JPH06222523A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photographic sensitive material for color prints capable of being rapidly processed, high in sensitivity, good in whiteness in nonimage parts, and small in scattering of sensitivity and fog due to the manufacture lots of the photographic sensitive materials, and a storage term and conditions after the manufacture. CONSTITUTION:The silver halide emulsion layer of the photosensitive material contains silver halide emulsion grains and a specified cyanine coloring matter and a specified N-containing mercapto compound, and the emulsion grains are formed in the presence of a specified grain growth controller and >=50% of the whole outer surfaces of the emulsion grains contain those composed of >=90mol% silver chloride comprising (111) faces, and the average bromine ion content in the surfaces of the emulsion grains amounts to >=2 times that of the whole emulsion grains, or thiocyanic salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic light-sensitive material capable of rapid processing and having high sensitivity, and more particularly to a photographic light-sensitive material for color printing.

[0002]

2. Description of the Related Art Color photographs are prepared by developing a light-sensitive material having a dye-forming coupler and a silver halide emulsion on a support with an aromatic primary amine type color developing agent.
It is well known that the method is a method of obtaining a dye image by reacting an oxidized product of a developing agent formed with a dye-forming coupler (hereinafter referred to as a coupler).

The simplification and speedup of this color development processing are
It is a very strong demand in the color photography industry, with so many improvements being made according to this demand, every few years,
New, simpler and faster systems are being developed. In order to speed up the processing, it is necessary to devise to shorten the time separately for each step of color development, bleach-fixing, washing with water and drying. As a method for accelerating the processing, for example, WO 87/04534 discloses a method of rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developing solution containing substantially no sulfite ion and benzyl alcohol. It is shown. It is known that the high silver chloride silver halide emulsion to be used in this method is generally low in sensitivity and easily fogged, and in order to put it into practical use, it has been a problem to overcome these points. Spectral sensitization is essential for silver halide emulsions for color light-sensitive materials, but in the case of high silver chloride having a silver chloride content of more than 90%, it is usually applied to emulsions mainly composed of silver bromide. In many cases, the spectral sensitization is significantly inferior even when the compound is subjected to spectral sensitization, and this tendency becomes remarkable as the silver chloride content increases. In order to put the high silver chloride silver halide emulsion into practical use, it was necessary to solve this point as well.

The high silver chloride emulsion grains usually tend to be cubic type crystal grains having a (100) outer surface, but the presence of a grain formation control agent may form grains having a (111) outer surface. It is possible. Since grains having a (111) outer surface are less likely to be fogged than grains having a (100) outer surface, in order to put a high silver chloride emulsion into practical use as a photographic emulsion, grains having a (111) outer surface are used. It is preferable to form an emulsion with. Various methods for preparing particles having such a characteristic (111) outer surface have been tried as described below.

For example, H. , Claes, etc.
physical Habit Modificastio
no of AgCl by Implements D
eating the Solvatio
n ”, The Journal of Photogra
pic Science, Volume 21, pages 39-50, 1
973 and "Influence of the
Absorption Spectra of Ab
"sorbed Sensitizing", The J
individual of Photographic Sc
ience, 21, p. 85-92, 1973, high silver chloride grains having (110) and (111) faces can be obtained by using grain growth control agents such as purine derivatives and thiourea derivatives. There is a description.

US Pat. No. 4,225,666 describes a method for obtaining high silver chloride octahedral grains having a (111) plane by using a merocyanine dye. U.S. Pat. No. 4,400,463 uses adenine and poly (3-thiapentyl acrylate) -co-acrylic acid-co-2-methacryloyloxyethyl-1-sulfonic acid sodium salt to prepare the (111) plane. There is a description of a method for obtaining tabular high silver chloride grains having a main plane.

US Pat. No. 4,801,523 describes a method for obtaining tabular high silver chloride grains having a high silver chloride octahedron and a (111) plane as a main plane by using an adenine derivative. JP-A-62-218959 and 62-
Nos. 213836 and 63-218938 describe a method of using thiourea or a thiourea derivative to obtain tabular high silver chloride grains having a (111) plane as a main plane.

JP-A-63-281149 discloses that in the presence of aminoazapyridine, pCl is 0-3 and pH is 2.5-2.5.
There is a description of a method of obtaining tabular high silver chloride grains having a (111) plane as a main plane by controlling the grain size to be 9.0. EP 0,227,444 discloses that particles are formed in the presence of at least 0.5 molar chloride ion in a dispersion medium containing a gelatin peptizer containing less than 30 μmol methionine per gram (11
1) There is a description of a method for obtaining tabular high silver chloride grains having a plane as a main plane.

US Pat. No. 4,399,215 describes pA.
There is a description of a method for obtaining tabular high silver chloride grains having a (111) plane as a main plane by controlling g to 6.5 to 10 and pH to 8 to 10 and forming grains in the presence of ammonia. U.S. Pat. No. 4,400,463 describes a method for obtaining tabular high silver chloride grains having a (111) plane as a principal plane by forming grains in the presence of a peptizer having an aminoazaindene and a thioether bond. There is.

JP-A-63-2043 discloses that particles are formed in the presence of a compound containing a sulfur atom in a heterocycle (11
1) There is a description of a method for obtaining tabular high silver chloride grains having a plane as a main plane. JP-A-63-41845 describes a method for obtaining tabular silver chloride grains having a (111) plane as a main plane by forming grains in the presence of a carbonyl compound or a sulfonyl compound containing a sulfur atom in the molecule. is there.

The grain formation control agent used for forming the (111) outer surface generally acts to suppress the adsorption of the sensitizing dye and thus causes a decrease in sensitivity and a fluctuation factor. As JP-A-2-000032
Japanese Patent No. 3187242 describes a method in which the grain formation control agent can be easily removed after grain formation. This method can be evaluated as an important first step for practical application of the (111) outer surface high silver chloride emulsion having a characteristic of low fog. However, the high silver chloride emulsion having a (111) outer surface has the drawback that the sensitizing dye is weakly adsorbed to the (100) outer surface high silver chloride emulsion even if no grain formation control agent is present, and the sensitivity is low. Overcoming all of these points remained an important issue.

Further, in JP-A-4-323645, emulsions stored in a solution state before coating and photographic sensitivity in the infrared region of a light-sensitive material during storage after coating are lowered and fog density is increased. For the purpose of providing a full-color photographic light-sensitive material containing a high-silver-chloride color photographic emulsion, the high-silver-chloride emulsion [normal crystal grains such as octahedrons and tetrahedrons having (111) faces or tabular grains] It is also proposed to include a thiocyanate or selenocyanate and a cyanine dye that spectrally sensitizes in the infrared region by J band sensitization, and an effective improving effect is recognized. In practical use, further improvement in photographic stability with the passage of time after adjustment of the coating liquid during production has been desired.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is to enable rapid processing, high sensitivity, good whiteness of non-image areas, and to vary between production lots of photographic light-sensitive materials, storage period after production, and storage conditions. An object of the present invention is to provide a photographic light-sensitive material for color prints, which has less variation in sensitivity and fog.

More specifically, an object of the present invention is to provide a photographic light-sensitive material for color prints, which uses high silver chloride grains having a (111) outer surface, has high sensitivity and low fog, and has a small change in sensitivity to various conditions. Is.

[0015]

As a result of intensive studies, the inventors of the present invention have found that the above objects can be solved by the following means. (1) A silver halide color photographic light-sensitive material having a cyan dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer and a yellow dye-forming coupler-containing silver halide emulsion layer on a reflective support. At least one of the silver halide emulsion layers contains a silver halide emulsion grain and a compound represented by the following general formulas [1] and [2], and the emulsion grain has the following general formula [3]. ], [4], [5], and [6] in the presence of at least one compound selected from the compounds, and more than 50% of the total outer surface of the emulsion grains ( 111) surface containing silver halide emulsion grains having a silver chloride content of 90 mol% or more. Further, the average bromine ion content on the surface of the emulsion grains has an average odor of the whole emulsion grains. A silver halide color photographic light-sensitive material characterized by having a content of elementary ions at least twice.

[0016]

[Chemical 9]

[0017]

[Chemical 10]

[0018]

[Chemical 11]

[0019]

[Chemical 12]

(2) Silver halide color having a cyan dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer and a yellow dye-forming coupler-containing silver halide emulsion layer on a reflective support. In the photographic light-sensitive material, at least one layer of the silver halide emulsion layer contains silver halide emulsion grains, at least one kind of thiocyanate, and a compound represented by the above general formula [1] or [2], and The emulsion grains are formed in the presence of at least one compound selected from the compounds represented by the general formulas [3], [4], [5] and [6], and the emulsion grains are Content of silver chloride is 90% or more of the total outer surface of (111)
A silver halide color photographic light-sensitive material comprising a silver halide emulsion grain of not less than mol%. (3) The silver halide color photographic light-sensitive material as described in (2) above, wherein the average bromine ion content on the surface of the emulsion grains is at least twice the average bromine ion content of the entire grains. (4) The color photographic light-sensitive material as described in any of (1) to (3) above, wherein the emulsion grains are tabular grains having an aspect ratio of 5 or more.

As the silver halide emulsion used in the present invention, it is necessary to use an emulsion composed of silver chloride, silver chlorobromide or silver chloroiodobromide and having an average silver chloride content of 90 mol% or more. It is more preferably 95 mol%. Here, the silver iodide content is preferably 1 mol% or less, more preferably 0.2 mol% or less. In the present invention, if the average silver chloride content is less than 90 mol%, the suitability for rapid processing tends to be poor.

The halogen composition of the emulsion may be different or the same between the grains, but it is preferable to use an emulsion having the same halogen composition between the grains because it is easy to make the properties of each grain uniform.

In the present invention, it is preferable that the bromine ions are localized on the particle surface, and the bromine ion content on the particle surface is at least twice the average bromine ion content on the entire particle. It is more preferably 3 times or more and 200 times or less, particularly preferably 5 times or more and 100 times or less. The surface defined in the present invention means XPS (X-ray Photoelectron).
The surface of the range measured by the Spectroscopy method is shown. This measuring method is specifically described in "Surface Analysis" by Someno and Yasumori, Kodansha (issued in 1977).

The high silver chloride emulsion grains preferably have a structure in which the silver bromide localized phase is layered or non-layered on the surface of the silver halide grain. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%.
These localized phases may be present on the edges, corners or planes of the grain surface, but one preferable example is a grain epitaxially grown on the corner portion of the grain. The high bromine ion concentration on the grain surface means that a poorly soluble bromide such as silver bromide or a water-soluble bromide such as potassium bromide, or U.S. Pat. No. 5,061, This is accomplished by adding a bromide ion donating compound, such as a bromide ion sustained release agent as described in No. 615.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodispersed coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

In the silver halide grains of the present invention, 50% or more of the total external surface area must be composed of (111) faces, but preferably 80% or more, more preferably 90% or more, most preferably 95%. % Or more. The ratio of the (111) plane to the total outer surface is defined as follows. That is, an electron micrograph of silver halide grains is taken (the number of grains is at least 50 or more), and the ratio of the outer surface area of (111) plane to the total outer surface area of all grains is determined. Whether or not a plane is composed of the (111) plane can be determined geometrically or crystallographically. The shape of the silver halide grains of the present invention is
If the ratio of (111) faces satisfies the above condition, it will be regular (regular) like a tetrahedron or octahedron.
r) Those having a crystal form, those having an irregular crystal form such as a plate shape, or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, among these, grains having the above-mentioned regular crystal form are contained in an amount of not less than 50% by weight, preferably not less than 70% by weight, more preferably not less than 90% by weight, based on all the silver halide grains in the same layer. .

In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% by weight of all grains is also preferably used. You can The silver chlorobromide emulsion used in the present invention is described in P. By Glafkides Ch
imieet Phisique Photograph
hique (Paul Montel, 1967
Year), G. F. Duffin Photo-grap
hic Emulsion Chemistry (F
Ocal Press, 1966), V.I. L. Z
by elikman et al Making and
Coating Photographic Emu
Ision (Focal Press, 1964
, Etc.) and the like. That is, any method such as an acidic method, a neutral method, an ammonia method, etc. may be used.As a method of reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion dopants can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include cadmium, zinc, lead, copper,
Salts such as thallium, or Group VIII elements iron, ruthenium, rhodium, palladium, osmium,
Examples thereof include salts of iridium and platinum or complex salts of these. In particular, the above-mentioned Group VIII element dopant can be preferably used. The addition amount of these compounds may vary over a wide range depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol per mol of silver halide.

It is preferable to use these metal ions in the form of complex ions, and the ligand is cyano,
Groups and molecules such as isocyano, thiocyano, nitrosyl, thionitrosyl, amine and hydroxyl are preferably used.

The silver halide grains of the present invention are present in the presence of at least one compound selected from the compounds represented by the above formulas [3], [4], [5] and [6] (grain formation inhibitors). Particles are formed.

The compounds selected from the general formulas [3] and [4] will be described in more detail below. A ₁ , A ₂ , A
₃ and A ₄ represent a non-metal atom group for completing the nitrogen-containing heterocycle, and other oxygen atom as a hetero atom,
It may contain a nitrogen atom and / or a sulfur atom, and the heterocycle may be further condensed with a benzene ring. A
_The heterocycle composed of ₁ , A ₂ , A ₃ and A ₄ may have a substituent, and each may be the same or different. Examples of the substituent include an alkyl group, an aryl group,
Aralkyl group, alkenyl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonic acid group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, Examples include an amino group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, and an arylthio group. Preferable examples of the nitrogen-containing heterocycle include a pyridine ring, an imidazole group, a thiazole ring, an oxazole ring, a pyridine ring, a pyrimidine ring, and other 5- to 6-membered rings, and more preferable examples include a pyridine ring. .

B represents a divalent linking group. Examples of the divalent linking group include an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, - S -, - CO
_{-, - NR 3 - (.} R 3 is an alkyl group, an aryl group or a hydrogen atom) can be mentioned those composed singly or in combination. These linking groups may be further substituted with a substituent such as a hydroxyl group. Preferred examples of B include alkylene and alkenylene.

R ₁ and R ₂ preferably have 1 or more carbon atoms and 2
It represents an alkyl group of 0 or less. R ₁ and R ₂ may be the same or different. The alkyl group includes substituted and unsubstituted alkyl groups, and the substituents are A ₁ , A ₂ , A ₃
And the substituents mentioned as the substituent of the nitrogen-containing heterocycle completed by A ₄ .

Preferred examples of R ₁ and R ₂ are alkyl groups having 4 to 10 carbon atoms. A more preferred example is an alkyl group substituted with a substituted or unsubstituted aryl group.

X represents an anion, and specific examples thereof include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate and oxalate. n represents 0 or 1, and in the case of an inner salt, n is 0. The compounds of the general formulas [3] and [4] can be synthesized by the method described in JP-A-2-32.

Specific examples of the compound represented by the general formula [3] or the general formula [4] are listed below, but the present invention is not limited to these compounds.

[0037]

[Chemical 13]

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043]

[Chemical 19]

The compound represented by the general formula (5) will be described in detail. R ₃ and R ₄ represent a hydrogen atom, an aryl group or an aralkyl group, and may be further substituted with a substituent. R ₃ and R ₄ may be the same or different. The substituents on the phenyl group of the aryl group and the aralkyl group include an alkyl group (methyl group, ethyl group, etc.), a hydroxyl group, a carboxyl group, a halogen atom (Cl,
Br etc.) and the like. R ₃ and R ₄ are preferably a hydrogen atom or a phenyl group.

R ₅ represents an amino group, a sulfonic acid group or a carboxyl group, the amino group may be alkyl-substituted, and the alkyl group represents an alkyl group having 1 to 5 carbon atoms. An unsubstituted amino group and a methyl-substituted amino group are preferred. o represents an integer of 1 to 5. It is preferably 2 to 3. The compound represented by the general formula (5) used in the present invention can be obtained by reacting a corresponding halide with a thiourea derivative or the like. O. Cl
inton et al. Am. Chem. So
c. Volume 70, p. 950 (1948) and D.I. G. D
ohterty et al. J. Am. Chem. S
oc. It can be synthesized by the method described in Volume 79, page 5670 (1957). Also, Japanese Patent Application No. 3-
It can also be synthesized by the method described in 70398.

Specific examples of the compound represented by formula (5) are listed below, but the invention is not limited thereto.

[0047]

[Chemical 20]

Next, the general formula (6) will be described. The amino group of X which may be alkyl-substituted and the alkyl group of the quaternary alkylammonium group may further have a substituent. Examples of the substituent include an alkylthio group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphono group and a halogen atom. A preferable example of X is an amino group which may be alkyl-substituted. The alkyl group preferably has 1 to 3 carbon atoms. L ¹ , L ² , L ³ , L
The alkylene group of ⁴ may be further substituted, and examples of the substituent of the alkylene group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphono group and a halogen atom. Preferable examples of L ¹ and L ² are an optionally substituted alkylene group, —O—, —CO—, and —N (R).
Examples thereof include a divalent organic group composed of-independently or in combination.

More preferred examples of L ¹ and L ² are an alkylene group which may be substituted, -N (R)-[wherein R is
Hydrogen atom, an alkyl group or -L ³ is - (S-L ⁴⁾ _p
Represents -X. At this time, L ³ and L ⁴ are preferably alkylene. ] Or a divalent organic group constituted by combining them. The alkylene group which may be substituted preferably has 1 to 5 carbon atoms. p is preferably 1 to 4.
The anion of Z represents, for example, chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, or oxalate.

The compound of formula (6) is disclosed in JP-A-3-212.
Known as No. 639. Specific examples of the compound represented by the general formula (6) are listed below, but the invention is not limited thereto.

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

The compound represented by the general formula (3) or (4), the compound represented by the general formula (5), or the compound represented by the general formula (6) is added until the grain formation is completed. While it may be added during any time, it is preferably added before the start of grain formation. The amount of the above compound added is
It is preferably from 10 ^-6 to 10 ^-1 mol, and more preferably from 10 ^{-5 to} 5 × 10 ^-2 mol, per mol of silver halide.

In realizing the effects of the present invention, the compound represented by the general formula (3) or (4), the compound represented by the general formula (5), or the compound represented by the general formula (6) Among them, the compound represented by the general formula (3) or (4) and the compound represented by the general formula (5) are preferable, and the compound represented by the general formula (3) or (4) is most preferable.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. In the chemical sensitization method, chalcogenide sensitization with sulfur, selenium, tellurium, etc., noble metal sensitization typified by gold sensitization, reduction sensitization, etc. can be used alone or in combination. Regarding compounds used for chemical sensitization, see Japanese Patent Application Laid-Open No.
2-215272 Publication, page 18, lower right column to second
Those described in the upper right column on page 2 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitization in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the target spectral sensitization. As the spectral sensitizing dye used in the present invention, at least one compound represented by the general formula [1] is used.

In the general formula (1), Z ₁₁ and Z ₁₂ may be the same or different and each represents a 5- or 6-membered nitrogen-containing heterocyclic nucleus-forming atom group, and l ₁₁ represents 0, 1 or 2. Represent As a more preferable heterocyclic nucleus, l ₁₁ is 0 or 1
In the case of, Z ₁₁ and Z ₁₂ may be the same or different,
Thiazole, benzothiazole, naphthothiazole, dihydronaphthothiazole, selenazole, benzoselenazole, naphthoselenazole, dihydronaphthoselenazone, oxazole, benzoxazole, naphthoxazole, benztomidazole, naphthimidazole,
A heterocyclic nucleus such as pyridine, quinoline, imidazo [4,5-b] quinoxaline or 3,3-dialkylindolenine, and when ₁₁ is 2, Z ₁₁ and Z ₁₂ may be the same or different. It is also possible to represent a heterocyclic nucleus such as benzothiazole, benzoselenazole, benzoxazole, naphthoxazole, benzimidazole or naphthimidazole.

The nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ may have one or more substituents. When the nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ is other than benzimidazole or naphthimidazole, examples of preferable substituents include a lower alkyl group (even if branched, further substituents {for example, hydroxy group, halogen Atoms, aryl groups, aryloxy groups, arylthio groups, carboxy groups, alkoxy groups, alkylthio groups, alkoxycarbonyl groups, etc., and more preferably an alkyl group having a total carbon number of 8 or less, for example, methyl. Group, ethyl group, butyl group, chloroethyl group, 2,2,3,3, -tetrafluoropropyl group, hydroxy group, benzyl group, carboxypropyl group, methoxyethyl group, ethylthioethyl group, ethoxycarbonylethyl group, etc. , Lower alkoxy group (which may further have a substituent. Examples of the substituent Like the same substituents as those listed as examples of the substituents of the alkyl group. Than the number preferably total carbon 8
The following alkoxy groups include, for example, methoxy group, ethoxy group,
Examples thereof include a pentyloxy group, an ethoxymethoxy group, a methylthioethoxy group, a phenoxyethoxy group, a hydroxyethoxy group and a chloropropoxy group. ), Hydroxy group, halogen atom, aryl group (for example, phenyl group, tolyl group, anisyl group, chlorophenyl group, carboxyphenyl group, etc.), aryloxy group (for example, tolyloxy group, anisyloxy group, phenoxy group, chlorophenoxy group, ), An arylthio group (for example, a tolylthio group, a chlorophenylthio group, a phenylthio group, etc.), a lower alkylthio group (which may be further substituted, examples of the substituent include those mentioned above as examples of the substituent of the lower alkyl group). Etc. More preferably, the total carbon number is 8.
The following alkylthio groups include, for example, methylthio group, ethylthio group, hydroxyethylthio group, carboxyethylthio group, chloroethylthio group, benzylthio group, etc., acylamino group (more preferably acylamino group having a total carbon number of 8 or less, such as acetyl). Amino group, benzoylamino group, methanesulfonylamino group, benzenesulfonylamino group, etc.), carboxy group, lower alkoxycarbonyl group (more preferably an alkoxycarbonyl group having a total carbon number of 6 or less, eg, ethoxycarbonyl group, butoxycarbonyl group, etc.) A perfluoroalkyl group (more preferably a perfluoroalkyl group having a total carbon number of 5 or less, such as a trifluoromethyl group, a difluoromethyl group, etc.) and an acyl group (more preferably, an acyl group having a total carbon number of 8 or less, such as an acetyl group. , Propi Group, a benzoyl group, benzenesulfonyl group, etc.). Further, when the nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ represents benzimidazole or naphthimidazole, examples of preferable substituents are:
_{When 11} is 0 or 1, a halogen atom, a cyano group,
A carboxy group, a lower alkoxycarbonyl group (more preferably an alkoxycarbonyl group having a total carbon number of 6 or less, such as an ethoxycarbonyl group, butoxycarbonyl group, etc.),
A purple oroalkyl group (more preferably a perfluoroalkyl group having a total carbon number of 5 or less, such as a trifluoromethyl group, a difluoromethyl group, etc.) and an acyl group (more preferably, an acyl group having a total carbon number of 8 or less, such as an acetyl group,
A propionyl group, a benzoyl group, a benzenesulfonyl group, etc.), and when l ₁₁ is 2, a halogen atom,
Examples thereof include a cyano group, a carboxy group, and a lower alkoxycarbonyl group having a total carbon number of 5 or less.

Specific examples of the nitrogen-containing heterocyclic nucleus represented by Z ₁₁ and Z ₁₂ include, for example, benzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-ethylbenzothiazole and 5,6-dimethylbenzo. Thiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-butoxybenzothiazole, 5,
6-dimethoxybenzothiazole, 5-methoxy-6-
Methylbenzothiazole, 5-chlorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5-phenylbenzothiazole, 5-acetylaminobenzothiazole, 6-propionylaminobenzothiazole,
5-hydroxybenzothiazole, 5-hydroxy-6
-Methylbenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d]
Thiazole, 5-methylnaphtho [1,2-d] thiazole, 8-methoxynaphtho [1,2-d] thiazole,
8,9-dihydronaphthothiazole, 3,3-diethylindolenine, 3,3-dipropylindolenine, 3,
3-dimethylindolenine, 3,3,5-trimethylindolenine, benzoselenazole, 5-methylbenzoselenazole, 6-methylbenzoselenazole, 5-methoxybenzoselenazole, 6-methoxybenzoselenazole, 5 -Chlorobenzoselenazole, 5,6-dimethylbenzelenazole, 5-hydroxybenzoselenazole, 5-hydroxy-6-methylbenzoselenazole, 5,6-dimethoxybenzoselenazole, 5-ethoxycarbonylbenzoselenazole, Naft [1,2-
d] selenazole, naphtho [2,1-d] selenazole, benzoxazole, 5-hydroxybenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole, 5-phenethylbenzoxazole, 5-phenoxybenzoxazole, 5-chloro Benzoxazole, 5-chloro-6-methylbenzoxazole, 5-phenylthiobenzoxazole, 6
-Ethoxy-5-hydroxybenzoxazole, 6-
Methoxybenzoxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] oxazole, 1-ethyl-5-cyanobenzimidazole, 1-ethyl-5- Chlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-6-chloro-5-cyanobenzimidazole, 1-ethyl-6-chloro-5-trifluoromethylbenzimidazole, 1-ethyl- 5,6
-Dichlorobenzimidazole, 1-ethyl-6-fluoro-5-cyanobenzimidazole, 1-propyl-
5-butoxycarbonylbenzimidazole, 1-benzyl-5-methylsulfonylbenzimidazole, 1-
Allyl-5-chloro-6-acetylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole, 1
-Ethylnaphtho [2,3-d] imidazole, 1-ethyl-6-chloronaphtho [2,3-d] imidazole, 2
-Quinoline, 4-quinoline, 8-fluoro-4-quinoline, 6-methyl-2-quinoline, 6-hydroxy-2-
Examples thereof include quinoline and 6-methoxy-2-quinoline.

R ₁₁ and R ₁₂ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms. More preferable substituents on the alkyl group and alkenyl group include, for example, a sulfo group,
Carboxy group, halogen atom, hydroxy group, carbon number 6
The following alkoxy groups, optionally substituted aryl groups having 8 or less carbon atoms (eg, phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, etc.), heterocyclic groups (eg, furyl group, thienyl group, etc.) An optionally substituted aryloxy group having 8 or less carbon atoms (for example, a chlorophenoxy group, a phenoxy group, a sulfophenoxy group,
Hydroxyphenoxy group), acyl group having 8 or less carbon atoms (eg, benzenesulfonyl group, methanesulfonyl group, acetyl group, propionyl group, etc.), alkoxycarbonyl group having 6 or less carbon atoms (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.) ), A cyano group, an alkylthio group having 6 or less carbon atoms (for example, a methylthio group, an ethylthio group, etc.), an optionally substituted arylthio group having 8 or less carbon atoms (for example, a phenylthio group, a tolylthio group, etc.), a carbon number of 8 Examples thereof include an optionally substituted carbamoyl group (eg, carbamoyl group, N-ethylcarbamoyl group, etc.), an acylamino group having 8 or less carbon atoms (eg, acetylamino group, methanesulfonylamino group, etc.) and the like. It may have one or more substituents.

Specific examples of the groups represented by R ₁₁ and R ₁₂ are:
For example, methyl group, ethyl group, propyl group, allyl group, pentyl group, hexyl group, methoxyethyl group, ethoxyethyl group, phenethyl group, tolylethyl group, sulfophenethyl group, 2,2,2-trifluoroethyl group, 2, Two
3,3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2- (2-hydroxyethoxy) ethyl group, carboxymethyl group, carboxyethyl group, ethoxycarbonylmethyl group, sulfoethyl group,
2-chloro-3-sulfopropyl group, 3-sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- (2,3-dihydroxypropyloxy) ethyl group or 2- [2-
(3-sulfopropyloxy) ethoxy] ethyl group and the like.

R ₁₃ and R ₁₅ represent a hydrogen atom. R ₁₃ is R
₁₁ and R ₁₅ may combine with R ₁₂ to form a 5- or 6-membered ring. Furthermore, when l ₁₁ is 2, R ₁₅ on the center side of the methine chain is a lower alkyl group (which may be substituted,
For example, methyl group, ethyl group, propyl group, methoxyethyl group, benzyl group, phenethyl group and the like. ) Is also represented. R
₁₄ represents a hydrogen atom or a substituent. As the substituent, an aryl group (for example, a phenyl group), an alkylthio group (for example, an ethylthio group), a lower alkyl group (which may be substituted, for example, a methyl group, an ethyl group, a propyl group, a methoxyethyl group, a phenethyl group and the like). More preferably, it is an alkyl group having a carbon number of 5 or less). Further, when l ₁₁ is 2, it means that R ₁₄ and R ₁₄ different from each other are connected to each other to form a 6-membered carbon ring.

X ₁₁ represents a counter ion necessary for neutralizing the electric charge. m ₁₁ represents 0 or 1, and 0 in the case of an inner salt.
Is.

Specific examples of the sensitizing dye represented by the general formula (1) are listed in order to more specifically explain the content of the present invention, but the present invention is not limited to these compounds.

[0065]

[Chemical formula 23]

[0066]

[Chemical formula 24]

[0067]

[Chemical 25]

[0068]

[Chemical formula 26]

[0069]

[Chemical 27]

[0070]

[Chemical 28]

[0071]

[Chemical 29]

[0072]

[Chemical 30]

[0073]

[Chemical 31]

[0074]

[Chemical 32]

[0075]

[Chemical 33]

[0076]

[Chemical 34]

[0077]

[Chemical 35]

[0078]

[Chemical 36]

[0079]

[Chemical 37]

[0080]

[Chemical 38]

[0081]

[Chemical Formula 39]

In order to incorporate the cyanine dye represented by the general formula (1) used in the present invention into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water or methanol. , Ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent.

Further, as described in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is used as an emulsion. Method of adding to the inside, JP-B-46-24,1
No. 85, etc., a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and the dispersion is added to an emulsion, JP-B-44-23,389 and JP-B-4.
4-27,555, JP-B-57-22,091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexistent to prepare an aqueous solution emulsion. Addition method, US Pat. No. 3,822,135
And U.S. Pat. No. 4,006,025, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion, JP-A-53-53.
-102,733 and JP-A-58-105,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, JP-A-51-
It is also possible to use a method in which a dye is dissolved using a compound that causes red shift as described in JP-A-74,624 and the solution is added to the emulsion.

Ultrasonic waves can also be used for dissolution. The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step of emulsion preparation which has been recognized to be useful so far. For example, US Pat. No. 2,735,766 and US Pat.
28,960, U.S. Pat. No. 4,183,756, U.S. Pat. No. 4,225,666, JP-A-58-184,14.
No. 2, JP-A-60-196749, and the like, as disclosed in the specification of JP-A-60-196,749 and the like, silver halide grain forming step and / or timing before desalting, JP-A-58-113,920 and the like. As disclosed in the above specification, the emulsion may be added at any time or step immediately before the chemical ripening or during the step, before the coating after the chemical ripening and before the coating. Also, U.S. Pat. No. 4,225,666, JP-A-5
As disclosed in the specification such as 8-7,629,
The same compound alone or in combination with a compound having a different structure, for example, divided into during the grain formation step and during the chemical ripening step or after the chemical ripening, or before or during the chemical ripening, or after the completion of the chemical ripening, etc. The compound may be divided and added in a divided manner, or the kind of the compound and the combination of compounds added in a divided manner may be changed and added.

The addition amount of the sensitizing dye represented by the general formula (1) used in the present invention varies depending on the shape and size of silver halide grains, but is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 5 × 10 ⁻⁵ to 2 × per mol of silver halide.
An addition amount of 10 ⁻³ mol and a particle surface coverage of 20 to 100% is preferable, and an addition amount of particle surface coverage of 30 to 90% is more preferable.

The thiocyanate compound used in the present invention may be either an inorganic salt or an organic salt. For example, potassium thiocyanate, sodium thiocyanate, etc.,
Alkaline metal salts such as alkali metal thiocyanates, calcium thiocyanate and magnesium thiocyanate,
Examples thereof include silver thiocyanate and ammonium salts such as ammonium thiocyanate.

When a thiocyanate compound is used in the present invention, as the thiocyanate compound used, the cyanine dye represented by the general formula (1) used in the present invention is added to the silver halide emulsion. It may be added before or after the addition is completed, or may be added simultaneously. Further, the sensitizing dye may be added continuously or dividedly from the time before addition of the sensitizing dye to the time after completion thereof, and the addition thereof is not particularly limited. However, the degree of suppression of chemical sensitization is reduced in the high silver chloride emulsion, although there is a difference depending on the amount added. Therefore, in order to obtain higher sensitivity, the period after the middle stage of the chemical sensitization step is more preferable.

The amount of the thiocyanate compound added varies depending on the shape and size of the silver halide grains.
2.5 × 10 ⁻⁵ to 2 × 10 per mol of silver halide
It can be used in an amount of ⁻² mol, preferably 5 × 10 ^{−4 to} 1.5 × 10 ⁻² mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount of 0.1 to 5 mol is preferable per 1 mol of silver halide occupying the total surface of the silver halide grains, and 0.25 is preferable. ˜2 mol is more preferred.

The silver halide emulsion of the present invention may contain a methine dye and / or a supersensitizer other than the cyanine dye according to the present invention for the purpose of expanding the light-sensitive wavelength range and supersensitizing. When containing silver halide grains other than the silver halide grains according to the present invention in the same layer or different layers,
The silver halide grains may be spectrally sensitized not only with the cyanine dye of the present invention but also with other methine dyes and supersensitizers.

Examples of dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a selenazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, a tellurazole nucleus and the like; Condensed nuclei; and nuclei in which aromatic hydrocarbon rings are condensed to these nuclei, that is, indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzimidazole nuclei, naphthimidazole nuclei, benzo A thiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzoterrazole nucleus and the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

For the merocyanine dye or the composite merocyanine dye, as the nucleus having a ketomethylene structure, any nucleus generally used for merocyanine dyes can be applied. Particularly useful nuclei include pyrazolin-5-one nuclei, thiohydantoin nuclei, and 2-thiooxazolidine-2,4-
Applying 5-membered and 6-membered heterocyclic nuclei such as dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazolidine-2,4-dione nucleus You can

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is
Especially, it is often used for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,22.
No. 9, No. 3,397,060, No. 3,522,052
Issue 3, Issue 3,527,641, Issue 3,617,293
No. 3,628,964, 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,703,377, No. 3,769,301
Nos. 3,614,609 and 3,837,862
No. 4,026,707 and British Patent 1,344,2.
No. 81, No. 1,507,803, Japanese Patent Publication No. 43-4.9
36, 53-12,375, JP-A-52-11.
0,618, 52-109,925 and the like.

As a typical example of the supersensitizer, Japanese Patent Application Laid-Open No. 59-59
-142,541 and the like, bispyridinium salt compounds, stilbene derivatives as described in JP-B-59-18,691 and the like, water-soluble bromides disclosed in JP-B-49-46,932 and US Pat. , 743, 510, and the like, condensates of aromatic compounds and formaldehyde, cadmium salts, azaindene compounds, and the like.

The timing of adding these methine dyes to the silver halide emulsion may be any stage of emulsion preparation known to be useful so far, and the addition method and the addition amount have been useful so far. Any method and amount known to be. Specifically, the addition timing of the cyanine dye represented by the general formula (1), the addition method,
In addition, the timing, the addition method, and the addition amount described as the addition amount can be mentioned.

The compound represented by formula (2) will be described in detail below. The heterocycle formed by Q includes, for example, imidazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring, benzimidazole ring, naphthimidazole ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole. Ring, benzoxazole ring and the like.

Examples of the cation represented by M include a hydrogen ion, an alkali metal (for example, sodium and potassium), an ammonium group and the like. The compound represented by the general formula (2) is further represented by the following general formulas (2-1) and (2
-2), (2-3) and (2-4) are respectively represented by mercapto compounds are preferable.

General formula (2-1)

[0098]

[Chemical 40]

In the formula, R _A represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group, and Z represents —NH— or —O. Represents-, or -S-, and M has the same meaning as M in formula (2). General formula (2-2)

[0100]

[Chemical 41]

In the formula, Ar is

[0102]

[Chemical 42]

R _B represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group,
It represents a carbamoyl group or a sulfonamide group. n is 0
Represents an integer of 2; M has the same meaning as M in formula (2).

In formulas (2-1) and (2-2), examples of the alkyl group represented by R _A and R _B include methyl, ethyl and butyl, and examples of the alkoxy group include methoxy and ethoxy. Examples of the salt of the carboxyl group or the sulfo group include sodium salt and ammonium salt.

In the general formula (2-1), examples of the aryl group represented by R _A include phenyl and naphthyl, and examples of the halogen atom include chlorine atom, bromine atom and the like. Examples of the acylamino group represented by R _B in the general formula (2-2) include methylcarbonylamino and benzoylamino, examples of the carbamoyl group include ethylcarbamoyl, phenylcarbamoyl, and examples of the sulfonamide group include methyl. Examples thereof include sulfonamide and phenyl sulfonamide.

The above-mentioned alkyl group, alkoxy group, aryl group, amino group, acylamino group, carbamoyl group, sulfonamide group and the like also include those further having a substituent. As the substituent, for example, when an amino group is taken as an example, it may be an amino group substituted with an alkylcarbamoyl group, that is, an alkyl-substituted ureido group. General formula (2-3)

[0107]

[Chemical 43]

In the formula, Z represents -N ( _RA1 )-, an oxygen atom or a sulfur atom. R is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -SR _A1 ,-
N (R _A2 ) R _A3 , —NHCOR _A4 , —NHSO ₂ R _A5 or a heterocyclic group, wherein R _A1 is a hydrogen atom, an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, -CO
R _A4 or —SO ₂ R _A5 is represented, R _A2 and R _A3 represent a hydrogen atom, an alkyl group, or an aryl group, and R _A4 and R ₄₅ represent an alkyl group or an aryl group. M has the same meaning as M in formula (2).

R, R _A1 in the general formula (2-3),
Examples of the alkyl group of R _A2 , R _A3 , R _A4 and R _A5 include methyl, benzyl, ethyl and propyl, and examples of the aryl group include phenyl and naphthyl. The alkenyl group for R and R _A1 is, for example, propenyl, and the cycloalkyl group is, for example, cyclohexyl. Further, examples of the heterocyclic group for R include furyl and pyridinyl.

The above R, R _A1 , R _A2 , R _A3 , R _A4 and R
_The alkyl group and aryl group represented by _A5 , the alkenyl group and cycloalkyl group represented by R and R _A1 and the heterocyclic group represented by R include those further having a substituent. General formula (2-4)

[0111]

[Chemical 44]

In the formula, R and M are each represented by the general formula (2-
It represents a group having the same meaning as R and M in 3). R _B1 and R _B2 each represent a group having the same meaning as R _A1 and R _A2 in formula (2-3). Specific examples of the compound represented by the general formula (2) are shown below, but the invention is not limited thereto.

[0113]

[Chemical formula 45]

[0114]

[Chemical formula 46]

[0115]

[Chemical 47]

[0116]

[Chemical 48]

[0117]

[Chemical 49]

[0118]

[Chemical 50]

[0119]

[Chemical 51]

The addition amount of the compound represented by the general formula (2) is 1 × 10 ^{-5 to} 5 × 10 ^-2 per mol of silver halide.
The amount is preferably mol, more preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol. The addition method is not particularly limited and it may be added during the formation of silver halide grains, during physical ripening, during chemical ripening, or during preparation of the coating solution.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 48 of the specification of Japanese Patent No. 15272 are preferably used.

The emulsion used in the present invention may be any type of so-called surface latent image type emulsion in which a latent image is mainly formed on the surface of a grain, or so-called internal latent image type emulsion in which a latent image is mainly formed inside a grain. May be

In the light-sensitive material according to the present invention, a hydrophilic colloid layer can be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving sharpness of an image. A dye (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, and a dihydric or tetrahydric alcohol (in the water resistant resin layer of the support ( For example, a titanium oxide surface-treated with trimethylolethane etc.
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

The high boiling point organic solvent for photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention is a compound which is immiscible with water and has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher. Any solvent can be used. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The melting point of the high boiling point organic solvent is preferably 160 ° C. or higher,
It is more preferably 170 ° C. or higher.

For details of these high-boiling point organic solvents, see JP-A-62-215272, No. 137.
It is described in the lower right column of the page to the upper right column of page 144. Cyan, magenta or yellow couplers are also loadable latex polymers in the presence or absence of the high boiling organic solvents described above (eg US Pat. No. 4,203,716).
No.) or dissolved with an insoluble polymer soluble in an organic solvent, and emulsified and dispersed in a hydrophilic colloid aqueous solution.

The homopolymers or copolymers described on pages 12 to 30 of US Pat. No. 4,857,449 and International Publication No. WO88 / 00723 are preferably used, more preferably a methacrylate type or acrylamide. It is preferable to use a styrene-based polymer, particularly an acrylamide-based polymer in terms of color image stabilization and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0277589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, by chemically bonding with the aromatic amine-based developing agent remaining after color development processing,
A compound chemically bonded to the compound in the above-mentioned patent specification which produces a substantially colorless compound and / or an oxidant of an aromatic amine color developing agent remaining after the color developing treatment It is possible to use the compounds in the above-mentioned patent specification, which form an inactive and substantially colorless compound, simultaneously or alone, for example, the reaction of the coupler with the residual color developing agent in the film or its oxidant and the coupler during storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of the coloring pigment.

Further, as a cyan coupler, there is disclosed in JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in Japanese Patent No. 33144, European Patent EP 0333185A2.
3-hydroxypyridine type cyan couplers described in the above specification (in particular, the couplers listed as specific examples (4
(2) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable)
And cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3,8,34 listed as specific examples), and pyrrolo described in European Patent EP0456226A1. Pyrazole type cyan coupler, European Patent EP044890
Pyrroylimidazole type cyan couplers described in No. 9, European Patent Nos. EP0488248 and EP04911.
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

Further, as the yellow coupler, in addition to the compounds described in the following table, European Patent EP0447969
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, Malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, US Pat. The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group, or a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

As the magenta couplers used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the publicly known documents of the following table are used. Among them, hue, image stability,
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring, as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A.

The method for processing the color light-sensitive material of the present invention is as follows:
In addition to the methods described in the table below, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A 4-97355, page 5, upper left column, line 17 to 18 The processing materials and processing methods described in the lower right column, line 20 are preferable.

Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

As a support used in the light-sensitive material of the present invention, a white polyester support or a layer containing a white pigment for a display is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable.

In exposure, US Pat. No. 4,88
It is preferable to use the band stop filter described in No. 0,726. This removes the light mixture,
Color reproducibility is significantly improved.

The exposed light-sensitive material is preferably subjected to bleach-fix processing after color development for the purpose of rapid processing. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less for the purpose of accelerating desilvering,
Furthermore, about 6 or less is preferable.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and a processing method applied to process the light-sensitive material. As the additives for treatment and treatment, those described in the following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-139544) are preferably used.

[0138]

[Table 1]

[0139]

[Table 2]

[0140]

[Table 3]

[0141]

[Table 4]

[0142]

[Table 5]

[0143]

【Example】

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. A multilayer color photographic paper (sample 101) was prepared. The polyethylene layer on the emulsion coated side of the paper support contained 13% by weight titanium dioxide and was laminated to a thickness of 30 microns. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-
2) 7.5 g, color image stabilizer (Cpd-3) 16.0 g, ethyl acetate 180.0 cc and solvent (Solv-1)
And (Solv-2) (25 g) were added and dissolved, and this solution was emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 60 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion A. On the other hand, a silver chlorobromide emulsion A as shown in Table 1 below was prepared.

The above-mentioned emulsion dispersion A and this silver chlorobromide emulsion A
And were mixed and dissolved, and a coating solution for the first layer was prepared so as to have the following composition. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. H-1 and H-2 were used as the gelatin hardening agent for each layer. Further, the total amount of Cpd-10 and Cpd-11 in each layer was 25.
It was added to a 0 mg / m ² and 50.0 mg / m ^2.

Silver chlorobromide emulsion of each light-sensitive emulsion layer (Table 1)
The following spectral sensitizing dyes were used for each.

[0147]

[Table 6]

[0148]

[Table 7]

[0149]

[Table 8]

Compound I-2-6 was added to the blue-sensitive emulsion layer (first layer), the green-sensitive emulsion layer (third layer) and the red-sensitive emulsion layer (fifth layer) per mol of silver halide. 8.5
× 10 ^-5 mol and 2.5 × 10 ^-4 mol were added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0151]

[Chemical 52]

(Layer Structure) The layer structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

[0153]

[Table 9]

[0154]

[Table 10]

[0155]

[Table 11]

[0156]

[Table 12]

[0157]

[Chemical 53]

[0158]

[Chemical 54]

[0159]

[Chemical 55]

[0160]

[Chemical 56]

[0161]

[Chemical 57]

[0162]

[Chemical 58]

[0163]

[Chemical 59]

[0164]

[Chemical 60]

The emulsion used in the present invention was prepared as follows. The average volume of the emulsion was measured by a Coulter counter manufactured by Coulter. The average surface area of each emulsion grain and the average ratio of the area of the (111) plane to the total surface area of the emulsion grains were determined by electron micrograph according to the method described in the text.

(Preparation of silver chlorobromide emulsion A) 1600 cc of a 3% aqueous solution of lime-processed gelatin was added with sodium chloride 17.6.
g was added, and the aqueous solution was heated to 75 ° C., and an aqueous solution containing 0.094 mol of silver nitrate and an aqueous solution containing 0.12 mol of sodium chloride were added with vigorous stirring while maintaining the temperature. Then, an aqueous solution containing 0.85 mol of silver nitrate and an aqueous solution containing 1.15 mol of sodium chloride were added.

After that, the temperature was lowered to 40 ° C. to perform desalting by washing with sedimented water, and then 90.0 g of lime-processed gelatin was added and dissolved. To this emulsion, 0.005 mol of a silver bromide fine grain emulsion having a side length of 0.05 μm was added at 50 ° C., and then a sulfur sensitizer and a gold sensitizer were added for ripening to obtain optimum sensitization. (Preparation of silver chlorobromide emulsion B1) In the method for preparing silver chlorobromide emulsion A, 1600 cc of a 3% aqueous solution of lime-processed gelatin
The temperature of the aqueous solution obtained by adding 17.6 g of sodium chloride to
Optimum sensitization was carried out according to the method for preparing the silver chlorobromide emulsion A except that the temperature was adjusted to 8 ° C.

(Preparation of silver chlorobromide emulsion B2) In the method for preparing silver chlorobromide emulsion B1, 1600 cc (containing sodium chloride) of 3% aqueous solution of lime-processed gelatin was mixed with 0.03 mg of silver nitrate.
After adding an aqueous solution containing 94 mol and an aqueous solution containing 0.12 mol of sodium chloride, the compound I-11 was further added in an amount of 0.
Optimal sensitization was performed in the same manner except that 27 g was added.

(Preparation of silver chlorobromide emulsions B3 to B10) Compound I-11 added to the method for preparing silver chlorobromide emulsion B2.
Silver chlorobromide emulsions B3 to B10 were prepared by optimally sensitizing in the same manner except that (grain formation control agent) was changed to that shown in Table 1. However, the grain forming temperature of Emulsion B10 was 59 ° C. (Preparation of silver chlorobromide emulsion B11) 3% of lime-processed gelatin
To 1600 cc of aqueous solution, 17.6 g of sodium chloride and 0.63 g of compound I-11 were added, and this aqueous solution was heated to 58 ° C. and vigorously stirred while containing 0.094 mol of silver nitrate and 0.12 mol of sodium chloride. And were added. Then, an aqueous solution containing 0.85 mol of silver nitrate and an aqueous solution containing 1.15 mol of sodium chloride were added.
Other than the above, a silver chlorobromide emulsion B11 comprising tabular grains having an average aspect ratio of 5.2 was optimally sensitized according to the method for preparing the silver chlorobromide emulsion B2.

(Preparation of silver chlorobromide emulsions B12 to B17 and B18) Emulsions B12 to B17 were optimally sensitized without adding the silver bromide fine grain emulsion added at the time of sensitization in the emulsion preparation method of B5 to B11. It was done. Emulsion 18 was prepared in the same manner as in preparation of emulsion B2, except that 0.05 g of adenine sulfate was added instead of compound I-11.

The Br ⁻ ion density on the surface was determined by the XPS method as a ratio to Ag. Also, the average Br
^-The ion density was similarly determined by the fluorescent X-ray method as a ratio to Ag. Table 1 shows a list of the obtained emulsions.

[0172]

[Table 13]

For the sample 101 thus obtained, the emulsion of the third layer (green sensitive emulsion layer) was changed as shown in Table 2, and otherwise the same as in the sample 101, the samples 102 to 142 were replaced. Obtained. Samples 112-129 and 136-14
No. 2 was thiocyanate (KSC) when the coating solution for the third layer was prepared.
N) 1% aqueous solution 1.2 × 1 per mol of silver halide
It was added so as to be 0 ^-3 mol.

[0174]

[Table 14]

[0175]

[Table 15]

Further, when coating the samples 101 to 142, a sample prepared in the same manner as the samples 101 to 142 except that the coating solution for the third layer was allowed to stand for 10 hours after the preparation, and samples 201 to 142 were prepared. It was set to 242. A standard subject is exposed using the obtained sample 101, and a solution having the following processing steps and processing compositions is used by using the automatic developing processor A for paper until the tank capacity for color development is doubled. A continuous process was carried out.

Treatment process Temperature Time Replenisher * Tank capacity (ml) (liter) Color development 35 ° C. 45 seconds 161 17 Bleach fixing 35 ° C. 45 seconds 215 17 rinses 35 ° C. 20 seconds −10 rinses 35 ° C. 20 seconds −10 Rinse 35 ° C., 20 seconds 360 10 Dry 80 ° C., 60 seconds * Replenishment amount per 1 m ² of light-sensitive material Rinsing from to tank 3 countercurrent system.

The composition of each processing liquid is as follows. [Color developer] Tank liquid Replenisher Water 700 ml 700 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disulfonic acid / 2Na salt 0.5 g 0.5 g Potassium bromide 0.01 g- Sodium chloride 1.6 g-potassium carbonate 27 g 27 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.1 g N, N-di (sulfoethyl) hydroxylamine 2Na salt 8.0 g 10.0 g sodium sulfite 0.1 g 0.2 g optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.5 g Water added 1000 ml 1000 ml pH (25 ° C) 10.05 10 .45

[Bleach-fixing solution] (tank solution and replenisher are the same) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Nitric acid (67%) ) 30 g Water was added to 1000 ml pH (25 ° C) (with acetic acid and aqueous ammonia) 5.8

[Rinse Solution] (tank solution and replenisher are the same) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less)

Next, FWH manufactured by Fuji Photo Film Co., Ltd.
Type sensitometer (light source color temperature of 3200 ° K.) was used to provide gradation exposure of a three color separation filter for sensitometry. The exposed sample was processed using the automatic developing processor for paper, which was previously placed in the running state as described above. The reflection density of the processed sample was measured with a TCD type density measuring device manufactured by Fuji Photo Film Co., Ltd., and the sensitivity and the minimum density (Dmin) were measured. The sensitivity was defined as the logarithm of the reciprocal of the exposure amount required to give a color density of 1.0, and was expressed as the difference when Sample 101 was set to 0. The minimum density is a value which is an index of fog of the emulsion.

Further, the difference in sensitivity and the difference in Dmin between the samples 201 to 242 corresponding to the samples 101 to 142 (the samples were left for 10 hours after adjusting the coating solution) are determined. The results obtained are shown in Table 3.

[0183]

[Table 16]

[0184]

[Table 17]

As is apparent from the results shown in Table 3, Samples 105 to 117 and 136 to 14 of the present invention using the particle formation control agent of the present invention and the mercaptoheterocyclic compound.
It can be seen that the sample No. 1 has a low Dmin and high sensitivity, and it is preferable that the photographic property is little changed even if the time from the preparation of the coating liquid to the coating is long. On the other hand, in Sample 142 using Emulsion B-18 composed of the dodecahedron grains formed in the presence of the grain formation controlling agent other than the present invention, the sensitivity was remarkably low even when used in combination with the mercapto heterocyclic compound, and It can be seen that the sensitivity of the coating solution changes with time.

Further, in Samples 101 to 104 using the emulsions B-1 to B-4 in which the proportion of the (111) plane was less than 50%, the fog (Dmin) was relatively high, and the change of the fog with the passage of time of the coating solution was large. It can be seen that it is large when used in combination with a mercapto heterocyclic compound. Also, pure silver chloride emulsions B-12 to B-17 having no silver bromide-rich phase on the surface of the grain are used,
It can be seen that in the light-sensitive materials 130 to 135 to which no thiocyanate is added, the sensitivity is low even when used in combination with the mercapto heterocyclic compound, and the sensitivity changes remarkably with time of the coating solution.

Further, in Samples 118 to 129 in which no mercaptoheterocyclic compound was used, the sensitivity was relatively low, the fog was high, and the fog increased remarkably with the passage of time of the coating solution. Example 2 Instead of Compound I-2-6 added to the blue-sensitive emulsion layer (first layer), the green-sensitive emulsion layer (third layer) and the red-sensitive emulsion layer (fifth layer) in Example 1, Compound I-2 was added. It carried out like Example 1 except having used -2-5. As a result, good results were obtained as in Example 1.

[0188]

By carrying out the present invention, it is possible to obtain a light-sensitive material having high sensitivity, less fog, and less change in photographic property with the passage of time after preparation of the coating solution during manufacturing, which causes less difference between manufacturing lots.

Claims (4)

[Claims] 1. A silver halide color photograph having a cyan dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer and a yellow dye-forming coupler-containing silver halide emulsion layer on a reflective support. In the light-sensitive material, at least one of the silver halide emulsion layers contains a silver halide emulsion grain and a compound represented by the following general formulas [1] and [2], and the emulsion grain has the following general formula. Formed in the presence of at least one compound selected from the compounds represented by [3], [4], [5] and [6], and 50% or more of the total outer surface of the emulsion grains Contains silver halide emulsion grains having a silver chloride content of 90 mol% or more and having a (111) face, and the average bromine ion content on the surface of the emulsion grains is A silver halide color photographic light-sensitive material having a content of at least twice the average bromine ion content. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] 2. A silver halide color photograph having a cyan dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer and a yellow dye-forming coupler-containing silver halide emulsion layer on a reflective support. In the light-sensitive material, at least one layer of the silver halide emulsion layer contains silver halide emulsion grains, at least one kind of thiocyanate and a compound represented by the following general formulas [1] and [2], and The emulsion grains are those formed in the presence of at least one compound selected from the compounds represented by the following general formulas [3], [4], [5] and [6]. 50 on all outer surfaces
% Of silver chloride consisting of (111) faces is 90 mol%
A silver halide color photographic light-sensitive material comprising the above silver halide emulsion grains. [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the average bromine ion content on the surface of the emulsion grains is at least twice the average bromine ion content of the entire emulsion grains. . 4. The color photographic light-sensitive material according to claim 1, wherein the emulsion grains are tabular grains having an aspect ratio of 5 or more.