exposed to white wedge and subjected to the following development processing. After drying, Xr
The blue light transmission density was measured by a densitometer manufactured by ITE to obtain sensitometry.

Sensitometric minimum concentration (fog) +
The sensitivity was obtained from the reciprocal of the exposure amount giving a density of 0.3, and the sensitivity was shown as a relative value when the value of sample 101 was set to 100.

<< Stability of Latent Image >> Each of the samples exposed to the same exposure as described above was treated at 40 ° C. and 80% RH (relative humidity) for 7 days.
After standing for a day, the same treatment as that of the sample immediately after coating was performed to determine the sensitivity. The sensitivity after storage when the sensitivity immediately after application of each sample was taken as 100 was shown as a relative value. A value closer to 100 indicates that the latent image storage stability is more excellent.

<< Reference Color Development Processing >> Processing Step Processing Time Processing Temperature Replenishment Quantity * Color Development 3 min 15 sec 38 ± 0.3 ° C. 780 ml Bleaching 45 sec 38 ± 2.0 ° C. 150 ml Fixing 1 min 30 sec 38 ± 2.0 ° C. 830 ml Stabilizing 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 55 ± 5.0 ℃ - * the replenishing amount is a value per photosensitive material 1 m ^2.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter, and potassium hydroxide or 20% sulfuric acid was added. Adjust pH to 0.06 using

Color developing replenisher Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and adjust the pH to 0.18 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid ammonium iron (III) salt 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Add water to make 1 liter, and use aqueous ammonia or glacial acetic acid. Adjust the pH to 4.4.

Bleach replenisher Water 700 ml 1,3-Diaminopropanetetraacetate ammonium iron (III) 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.4 using aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml After adding water to 1 liter, the pH is adjusted to 8.5 using ammonia water or 50% sulfuric acid.

[0228]

[Table 2]

From Table 2, it is clear that the sample of the present invention has high sensitivity, good latent image stability, and low fog as compared with the comparative sample.

[0230]

According to the present invention, a silver halide color photographic light-sensitive material having high sensitivity, low fog and improved latent image stability can be provided.

[Brief description of the drawings]

FIG. 1A is a schematic view of a high-speed stirring type disperser preferably used in the present invention, and FIG. 1B is a perspective view of an impeller.

[Explanation of symbols]

 Reference Signs List 1 tank 2 dissolver 3 vertical axis 4 dispersion liquid 5 impeller 6, 7 blades

[Procedure amendment]

[Submission date] April 5, 2001 (2001.4.5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0161

[Correction method] Change

[Correction contents]

[0161]

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──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/08 G03C 1/08 1/09 1/09 1/16 1/16 1/29 1/29 1 / 34 1/34 7/26 7/26 7/392 7/392 A

Claims (8)

[Claims] At least one side of each of the supports is at least 2
In a silver halide color photographic light-sensitive material having a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, the blue light-sensitive layer has the following general formula (Y-1) or (Y- 2)
And silver halide grains containing at least one yellow coupler selected from the group consisting of (Y-3) and reduction sensitized silver halide grains. Photosensitive material. Embedded image [Wherein, R ₁ represents a substituent, and R ₂ represents an alkyl group having 7 to 20 carbon atoms. R ₃ represents a hydrogen atom or a halogen atom, and m represents an integer of 1 to 5. Z ₁ is> NR ₄ (R
₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or -O- and, Z ₂
Is> NR ₅ (R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or> C
(R ₆ ) (R ₇ ) (R ₆ and R ₇ represent a hydrogen atom or a substituent). [Chemical formula 2] [Wherein, R ₁ represents a substituent, and R ₈ represents an alkyl group, a cycloalkyl group, or an aryl group. R ₉ represents an alkyl group or a cycloalkyl group, and the sum of the carbon numbers of R ₈ and R ₉ is 7 to 20. R ₃ represents a hydrogen atom or a halogen atom, and m represents an integer of 1 to 5. Z ₁ is> NR ₄ (R
₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or -O- and, Z ₂
Is> NR ₅ (R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or> C
(R ₆ ) (R ₇ ) (R ₆ and R ₇ represent a hydrogen atom or a substituent). [Chemical formula 3] [Wherein, R ₁₀ represents an alkyl group having diffusion resistance;
₃ represents a hydrogen atom or a halogen atom. And Z _1> N-R
₄ (R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or -O-,
Z ₂ is> NR ₅ (R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or> C (R ₆ ) (R ₇ ) (R ₆ and R ₇ are hydrogen Represents an atom or a substituent). ] 2. The method according to claim 1, wherein at least one side of the support has at least two
In a silver halide color photographic light-sensitive material having a photographic constituent layer composed of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, the blue-sensitive layer has the formula (Y-
1) a spectral sensitizing dye containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3), and represented by the following general formula (S-1); 2
A silver halide color photographic light-sensitive material characterized by containing at least one species. Embedded image [In the formula, Y ₁ and Y ₂ independently represent an oxygen, a sulfur atom, a selenium atom or —N (R ₃ ) —. Z ₁ and Z ₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring. R ₁ and R ₂ each represent an aliphatic group, and R ₃ represents a lower alkyl group. X ₁ represents a charge balancing counter ion;
n1 represents an integer for neutralizing the charge of the whole molecule. ] 3. The silver halide color photograph according to claim 2, wherein the spectral sensitizing dye represented by the general formula (S-1) is represented by the following general formula (S-2). Photosensitive material. Embedded image [In the formula, Y ₁ represents an oxygen atom, Y ₂ represents a sulfur atom, a selenium atom or —N (R ₃ ) —. Z ₁ and Z ₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring. R ₁ and R ₂ each represent an aliphatic group, and R ₃ represents a lower alkyl group. X ₁ represents a charge-balancing counter ion;
Represents the number required to neutralize the charge of the whole molecule. ] 4. The silver halide color photographic light-sensitive material according to claim 3, which contains reduction sensitized silver halide grains. 5. On each side of the support, at least two
In a silver halide color photographic light-sensitive material having a photographic constituent layer composed of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, the blue-sensitive layer has the formula (Y-
1) A silver halide containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3), and containing the following silver halide emulsion 1. Color photographic light-sensitive material. (Silver halide emulsion 1) [The variation coefficient of the particle size of all silver halide grains is 20% or less, and 50% or more of the projected area of all silver halide grains has a tabular halide having an aspect ratio of 5 or more. 30% or more (number ratio) of the silver halide grains and tabular silver halide grains have dislocation lines in the central region of the main plane and the fringe portion, and further have 20 or more transition lines in the fringe portion per grain. Silver halide emulsion present. ] 6. On each side of the support at least two
In a silver halide color photographic light-sensitive material having a photographic constituent layer composed of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, the blue-sensitive layer has the formula (Y-
1) containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3), and represented by the following general formula (A-1) or (A-2) Silver halide color photographic light-sensitive material comprising at least one compound selected from the group consisting of: Embedded image Wherein, R _A11, R _A12 each represents a substituent, R _A13
To R _A16 each represent a substituent or a hydrogen atom. [Formula 7] [Wherein, R _{A21 to} R _A25 each represent a hydrogen atom or a substituent. ] 7. On each side of the support, at least two
In a silver halide color photographic light-sensitive material having a photographic constituent layer composed of a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-light-sensitive layer, the blue-sensitive layer has the formula (Y-
1) containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3) and a compound represented by the following formula (I), and selenium-sensitized; A silver halide color photographic material comprising silver halide grains. Formula (I) R _1- (S) _m -R ₂ [wherein, R ₁ and R ₂ are each an aliphatic group, an aromatic group, a heterocyclic group, or can be bonded to each other to form a ring Represents an atomic group. R ₁ and R ₂ may be the same or different, and when R ₁ and R ₂ are an aliphatic group, they may combine with each other to form a ring. m represents an integer of 2 to 6. ] 8. On each side of the support at least two
In a silver halide color photographic light-sensitive material having a photographic constituent layer consisting of a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, the blue light-sensitive layer has the general formula (Y
-1) containing at least one yellow coupler selected from the group consisting of (Y-2) and (Y-3), and silver halide grains containing a compound represented by the following formula (II): And during the preparation of the silver halide grains, the compound represented by the general formula (II) is added between the addition of a sensitizing dye and the addition of a chalcogen sensitizer. Silver color photographic light-sensitive material. Embedded image [Wherein, X represents N or CR ′, R ′ is a hydrogen atom,
Represents an alkyl group or an aryl group. R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. n is 0 or 1
Represents R ₃ and R ₄ -SO ₃ H, -COOH, -O
H, -NHR ₅ and has at least one group selected from the group consisting of salts thereof. R ₅ represents an aliphatic group or an aromatic group. ]