JPH05204071A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material excellent in sharpness, whitenss of base, and production stability with which stable picture images can be obtd. even for exposure and processing of lots of sheets by incorporating such silver halide emulsion particles that has a part containing a specified amt. of silver bromide and consists of a specified amt. of silver chloride into a silver halide emulsion layer having high chloride content, and further incorporating a specified compd. into layers. CONSTITUTION:The silver halide emulsion layer having high chloride content contains silver halide emulsion particles comprising 98-99.9mol% silver chloride and having a part containing >=30mol% silver bromide. This silver halide emulsion layer or one of other photographic layers contains at least one kind of compd. expressed by formulae I-III. In formulae I-III, V1 and V2 are hydrogen atoms, cyano groups, etc., W1 and W2 are hydrogen atoms,-NR3R4, etc., X1 and X2 are hydrogen atoms, cyano groups, etc., L1-L9 are methine groups, (m), (l) and (k) are 0, 1 or 2, (n) is 1, 2 or 3, M<n+> is a n-valent cation, and Y1 and Y2 are oxygen atoms or NR13.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material which is excellent in sharpness, whiteness and manufacturing stability, and which can provide a stable image even during continuous exposure and development of a large number of sheets. It is a thing.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials, especially silver halide color photographic light-sensitive materials are used very much today because of their high sensitivity, excellent gradation and sharpness.

However, the development processing of a silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare the processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, and a dark room is required. There are drawbacks such as a long time from the start of operation until the first print is obtained. In order to make up for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, until now, engineers who were skilled in everything from the development of color negatives to the production of color prints have focused exclusively on a small number of large development laboratories. The method of doing has been adopted.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. Therefore, a so-called minilab, which is capable of consistently performing from color negative development to color print production in a small space such as at a photo shop, is rapidly becoming popular.

In the photo shops where these mini laboratories are installed, the usage for producing a large number of prints of the same scene such as a postcard is increasing due to the diversification of print use purposes, and the development time at the time of print production is quick. This has created a demand for improving the stability of an image when continuously exposing and developing a large number of identical scenes.

In order to improve the sharpness of the silver halide photographic light-sensitive material, antihalation dyes and antiirradiation dyes are effectively used.

The dye used for such a purpose has good spectral absorption characteristics according to the purpose of use, is completely eluted or decolorized in a photographic processing solution, and has no residual color contamination by the dye after processing. Various conditions such that the photographic emulsion that has been spectrally sensitized does not have adverse photographic effects such as increase or decrease in sensitivity and fog, and that it has excellent stability over time in the light-sensitive material and does not discolor or fade. Must be satisfied.

A large number of dyes have been proposed to date for the purpose of finding a dye satisfying the above conditions,
For example, U.S. Pat. Nos. 506,385, 3,247,127 and Japanese Patent Publication No. 43.
Oxonol dyes described in No. 13168 and the like,
Styryl dyes represented by US Pat. No. 1,845,404, US Pat. Nos. 2,493,745, 3,148,187, and 3,282,69.
Merocyanine dyes described in US Pat.
Anthraquinone dye represented by 5,752, U.S. Pat.
40,887, 3,544,325, JP-B 31-10578 and JP-A 51-3623 include benzylidene dyes and the like. Among them, the oxonol dye is known as a dye excellent in the above-mentioned various properties.

However, in the case of the method of adding these dyes by dissolving them in water or an organic solvent miscible with water, which is a general addition method in the photographic constituent layers, the dye is not limited to the layer to be dyed. In the case of a silver halide emulsion that has been spectrally sensitized by diffusing into the silver halide emulsion layer, it may cause spectral sensitization to an unfavorable area or increase in fog, and images during continuous exposure and development It has the drawback of lacking stability.

On the other hand, the development processing time has been remarkably shortened by employing a silver halide emulsion containing silver chloride at a high concentration. However, a silver halide emulsion containing a high concentration of silver chloride has a drawback that it changes during storage over time and stable performance cannot be obtained during production.

In JP-A-1-183647, 70 mol% or more of all grains are composed of silver chloride, and a silver bromide localized phase having a silver bromide content of less than 70 mol% is present inside or on the grains. Further, it is disclosed that a silver halide photographic light-sensitive material containing iron ions in the grains has high sensitivity, high contrast, and changes in photographic performance due to temperature and humidity during exposure are small.
When this silver halide emulsion is used, high sensitivity is obtained and reciprocity law failure is also improved. However, the above-mentioned specification does not mention about the stability of an image during continuous exposure and development of a large number of sheets.

[0012]

It is an object of the present invention to provide a silver halide photographic light-sensitive material which is excellent in sharpness, whiteness and manufacturing stability and which can form a stable image even when a large number of continuous exposures / processings are performed. To do.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The present inventor has diligently studied a silver halide photographic light-sensitive material using a high chloride silver halide emulsion, and the object of the present invention was to find out that at least one high chloride halogenated material was formed on a support. In a silver halide photographic light-sensitive material having a silver emulsion layer and other photographic constituent layers, the high chloride silver halide emulsion layer contains 98 to 99.9 mol% having a portion having a silver bromide content of 30 mol% or more. At least one of the high chloride silver halide emulsion layers or other photographic constituent layers contains the following general formula [I].
The present invention has been completed by finding out that it can be achieved by a silver halide photographic light-sensitive material characterized by containing at least one kind of compounds represented by the formulas [III] to [III].

[0014]

[Chemical 4]

[In the formula, V ₁ and V ₂ are a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, -COOR ₁ and -C, respectively.
OR ₁ , -CONR ₁ R ₂ , -OR ₁ , -NR ₁ R ₂ , -NR ₁ COR ₂ , -NR ₁ SO ₂ R
₂ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group, W ₁ and W ₂ are a hydrogen atom, —NR ₃ R ₄ , —NR ₃ COR ₄ , and —NR _{3, respectively.} SO ₂ R ₄ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group is represented, and X ₁ and X ₂ are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, -COOR.
₅ , -COR ₅ , -CONR ₅ R ₆ , -NR ₅ R ₆ , -NR ₅ COR ₆ , -NR ₅ SO ₂
R ₆ , SO ₂ R ₅ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, L ₁ , L ₂ and L ₃ each represent a methine group, and m is 0, 1 or 2. , N represents 1, 2 or 3, and M ^{n +} represents an n-valent cation.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R
₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ may be linked to form a 5- or 6-membered ring.

However, at least one of V ₁ , V ₂ , W ₁ , W ₂ , X ₁ and X ₂ represents a group containing a carboxyl group or a sulfo group. ]

[0018]

[Chemical 5]

[Wherein, R ₇ represents an alkyl group, an aryl group or a heterocyclic group, and R ₈ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, —COR ₁₀ or —SO ₂ R, respectively. _Ten
The stands, each R ₉ is a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl _{group, -COOR 10, -CONR 11 R 12} , -OR
₁₀ , -NR ₁₁ R ₁₂ , -NR ₁₁ COR ₁₂ , -NR ₁₁ SO ₂ R ₁₂ , -NR ₁₁ CON
R ₁₁ R ₁₂ represents an alkyl group or an aryl group, L ₄ , L ₅ , L ₆
Each represent a methine group, and l represents 0, 1 or 2. Y ₁ ,
Y ₂ represents an oxygen atom or NR ₁₃ .

R ₁₀ represents an alkyl group or an aryl group,
R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group or an aryl group. R ₁₃ represents a non-metal atomic group necessary for forming a 5-membered ring by linking with R ₇ .

However, at least one of R ₇ , R ₈ and R ₉ represents a group containing at least one carboxyl group or sulfo group. ]

[0022]

[Chemical 6]

[Wherein R ₁₃ and R ₁₄ are respectively —CN, —COR ₁₇ ,
Represents --COOR ₁₇ or --CONR ₁₈ R ₁₉ , and R ₁₅ and R ₁₆ respectively represent
It represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, L ₇ , L ₈ and L ₉ each represent a methine group, and k represents 0, 1 or 2. R ₁₇ represents an alkyl group or an aryl group. R ₁₈ and R ₁₉ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group,
One of R ₁₈ and R ₁₉ is a hydrogen atom.

However, at least one of R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ represents a water-soluble group or a substituent containing a water-soluble group. The present invention will be specifically described below.

First, the compound represented by the general formula [I] will be described.

In the formula, V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R _{1 to} R ₆
Examples of the alkyl group represented by include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc., and these alkyl groups further include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom (for example, fluorine,
Chlorine, bromine, etc.), alkoxy groups (eg, methoxy, ethoxy, etc.), aryloxy groups (eg, phenoxy,
4-sulfophenoxy, 2,4-disulfophenoxy, etc.),
Aryl groups (e.g., phenyl, 4-sulfophenyl, 2,
5-disulfophenyl etc.), a cyano group, an alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.) aryloxycarbonyl group (eg phenoxycarbonyl) etc. may be substituted.

Examples of the aryl group represented by V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R _{1 to} R ₆ include phenyl, 2-methoxyphenyl, 4-nitrophenyl and 3- Chlorophenyl,
4-cyanophenyl, 4-hydroxyphenyl, 4-methanesulfonylphenyl, 4-sulfophenyl, 3-sulfophenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3- Sulfophenyl, 2-chloro-5-sulfophenyl, 2-methoxy-5-
Sulfophenyl, 2-hydroxy-4-sulfophenyl,
2,5-dichloro-4-sulfophenyl, 2,6-diethyl-4
-Sulfophenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 2,4-disulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 4-carboxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 3,6-disulfo-α- Examples thereof include naphthyl, 8-hydroxy-3,6-disulfo-α-naphthyl, 5-hydroxy-7-sulfo-β-naphthyl and 6,8-disulfo-β-naphthyl.

Examples of the heterocyclic group represented by V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R _{1 to} R ₆ include pyridyl groups (2-pyridyl, 3-pyridyl, 4- Pyridyl, 5-sulfo-2-pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2-
Pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-
Pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, 3
-Nitro-2-pyridyl, etc.), oxazolyl group (5-sulfo-2-benzoxazolyl, 2-benzoxazol, 2
-Oxazolyl etc.), thiazolyl group (5-sulfo-2-benzothiazolyl, 2-benzothiazolyl, 2-thiazolyl etc.), imidazolyl group (1-methyl-2-imidazolyl,
1-methyl-5-sulfo-2-benzimidazolyl etc.),
Furyl group (3-furyl etc.), pyrrolyl group (3-pyrrolyl etc.), thienyl group (2-thienyl etc.), pyrazinyl group (2
-Pyrazinyl etc.), pyrimidinyl group (2-pyrimidinyl,
4-chloro-2-pyrimidinyl etc.), pyridazinyl group (2-
Pyridazinyl etc.), purinyl group (8-purinyl etc.), isoxazolinyl group (3-isoxazolinyl etc.), selenazolyl group (5-sulfo-2-selenazolyl etc.), sulforanyl (3-sulfolanyl etc.), piperidinyl Group (1-
Methyl-3-piperidinyl etc.), pyrazolyl (3-pyrazolyl etc.), tetrazolyl group (1-tetrazolyl etc.) and the like. The methine groups represented by L ₁ , L ₂ and L ₃ include those having a substituent (eg, methyl group, ethyl group, phenyl group, chlorine atom, etc.).

As the n-valent cation represented by M ^{n +} ,
For example, Na ⁺ , K ⁺ , Ca ²⁺ , NH ₄ ⁺ , HN (C ₂ H ₅ ) ₃ ⁺ , C ₅ H ₆ N ^+, etc. are represented. Typical specific examples of the dye of the present invention represented by the general formula [I] are shown below, but the dye of the present invention is not limited thereto.

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical formula 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

These dyes are described in British Patent 1,278,621,
It can be synthesized using the method described in Nos. 1,512,863 and 1,579,899.

Next, the compound represented by the general formula [II] will be described.

In the formula, the alkyl groups represented by R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are V ₁ , V ₂ , W ₁ and W _{2 in the} above general formula [I]. , X ₁ , X ₂ , R _{1 to} R ₆ include the same groups as the alkyl groups described above.

The aryl group represented by R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ includes V ₁ , V ₂ and V ₁ in the above general formula [I].
The same groups as the aryl groups described for W ₁ , W ₂ , X ₁ , X ₂ , and R _{1 to} R ₆ can be mentioned.

The heterocyclic groups represented by R ₇ and R ₈ include V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ and R _{1 in} the above formula [I].
The same groups as the heterocyclic groups described for R ₆ can be mentioned.

The methine groups represented by L ₄ , L ₅ and L ₆ include those having a substituent (eg, methyl group, ethyl group, phenyl group, chlorine atom).

Typical specific examples of the dye of the present invention represented by the general formula [II] are shown below, but the dye of the present invention is not limited thereto.

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

These dyes can be synthesized by reacting a dioxopyrazolopyridine compound with an appropriate monomethine source, trimethine source or pentamethine source compound, and specifically, Japanese Patent Publication No. 39-22069, 43-3504
No. 52-38056, 54-38129, 55-10059,
JP-A-49-99620, JP-A-59-16834 or U.S. Pat.
It can be synthesized using the method described in 181,225 or the like.

Next, the compound represented by the general formula [III] will be described.

In the formula, the alkyl groups represented by R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ include V ₁ and R ₁ in the above general formula [I].
The same groups as the alkyl groups described for V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R _{1 to} R ₆ can be mentioned.

The aryl groups represented by R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ include V ₁ , V ₂ and R ₁ in the above general formula [I].
The same groups as the aryl groups described for W ₁ , W ₂ , X ₁ , X ₂ , and R _{1 to} R ₆ can be mentioned.

Examples of the alkenyl group represented by R ₁₈ and R ₁₉ include vinyl and allyl.

The heterocyclic groups represented by R ₁₅ , R ₁₆ , R ₁₈ and R ₁₉ include V ₁ , V ₂ , W ₁ and W ₂ , in the above general formula [I].
The same groups as the heterocyclic groups described for X ₁ , X ₂ , and R _{1 to} R ₆ can be mentioned.

Examples of the cycloalkyl group represented by R ₁₅ and R ₁₆ include cyclopentyl and cyclohexyl.

Typical specific examples of the dye of the present invention represented by the general formula [III] are shown below, but the dye of the present invention is not limited thereto.

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

These dyes are described in JP-A-58-143342 and JP-A-6-143342.
It can be synthesized using the method described in 2-165656 or the like.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is characterized in that it contains 98 to 99.9 mol% of silver chloride, but it does not substantially contain silver iodide. Silver halide is preferred. The content of silver chloride is 99.5-99.9
Mol% is more preferred.

The silver halide grains according to the present invention are characterized by having a portion having a silver bromide content of 30 mol% or more. The portion containing silver bromide in a high concentration may be epitaxy bonded to silver halide emulsion grains or may be a so-called core-shell emulsion, or may be a partial composition without forming a complete layer. There may be only different areas of. The portion in which silver bromide is present at a high concentration may be formed in the step of forming silver halide grains, the chemical ripening step thereafter, or the coating solution preparation step. Further, when the composition of the inside of the particle is different from that of the surface, the composition may change continuously or discontinuously.

When the silver bromide content is about 1 mol%, the silver bromide content of the portion containing a high concentration of silver bromide is 40% though it depends on the composition of the entire silver halide emulsion grain. It is preferably at least mol%. Examples of such silver halide grains include those described in JP-A Nos. 58-95736, 58-108533, and 1-183647. The silver bromide content of a portion containing a high concentration of silver bromide can be determined by the method described in JP-A 1-183647, page 22, upper right column. When the silver bromide content thus obtained has a wide range, the silver bromide content in the portion containing silver bromide at a high concentration as used in the present application means the maximum value.

Heavy metal ions may be contained in the silver halide emulsion according to the present invention. These compounds are useful in improving reciprocity failure. Examples of heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and Group VIII metals such as cobalt, and cadmium,
Examples thereof include Group II transition metals such as zinc and mercury, and ions of lead, rhenium, molybdenum, tungsten, and chromium. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt. Above all, it is preferable to add it to the emulsion in the form of a complex salt because it is easily incorporated into the silver halide emulsion and the effect of the present invention becomes large.

When the heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Among them, thiocyanate ion, isothiocyanate ion, cyanate ion and the like are preferable.

The heavy metal compounds which can be preferably used in the silver halide emulsion according to the present invention are shown below, but the present invention is not limited thereto.

(1) FeCl ₂ (2) FeCl ₃ (3) (NH ₄ ) Fe (SO ₄ ) ₂ (4) K ₃ [Fe (CN) ₆ ] (5) K ₄ [Fe (CN) ₆ ] (6) K ₂ [IrCl ₆ ] (7) K ₃ [IrCl ₆ ] (8) K ₂ [PtCl ₆ ] (9) K ₂ [Pt (SCN) ₄ ] (10) K ₂ [NiCl ₄ ] (11 ) K ₂ [PdCl ₆ ] (12) K ₃ [RdCl ₆ ] (13) CdCl ₂ (14) ZnCl ₂ (15) K ₂ [Mo (CO) ₄ (CNO) ₂ ] (16) K ₃ [Re ( CNO) ₆ ] (17) K ₃ [Mo (OCN) ₆ ] (18) K ₄ [Fe (CNO) ₆ ] (19) K ₂ [W (CO) ₄ (CNO) ₂ ] (20) K ₂ [ Cr (CO) ₄ (CNO) ₂ ] (21) K ₄ [Ru (CNO) ₆ ] (22) K ₂ [Ni (CN) ₄ ] (23) PbCl ₂ (24) K ₃ [Co (NH ₃ ) _{6] (25) K 5 [} Co 2 (CNO) 11] (26) K 3 [Re (CNO) 6] (27) K 4 [ _{s (CNO) 6] (28} ) K 2 [Cd (CNO) 4] (29) K 2 [Pt (CNO) 4] (30) K 3 [IrBr 6] The silver halide emulsion to heavy metal ions according to the present invention In order to contain the above, the heavy metal compound may be added at any place in each step before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. .. For this purpose, for example, this heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, it may be dissolved together with the halide salt and added continuously during the grain formation process.

The amount of the heavy metal ions added to the silver halide emulsion is more preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and particularly preferably 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferably 1 × 10 ⁻³ mol or less.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. Also,
U.S. Pat.Nos. 4,183,756, 4,225,666, JP-A-55-26589,
Japanese Examined Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39 (19
It is also possible to prepare particles having an octahedral shape, a tetradecahedral shape, a dodecahedron shape or the like by the method described in the literature such as 73) and use them. Further, grains having twin planes may be used.

The silver halide grains according to the present invention may be grains having a single shape, or may be a mixture of grains having various shapes.

The grain size of the silver halide grains according to the present invention is not particularly limited, but considering other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2. The range is to 1.0 μm. The particle size can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis” (ASTM Symposium on Light Microscopy, 94-122).
Page, 1955) or "Theory of Photographic Processes, 3rd Edition"
(Mies and James, co-authored, Chapter 2, Macmillan, 1966).

This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately represented by diameter as the projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The coefficient of variation is preferably 0.22 or less, more preferably 0.15.
The following are monodisperse silver halide grains. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size as used herein means the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method of making seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

A device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor as described in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, etc., and taking out the reaction mother liquor outside the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

A known method can be used for chemically sensitizing the silver halide emulsion according to the present invention. That is, the sulfur sensitizing method, selenium sensitizing method, reduction sensitizing method, gold and other noble metal sensitizing methods can be used alone or in combination, but the gold sensitizing method can be used alone or in combination with other sensitizing methods. It is preferable to use the combination of the above in order to obtain the effects of the present invention.

Known sulfur sensitizers can be used for the silver halide emulsion according to the present invention.
For example, thiosulfate, allylthiocarbazide, thiourea,
Examples include allyl isothiocyanate, cystine, p-toluene thiosulfonate, and rhodanine. Other, U.S. Patents 1,574,944, 2,410,689, 2,278,947, 2,7
The sulfur sensitizers described in 28,668, 3,501,313, 3,656,955, West German Laid-Open Application (OLS) 1,422,869, JP-A-56-24937 and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is 1 per mol of silver halide.
It is preferably from 10 ^-1 to 1 10 ^-7 mol.

Known selenium sensitizers can be used in the silver halide emulsion according to the present invention. Aliphatic isoselencyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylates and esters, selenophosphates, diester selenides,
Selenides such as diethyl diselenide can be used, and specific examples thereof include U.S. Pat. Nos. 1,574,944 and 1,6
02,592 and 1,623,499.
Known reduction sensitizers can be used for the silver halide emulsion according to the present invention. Examples thereof include stannous chloride, thiourea dioxide, hydrazine and polyamine.

Known gold sensitizers can be used for the silver halide emulsion according to the present invention. For example, it can be used as various other gold complexes such as chloroauric acid, gold sulfide, and gold thiosulfate, and examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. it can. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 −4 per mol of silver halide.
It is preferably from mol to 1 × 10 -8 mol. More preferably, it is 1 × 10 −5 mol to 1 × 10 −8 mol.

The gold compound is preferably added to the silver halide emulsion after being dissolved in water or a water-miscible solvent such as methanol, ethanol, or fluorinated alcohol, alone or in a mixed solvent. Further, in the case of a compound which is hardly soluble in a suitable solvent, it may be added in the form of a dispersion. The gold compound can be added at any time during the emulsion production process, but it is preferable to add the gold compound at the start of chemical ripening and during the process.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A No. 2-146036, page 7, lower column, and specific compounds thereof include , (IIa-1) to (IIa-) described on page 8 of the publication.
8), compounds of (IIb-1) to (IIb-7), and
Examples thereof include 1- (3-methoxyphenyl) -5-mercaptotetrazole. These compounds are added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 mol per mol of silver halide is used.
It is preferably used in an amount of about 10 ^-4 mol. When added at the end of chemical sensitization, 1 x 1 per mol of silver halide
The amount is preferably about 0 ^-6 mol to 1 × 10 ^-2 mol, more preferably 1 × 10 ^-5 mol to 5 × 10 ^-3 mol. When added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 mol to 1 × 10 ⁻² mol is more preferable.
When added to a layer other than the silver halide emulsion layer,
The amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, known dyes can be used, but a dye forming a J aggregate is preferably used. Specific examples of the dye will be given below.

[0092]

[Chemical formula 26]

[0093]

[Chemical 27]

[0094]

[Chemical 28]

[0095]

[Chemical 29]

[0096]

[Chemical 30]

[0097]

[Chemical 31]

[0098]

[Chemical 32]

[0099]

[Chemical 33]

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength region of 600 to 750 nm.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula (YI) described on page 8 of Japanese Patent Application No. 2-234208. Can be mentioned.
Specific compounds are described on pages 9 to 11 of the same specification in YC-1 to
The thing described as YC-9 can be mentioned. Among them, YC-described on page 11 of the same specification
8 and YC-9 are preferable because they can reproduce a preferable yellow color.

As magenta couplers that can be preferably used in the silver halide photographic light-sensitive material according to the present invention, there are described general formulas (M-I) and (M-II) described on page 12 of Japanese Patent Application No. 2-234208. ) And a coupler represented by Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are preferable because they are excellent in the reproduction of colors ranging from blue to purple and red and are excellent in the depiction of details.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Japanese Patent Application No. 2-234208, the general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in C of page 18 to 21 of the same specification.
The thing described as C-1 to CC-9 can be mentioned.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used to dissolve and disperse the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'-1) described on page 35 of the specification. And other compounds can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.

For the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin, etc. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can be used.

As the reflective support according to the present invention, any material may be used, such as white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable. As the white pigment used for the reflective support according to the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Titanium, zinc oxide, talc,
Examples include clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer, and further, It is preferable that the content is 13% by weight or more, and 15
More preferably, it is at least wt%. The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention is
It can be measured by the method described in JP-A 2-28640.
When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

In the silver halide photographic light-sensitive material according to the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property and / or other property) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material according to the present invention include aminophenol and p-phenylenediamine which are widely used in various color photographic processes. A compound is used. In particular, aromatic primary amine type color developing agents are preferably used. To the color developing solution, a known developing solution component compound can be added in addition to the above color developing agent.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed at the same time as the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative of a washing process. As the development processing device used for the development processing of the silver halide photographic light-sensitive material of the present invention, the light-sensitive material is fixed to the belt even if it is a transport roller transport type with the light-sensitive material sandwiched between the rollers arranged in the processing tank. Although it may be an endless belt method in which the processing tank is conveyed, the processing tank is formed into a slit shape,
A method of supplying the processing liquid to the processing tank and conveying the photosensitive material may be used.

[0114]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. Each layer having the constitution shown below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to 6.67 g of the boiling point organic solvent (DNP) and dissolved, and this solution was dissolved in 9.5 ml of 15% surfactant (SU-1).
A yellow coupler dispersion liquid was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing a using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (S
U-3) was added to adjust the surface tension.

The layer structure is as shown in the table below.

[0118]

[Table 1]

[0119]

[Table 2]

[0120]

[Chemical 34]

[0121]

[Chemical 35]

[0122]

[Chemical 36]

[0123]

[Chemical 37]

[0124]

[Chemical 38]

(Preparation of blue-sensitive silver halide emulsion) The following (solution A) was added to 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C.
And while controlling (B liquid) to pH = 6.5 and pH = 3.0, 30
Simultaneously added over a minute, and then (C solution) and (D
(Solution) was simultaneously added over 180 minutes while controlling pH = 7.3 and pH = 5.5. At this time, the pH was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) 3.42 g of sodium chloride potassium bromide
0.07g Water added 200ml (B solution) Silver nitrate 10g Water added 200ml (C solution) Sodium chloride 102.7g Potassium bromide 2.10g Water added 600ml (D solution) Silver nitrate 300g Water added 600ml After addition is complete After desalting using a 5% aqueous solution of Demol N and a 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas, the mixture was mixed with a gelatin aqueous solution to obtain an average particle size of 0.85 μm and a coefficient of variation (S / R) = 0.07. A monodisperse cubic emulsion EMP-1 having a silver chloride content of 99.0 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye SPS-I-3 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye SPS-I-6 1 × 10 ^-4 mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) were changed in the same manner as in EMP-1, except that the average particle size was 0.43 μm.
m, coefficient of variation (S / R) = 0.07, silver chloride content 99.0 mol%
To obtain a monodisperse cubic emulsion EMP-2.

For EMP-2, the following compounds were used.
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye SPS-II-1 4 × 10 ⁻⁴ mol / mol AgX (Method for preparing red-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as in EMP-1, except that the average particle size is 0.50 μm.
m, coefficient of variation (S / R) = 0.08, silver chloride content 99.0 mol%
To obtain a monodisperse cubic emulsion EMP-3.

For EMP-3, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0133]

[Chemical Formula 39]

1000% 2% gelatin aqueous solution kept at 40 ° C
The following (Solution E) and (Solution F) were added in ml to pH = 6.5 and pH = 3.0.
Controlled to 30 minutes at the same time, the following (G
(Solution) and (solution H) while controlling the pH to 7.3 and pH = 5.5
Simultaneously added over 180 minutes. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide. Next, (solution I) and (solution J) were simultaneously added over 2 minutes.
Thus, average particle size 0.43μm, coefficient of variation (S / R) = 0.0
8. Monodisperse cubic emulsion EMP with a silver chloride content of 99.0 mol%
-4 was obtained. Analysis using X-ray revealed that the maximum silver bromide content in the portion containing a high concentration of silver bromide was 61 mol%.

(Solution E) Sodium chloride 3.44 g Water was added to 200 ml (Solution F) Silver nitrate 9.9 g Water was added to 200 ml (Solution G) Sodium chloride 103.2 g (Solution K) 50 ml Water was added to 600 ml (Solution H) ) Silver nitrate 297 g Water added 600 ml (solution I) Potassium bromide 2.17 g Water added 15 ml (solution J) Silver nitrate 3.1 g Water added 15 ml (solution K) 1-phenyl-5-mercaptotetrazole methanol solution (1 %) In the preparation of the green-sensitive emulsion (Em-G1), the emulsion (EM
A green-sensitive emulsion (Em-G2) was prepared in the same manner except that the emulsion (EMP-4) was used instead of P-2).

In the preparation of Sample 101, the green photosensitive emulsion (Em-G1), the anti-irradiation dye (AI-3) contained in the second layer, and the anti-irradiation contained in the fourth layer Samples 102 to 1 were prepared in the same manner except that the dye (AI-2) and the anti-irradiation dye (AI-1) contained in the sixth layer were changed as shown in Table 3.
19 was produced.

[0137]

[Table 3]

(1) Image stability during continuous exposure and development (density fluctuation during continuous processing) For each sample, the scene was exposed through a color negative film and processed until replenishment of 3 times the tank capacity of color developer. I went. Next, 50 sheets were continuously exposed and developed through a negative film photographed by a Macbeth color checker. The processing steps are shown below.

(Processing step) Processing step Processing temperature Time Replenishment amount Color development 35.0 ± 0.3 ℃ 45 seconds 162ml / m ² Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds 216ml / m ² Washing 30-34 ℃ 90 seconds 248ml / m ² Drying The composition of the development processing solution is shown below.

Color developer tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyl ethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-diphosphonate disodium 1.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbene sulfonate derivative ) 1.0g Potassium carbonate 27g Add water to make the total volume 1 liter and adjust to pH = 10.60.

Color developer replenisher Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.4 g 1-Hydroxylethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-diphosphone Sodium acid salt 1.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.3g Potassium carbonate 30g Water In addition, adjust the total volume to 1 liter and adjust the pH to 10.60.

Bleach-fixing solution Tank solution and replenishing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to bring the total volume to 1 Adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

Washing liquid tank liquid and replenishing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Hydroxylation Ammonium (20% aqueous solution) 3.0 g Fluorescent brightener (4,4′-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Using the PDA-65 densitometer (manufactured by Konica Corporation), the 1st, 10th, and 50th samples of the obtained sample were grayed out by Macbeth Color Checker (Neutral 8, Neutral).
al5) and the green density of the black (Black) patch was measured, and 1
The density of the first sheet was subtracted from the densities of the 0th sheet and the 50th sheet to obtain the amount of change in the density.

(2) White Background (Minimum Density) Each sample was developed with the above-mentioned processing steps while being unexposed, and the red light reflection density, green light reflection density and blue light reflection density were measured by X-light 310TF. Then, the respective minimum densities were defined as DminR, DminG, and DminB.

(3) Sharpness A sample was prepared by printing a resolution test chart on each sample through a negative film having been photographed. The density of the obtained image was measured with a microphotometer, and the value represented by the following formula was defined as the sharpness.

[0147] (in a large area portion D _max -D _min) sharpness = (D _max -D _min of dense lines printed image of five / mm) / D _max: maximum density D _min: large minimum density this value The higher the sharpness, the better.

Tables 4 to 7 collectively show the results of the density change, whiteness, and sharpness of the obtained singular baking.

[0149]

[Table 4]

[0150]

[Table 5]

[0151]

[Table 6]

[0152]

[Table 7]

As can be seen from the results of Tables 4 to 7, in Sample 101 using the comparative dye and the comparative emulsion, the white background and the sharpness were not sufficient, and the density fluctuation was large and stable during continuous exposure and processing. You can see that the finish is not obtained. Sample 10
In Nos. 2 to 106, the use of the dye of the present invention improves whiteness and sharpness, but it is clear that a stable finish cannot be obtained during continuous exposure and processing. In Sample 107, although the emulsion of the present invention is used, the dye is conventional, the white background and the sharpness are inferior, and the stability of finish during continuous exposure and processing is not sufficient. It can be seen that Samples 108 to 119 using the dye of the present invention and the emulsion of the present invention are excellent in whiteness and sharpness, have little variation in density during continuous exposure and processing, and have excellent finish stability.

Then, in the above-mentioned preparation of (EMP-4), the average particle diameter was similarly changed except that the addition time was changed.
0.85 μm, coefficient of variation (S / R) = 0.07, silver chloride content 99.0
A monodisperse cubic emulsion was obtained in which the maximum silver bromide content in the portion containing a high concentration of silver bromide was 61 mol%, and was prepared in the same manner as the blue-sensitive emulsion (Em-B1). In the preparation of the blue-sensitive emulsion and the above (EMP-4), the average grain size was 0.50 μm, the variation coefficient (S / R) = 0.07, the silver chloride content was 99.0 mol% in the same manner except that the addition time was changed. A monodisperse cubic emulsion having a maximum silver bromide content of a portion containing a high concentration of silver bromide of 61 mol% was obtained, and the red-sensitive emulsion (Em-
When a red-sensitive emulsion prepared in the same manner as in R1) was evaluated in the same manner, it was confirmed that the effects of the present invention were obtained regardless of the color sensitivity.

Example 2 In the preparation of the monodisperse emulsion (EMP-1) of Example 1,
Other than changing the amounts of sodium chloride and potassium bromide in (A liquid) and (C liquid), the addition time of (A liquid) and (B liquid), and the addition time of (C liquid) and (D liquid) Similar to EMP-1, average particle size 0.43 μm, coefficient of variation (S / R) = 0.07,
Monodispersed cubic emulsion with silver chloride content of 97.0 mol% (EMP-
5) was obtained. In the preparation of the green-sensitive emulsion (Em-G1) of Example 1, an emulsion (EMP-2) was used instead of the emulsion (EMP-2).
-5) was used in the same manner as above except that the green-sensitive emulsion (Em-G
3) was prepared.

Next, a 2% gelatin aqueous solution kept at 40 ° C.
The following (solution L) and (solution M) in 1000 ml have pAg = 6.5, p
Simultaneously added over 30 minutes while controlling H = 3.0, the following (N solution) and (O solution) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid L) Sodium chloride 3.44 g Water was added to 200 ml (M liquid) Silver nitrate 10 g Water was added to 200 ml (N liquid) Sodium chloride 103.2 g Water was added to 600 ml (O liquid) Silver nitrate 300 g Water was added After the addition of 600 ml, desalting was carried out using a 5% aqueous solution of Demol N and a 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.43 μm and a coefficient of variation (S / R). ) = 0.07 and a silver chloride content of 100.0 mol% to obtain a monodisperse cubic emulsion EMP-6. A green-sensitive emulsion (Em-G4) was prepared in the same manner as in the preparation of the green-sensitive emulsion (Em-G1) of Example 1 except that the emulsion (EMP-6) was used in place of the emulsion (EMP-2). ..

A green sensitive emulsion (Em-G5) was obtained in the same manner as in the preparation of the green sensitive emulsion (Em-G2) of Example 1 except that the chemical ripening process was changed to the following.

The following compounds are added and chemical ripening is carried out at 55 ° C. for 120 minutes.

Sodium thiosulfate 2.3 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye SPS-II-1 1 × 10 ⁻⁴ mol / mol AgX Monodisperse emulsion of Example 1 ( In the preparation of EMP-4), the addition time of (E liquid) and (F liquid), the amount of sodium chloride in (G liquid), the addition time of (G liquid) and (H liquid), and the bromination of (I) liquid An average particle size of 0. is obtained in the same manner as in (EMP-4) except that the amount of potassium and the addition time of (solution I) and (solution J) are changed.
A monodisperse cubic emulsion EMP-7 having a thickness of 43 μm, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 97.0 mol% was obtained. Analysis using X-ray revealed that the maximum silver bromide content in the portion containing a high concentration of silver bromide was 61 mol%. In the preparation of the green-sensitive emulsion (Em-G1) of Example 1, the emulsion (EMP
A green-sensitive emulsion (Em-G6) was prepared in the same manner except that the emulsion (EMP-7) was used instead of -2). The contents of each green-sensitive emulsion are shown in Table 8 below.

[0161]

[Table 8]

Samples 201 to 205 were prepared in the same manner as in the preparation of Sample 114 of Example 1 except that the green-sensitive emulsion (Em-G2) was changed as shown in Table 9. In addition, Samples 208 and 209 were prepared in the same manner as in the above-described Preparation of Sample 114, except that the sensitizing dye (SPS-II-1) added during chemical ripening was changed as shown in Table 9.

In the preparation of the monodisperse emulsion (EMP-4) of Example 1, the addition time of (solution E) and (solution F), the addition time of (solution G) and (solution H) and (solution I) ( Same as (EMP-4) except that the addition time of liquid J) was changed, the average particle diameter was 0.85 μm, the coefficient of variation (S / R) = 0.08, and the silver chloride content was 99.
0 mol% of monodisperse cubic emulsion EMP-8 was obtained. Analysis using X-ray revealed that the maximum silver bromide content in the portion containing a high concentration of silver bromide was 61 mol%.

In the preparation of the blue-sensitive emulsion (Em-B1) of Example 1, the emulsion (EMP-1) was replaced with an emulsion (EMP-E1).
-8), except that the blue-sensitive emulsion (Em-B) was used.
2) was prepared.

In preparing Sample 114 of Example 1, except that the blue-sensitive emulsion (Em-B1), the sensitizing dyes (SPS-I-3) and (SPS-I-6) were changed as shown in Table 9. Samples 206, 207, 210 and 211 were prepared in the same manner.

[0166]

[Table 9]

This sample was subjected to the same exposure and development treatment as in Example 1 and continuous exposure, and the results of evaluation of image stability during the treatment are shown in Table 10.

[0168]

[Table 10]

From the results in Table 10, it can be seen that Samples 201, 204 and 206 to 211 using the emulsion of the present invention are excellent in image stability during continuous exposure and processing. Further, it can be seen that the effect of the present invention is obtained regardless of the added sensitizing dye.

Then, the dyes I-2, I-10 of the present invention,
I-11, I-38, II-26, III-20, II
When similar samples were prepared and evaluated for I-25 and III-32, it was confirmed that the effects of the present invention were obtained with any of the dyes.

Example 3 (Em-G1) prepared in Example 1 was newly prepared 6 times, and using the emulsion, Sample 114 of Example 1 was newly prepared 6 times to prepare Samples 301-1 to 301. -6. Samples 301-1 to 3 above
The green-sensitive emulsion (Em-G1) of 01-6 was newly prepared 6 times, and the samples 302-1 to 302-10 were simply changed to (Em-G2), (Em-G4) and (Em-G6) respectively. , 303-1 ~ 303-
10 and 304-1 to 304-10 were produced.

These samples were subjected to an exposure time of 0.5 by a conventional method.
After optical wedge exposure for 2 seconds, development processing was performed by the development processing step of Example 1.

The green density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation). Sensitivity is defined based on the reciprocal of the exposure amount that gives a density of 0.75, and is expressed as a relative value when the sample created at the first time is set to 100. The gradation is the average between the density of 0.7 and the density of 1.75 on the characteristic curve. It was defined by the gradient. These samples 301-1 to 301-10, sample 302
-1 to 302-10, Samples 303-1 to 303-10 and Samples 304-1 to 304-10
The sensitivities, gradations and standard deviations thereof were calculated and the results are shown in Tables 11 and 12.

[0174]

[Table 11]

[0175]

[Table 12]

As is clear from these results, Sample 301 has a small standard deviation and excellent manufacturing stability.

Then, similar emulsions were prepared from the blue-sensitive emulsion and the red-sensitive emulsion layer and evaluated. It was confirmed that the effects of the present invention were obtained regardless of the color sensitivity.

[0178]

According to the present invention, there is provided a silver halide photographic light-sensitive material which is excellent in sharpness, whiteness and manufacturing stability, and which can supply a stable image even during continuous exposure and development of a large number of sheets. I was able to do it.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Murakami 1st Sakura-cho, Hino City, Tokyo Konica Stock Company In-house

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one high chloride silver halide emulsion layer and another photographic constituent layer on a support, wherein the high chloride silver halide emulsion layer comprises 30 mol%. 98-having the above silver bromide content
99.9 mol% contains silver halide emulsion grains consisting of silver chloride, and at least one of the high chloride silver halide emulsion layers or other photographic constituent layers has the following general formulas [I] to [II].
A silver halide photographic light-sensitive material containing at least one compound represented by the formula [I]. [Chemical 1] [In the formula, V ₁ and V ₂ are each a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, —COOR ₁ , —COR ₁ , and —CONR _{1
R 2, -OR 1, -NR 1} R 2, -NR 1 COR 2, represent -NR ₁ SO ₂ R _2, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group, W ₁ and W ₂ are each a hydrogen atom, —NR ₃ R ₄ , —NR ₃ COR ₄ , —NR ₃ SO ₂ R ₄ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group. In the formula, X ₁ and X ₂ are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, —COOR ₅ , —COR ₅ ,
-CONR ₅ R ₆ , -NR ₅ R ₆ , -NR ₅ COR ₆ , -NR ₅ SO ₂ R ₆ , SO ₂ R ₅ ,
It represents an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, L ₁ , L ₂ and L ₃ each represent a methine group, m represents 0, 1 or 2 and n represents 1, 2 or 3 and M ^{n +} represents an n-valent cation. R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆
May combine to form a 5- or 6-membered ring. However, V
_At least one of ₁ , V ₂ , W ₁ , W ₂ , X ₁ and X ₂ represents a group containing a carboxyl group or a sulfo group. ] [Chemical 2] [In the formula, R ₇ represents an alkyl group, an aryl group or a heterocyclic group, and R ₈ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, —COR ₁₀ or —SO ₂ R ₁₀ . , R ₉ are each a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, —COOR ₁₀ , —CONR ₁₁ R ₁₂ , —OR ₁₀ , —NR ₁₁ R ₁₂ ,
-NR ₁₁ COR ₁₂ , -NR ₁₁ SO ₂ R ₁₂ , -NR ₁₁ CONR ₁₁ R ₁₂ , an alkyl group, an aryl group, L ₄ , L ₅ and L ₆ each represent a methine group, and l is 0, 1 Or represents 2. Y ₁ and Y ₂ represent an oxygen atom or NR ₁₃ . R ₁₀ represents an alkyl group or an aryl group, and R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group or an aryl group. R ₁₃ represents a non-metal atomic group necessary for forming a 5-membered ring by linking with R ₇ . However, at least one of R ₇ , R ₈ and R ₉ represents a group containing at least one carboxyl group or sulfo group. ] [Chemical 3] [In the formula, R ₁₃ and R ₁₄ each represent —CN, —COR ₁₇ , —COOR ₁₇ , or —CONR ₁₈ R ₁₉ , and R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Represents a group or a heterocyclic group, L ₇ , L ₈ and L ₉ each represent a methine group, k represents 0,
Represents 1 or 2. R ₁₇ represents an alkyl group or an aryl group. R ₁₈ and R ₁₉ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and one of R ₁₈ and R ₁₉ is a hydrogen atom. However, R ₁₃ , R ₁₄ and R
_At least one of ₁₅ and R ₁₆ represents a water-soluble group or a substituent containing a water-soluble group. ]