JPH04335339A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance rapid processability and sensitivity and to reduce variation of sensitivity by incorporating a specified compound and silver halide grains containing silver chloride in an amount of >=90mol% in a photosensitive emulsion layer and sensitizing the emulsion by a selenium compound. CONSTITUTION:The photosensitive emulsion layer contains at least one of the compounds represented by formulae I-III and the silver halide grains containing silver chloride in an amount of >=90mol%, and the silver halide emulsion is sensitized by using the selenium compound. In formulae I-III, X<1> is NR<15>R<16> or the like; Y<1> is OH or same as X<1>; each of R<11>-R<16> is H or a specified group; each of X<2> and Y<2> is OH, -NR<23>R<24>, or the like; each of R<21>-R<24> is H or a specified group; X<3> is OH, -NR<32>R<33>, or the like; Y<3> is -CO- or -SO2-; R<31> is H or an optional substituent; each of R<32> and R<33> is H, alkyl, or the like. These compounds may be directly dispersed into the emulsion or dissolved in water or methanol and added to the emulsion.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has excellent rapid processing properties, high sensitivity, and little change in sensitivity due to changes in humidity during exposure.
Furthermore, the present invention relates to a silver halide photographic light-sensitive material that exhibits little increase in fog density even when the light-sensitive material is stored for a long period of time.

0002

BACKGROUND OF THE INVENTION Currently commercially available silver halide photographic materials and image forming methods using the same are diverse and are used in all fields. The halogen composition of the silver halide emulsions used in many of these light-sensitive materials, especially in the case of photographic materials, is often silver iodobromide, mainly consisting of silver bromide, in order to achieve high sensitivity. . On the other hand, in products used in markets where there is a strong demand for completing large quantities of prints in a short lead time, such as light-sensitive materials for color photographic paper, it is necessary to speed up the development process, so the use of bromide containing virtually no silver iodide is required. Silver or silver chlorobromide is used. In recent years, there has been an increasing demand for improved rapid processing performance of color photographic paper, and much research has been conducted. It is known that increasing the silver chloride content of the silver halide emulsion used dramatically improves the development speed. It is known that silver chloride emulsions generally have the drawback of low sensitivity, and in order to overcome this drawback, various techniques have been disclosed for increasing the sensitivity of silver halide emulsions with a high silver chloride content. ing.

Selenium sensitization is known as a technique for increasing the sensitivity of silver halide emulsions, and the present inventors applied selenium sensitization to silver halide emulsions with a high silver chloride content, and found that the sensitivity increased. We confirmed the effect of However, as a photosensitive material for color photographic paper, it is required that there is little change in photographic performance even after long-term storage. In the case of photosensitive materials using silver emulsions, it has been found that fog density tends to increase with long-term storage, which is a problem. Furthermore, when color photographic paper is printed in a laboratory, it is desirable that its photographic performance does not change due to changes in humidity. This is very important in maintaining constant quality at all times. In light-sensitive materials using selenium-sensitized high-silver chloride emulsions, selenium sensitization must be carried out sparingly in order to reduce the increase in fog density caused by long-term storage. However, it has also become clear that if selenium sensitization is applied sparingly in this manner, a problem arises in that sensitivity changes due to changes in humidity during exposure become large.

0004

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a photosensitive material with excellent rapid processing properties and high sensitivity, with little change in sensitivity due to fluctuations in humidity during exposure, and even when stored for a long period of time. An object of the present invention is to provide a silver halide photographic material in which an increase in fog density is suppressed.

[0005]

[Means for Solving the Problems] The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer containing a silver halide emulsion on a support. (I), at least one compound represented by general formula (II) and general formula (III), and silver halide grains having a silver chloride content of 90 mol% or more, and chemically amplified using a selenium compound. This was achieved by a silver halide photographic material containing a sensitive silver halide emulsion. General formula (I)

[0006]

[C4]

[0007] In the formula, X1 represents -NR15R16 or -NHSO2 R17, and Y1 is a hydroxyl group or
Represents a group with the same meaning as 1. R11, R12, R13, R
14 each represents a hydrogen atom or an arbitrary substituent,
R11 and R12, R13 and R14 may jointly form a carbon ring. R15 and R16 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group;
15 and R16 may jointly form a nitrogen-containing heterocycle. R17 represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (II)

[0008]

[C5]

[0009] In the formula, X2 and Y2 are each a hydroxyl group,
-NR23R24 or -NHSO2 R25. R21 and R22 each represent a hydrogen atom or an arbitrary substituent, and R21 and R22 may jointly form a carbocycle or a heterocycle. R23 and R24 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R23 and R24 may jointly form a nitrogen-containing heterocycle. R25 represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (III)

0010

[C6]

In the formula, X3 is a hydroxyl group or -NR32R
33, and Y3 represents -CO- or -SO2-. R31 represents a hydrogen atom or an arbitrary substituent, and n is 0 or 1. R32 and R33 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R31 and R32, and R32 and R33 may jointly form a nitrogen-containing heterocycle.

In order to incorporate the compounds represented by the general formula (I), general formula (II) and general formula (III) into the silver halide emulsion layer, they may be directly dispersed in the emulsion, or they may be directly dispersed in the emulsion. It may be added to the emulsion after being dissolved in a solvent such as water or methanol alone or in a mixed solvent. Further, although it may be added to the emulsion at any stage from emulsion preparation to immediately before coating, it is preferable to add it at the time of coating liquid preparation. The amount of the compound represented by general formula (I), general formula (II) and general formula (III) to be added is preferably 1 x 10-5 to 1 mol per mol of silver halide, and 1 x 10-5 to 1 mol per mol of silver halide. More preferably, the amount is 3 to 5×10 −1 mol. Among the compounds represented by general formula (I), general formula (II), and general formula (III), these compounds are effective for changes in sensitivity due to changes in humidity during exposure and for increases in fog density when photosensitive materials are stored for a long period of time. The suppressing effect is greatest for the compound represented by the general formula (III), and it is most preferable to contain at least one compound represented by the general formula (III).

Formula (I) will be explained in more detail. In the formula, X
1 represents -NR15R16 or -NHSO2 R17, and Y1 represents a hydroxyl group or a group having the same meaning as X1. R11, R12, R13, and R14 each represent a hydrogen atom or an arbitrary substituent. Examples of optional substituents include alkyl groups (preferably those having 1 to 20 carbon atoms, such as methyl, ethyl, octyl, hexadecyl, and t-butyl), aryl groups (preferably those having 6 to 20 carbon atoms,
For example, phenyl, p-tolyl), amino group (carbon number 0 to
20 are preferred, such as amino, diethylamino, diphenylamino, hexadecylamino), amide groups (preferably those with 1 to 20 carbon atoms, such as acetylamino, benzoylamino, octadecanoylamino, benzenesulfonamide), alkoxy Group (1 to 2 carbon atoms
0 is preferable, for example methoxy, ethoxy, hexadecyloxy), alkylthio group (preferably one with 1 to 20 carbon atoms, for example methylthio, butylthio, octadecylthio), acyl group (preferably one with 1 to 20 carbon atoms). , for example, acetyl, hexadecanoyl, benzoyl, benzenesulfonyl), carbamoyl group (with 1 to 1 carbon atoms),
20 are preferred, such as carbamoyl, N-hexylcarbamoyl, N,N-diphenylcarbamoyl)
, alkoxycarbonyl group (preferably one with 2 to 20 carbon atoms, such as methoxycarbonyl, octyloxycarbonyl, etc.), hydroxyl group, halogen atom (F, Cl, Br
), cyano group, nitro group, sulfo group, carboxyl group, etc. These substituents may be further substituted with another substituent (for example, those listed as R11). Further, R11 and R12, and R13 and R14 may jointly form a carbon ring (preferably a 5- to 7-membered ring). R15 and R16 are hydrogen atoms, alkyl groups (preferably those with 1 to 10 carbon atoms, such as ethyl, hydroxyethyl, and octyl), aryl groups (preferably those with 6 to 10 carbon atoms, such as phenyl, naphthyl), or heterocycles. Group (preferably one having 2 to 10 carbon atoms, for example 2-
furanyl, 4-pyridyl), which may be further substituted with a substituent (for example, those listed as R11). R15 and R16 may jointly form a heterocycle (preferably a 5- to 7-membered ring). R17 is an alkyl group (preferably one with 1 to 20 carbon atoms, e.g. ethyl, octyl, hexadecyl), an aryl group (preferably one with 6 to 20 carbon atoms, e.g. phenyl, p-tolyl, 4-dodecyloxyphenyl) , an amino group (preferably one with 0 to 20 carbon atoms, such as N,N-diethylamino, N,N-diphenylamino, morpholino) or a heterocyclic group (preferably one with 2 to 20 carbon atoms,
For example, 3-pyridyl), which may be further substituted.

In formula (I), X1 is preferably -NHS
O2 represents R17, R11, R12, R13, R1
4 preferably represents a hydrogen atom, an alkyl group, an amide group, a halogen atom, a sulfo group or a carboxyl group. Formula (II) will be explained in more detail. In the formula, X2, Y2
are hydroxyl group, -NR23R24 or -NHSO, respectively
2 represents R25. R21 and R22 represent a hydrogen atom or an arbitrary substituent. The optional substituents include, for example, R11
These include the substituents listed in the explanation of . Also, R21 and R2
2 jointly represents a carbocyclic ring or a heterocyclic ring (both preferably 5 to 5).
7-membered ring). R23 and R24 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the details thereof are the same as those for R15. R23 and R24 jointly represent a nitrogen-containing heterocycle (preferably 5
~7-membered ring). R25 represents an alkyl group, an aryl group, an amino group or a heterocyclic group, and the details are the same as R17.

In formula (II), X2 is preferably -NR
23R24 or -NHSO2 R25, R2
1 and R22 preferably represent a hydrogen atom, an alkyl group, or an aryl group, or together form a carbocycle or a heterocycle. Details of these groups are the same as R15. Formula (III)
will be explained in more detail. In the formula, X3 is a hydroxyl group or -N
Represents R32R33, and Y3 is -CO- or -SO
2 represents -. R31 is a hydrogen atom or any substitution (
For example, those listed in the explanation of R11), and n is 0 or 1. R32 and R33 represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the details thereof are the same as those for R15. Further, R31 and R32, and R32 and R33 may jointly form a heterocycle (preferably a 5- to 7-membered ring). In formula (III), X3 preferably represents -NR32R33, and Y3 preferably represents -
Represents CO-. R31 preferably represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group,
They may be further substituted with any substituent (for example, those listed in the explanation of R11). R32 and R33 preferably represent a hydrogen atom or an alkyl group.

[0016] Below, formula (I) used in the present invention, (
Specific examples of compounds represented by II) and (III) are listed below, but the present invention is not limited thereto.

[0017]

[C7]

[0018]

[Chemical formula 8]

[0019]

[Chemical formula 9]

[0020]

[Chemical formula 10]

[0021]

[Chemical formula 11]

[0022]

[Chemical formula 12]

[0023]

[Chemical formula 13]

[0024]

[Chemical formula 14]

[0025]

[Chemical formula 15]

[0026]

[Chemical formula 16]

The average halogen composition of the silver halide grains contained in at least one emulsion used in the present invention requires that the silver chloride content be 90 mol % or more. Further, it is preferable that the average halogen composition of all the silver halide constituting the silver halide grains of the emulsion is 95 mol % or more of silver chloride and substantially no silver iodide. Here, "substantially no silver iodide" means that the silver iodide content is 1.
It is preferably 0 mol% or less. A more preferable halogen composition of the silver halide grains is that 98 mol% or more of the total silver halide constituting the silver halide grains is silver chloride and is silver chlorobromide or silver chloride containing substantially no silver iodide. .

The silver halide grains of the present invention preferably have a localized phase of at least 10 mol % in terms of silver bromide content. In order to exhibit the effects of the present invention, the localized phase having a high silver bromide content must be located near the grain surface from the viewpoint of pressure resistance, treatment liquid composition dependence, etc. Here, the term "near the grain surface" refers to a position within 1/5 of the grain size of the silver halide grain used, measured from the outermost surface. The position is preferably within 1/10 of the grain size of the silver halide grains used, as measured from the outermost surface. The most preferred arrangement of the localized phase with a high silver bromide content is one in which the localized phase with a silver bromide content of at least 10 mol % is epitaxially grown at the corners of cubic or tetradecahedral silver chloride grains.

It is preferable that the silver bromide content of the localized phase with a high silver bromide content exceeds 10 mol %, but if the silver bromide content is too high, the silver bromide content decreases when pressure is applied to the photosensitive material. Undesirable characteristics may be imparted to the photographic material, such as the sensitivity and gradation greatly changing due to changes in the composition of the processing solution. Taking these points into consideration, the silver bromide content of the localized phase with a high silver bromide content is preferably in the range of 10 to 60 mol%, and 2
A range of 0 to 50 mol% is most preferred. The silver bromide content of the localized phase with a high silver bromide content can be determined using the X-ray diffraction method (for example,
It can be analyzed using methods such as those described in "Structural Analysis", New Experimental Chemistry Course 6, edited by the Chemical Society of Japan, published by Maruzen.

The localized phase having a high silver bromide content is 0.0% of the total silver amount constituting the silver halide grains contained in the emulsion of the present invention.
Preferably, it is composed of 1 to 20% silver;
More preferably, it consists of 0.5 to 7% silver. The interface between such a localized phase with a high silver bromide content and other phases may have a clear phase boundary or a transition region where the halogen composition gradually changes. good. Various methods can be used to form such a localized phase with a high silver bromide content. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, the localized phase can also be formed using a conversion method in which silver halide grains that have already been formed are converted into silver halide having a lower solubility product. For example, by adding an aqueous bromide solution to cubic or tetradecahedral silver halide host grains, or by adding a silver bromide or chloride solution having a smaller average grain size and a higher silver bromide content than the silver halide host grains. By mixing silver fine particles and then ripening, a localized phase with a high silver bromide content can be formed.

The formation of a localized phase with a high silver bromide content is preferably carried out in the presence of an iridium compound. Formation of the localized phase in the presence of an iridium compound means that
This refers to supplying an iridium compound simultaneously with, immediately before, or immediately after supplying silver or halogen to form a localized phase. For example, when forming a localized phase with a high silver bromide content by adding an aqueous bromide solution, the solution should contain an iridium compound in advance, or another solution containing an iridium compound should be added at the same time. Addition is preferably carried out. After mixing silver halide fine grains with a smaller average grain size and a higher silver bromide content than the silver halide host grains,
When a localized phase with a high silver bromide content is formed by ripening, it is also preferable to preliminarily contain an iridium compound in the silver halide fine grains with a high silver bromide content. An iridium compound may be present during phase formation other than the formation of a localized phase with high silver bromide content, but the localized phase with high silver bromide content is formed with at least 50% of the total iridium added. It is preferable. Most preferably, it is formed with at least 80% of the total iridium added.

The silver halide grains of the present invention have (
Whether it has a (100) surface, a (111) surface, or both, or even a surface that contains higher-order surfaces. Good, but mainly a cube consisting of (100) planes or 1
A tetrahedron is preferred. The size of the silver halide grains of the present invention may be within a commonly used range, but it is preferable that the average grain size is from 0.1 μm to 1.5 μm. The particle size distribution may be polydisperse or monodisperse, but monodisperse is preferable. In the particle size distribution representing the degree of monodispersity, the ratio (s/d) between the statistical standard deviation (s) and the average particle size (d) is preferably 0.2 or less, and 0.2 or less.
More preferably 15 or less. It is also preferable to use a mixture of two or more types of monodispersed emulsions.

The silver halide emulsion of the present invention is subjected to selenium sensitization. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. Selenium sensitization is usually carried out by adding an unstable selenium compound and/or a non-unstable selenium compound to a silver halide emulsion and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. As the unstable selenium compound, it is preferable to use the compounds described in Japanese Patent Publication No. 15748/1980, Japanese Patent Publication No. 13489/1982, Japanese Patent Application No. 130976/1997, Japanese Patent Application No. 229300/1999, and the like. Specific unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g., bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, phosphine selenides, colloidal metal selenium, etc. can give.

Although preferred types of unstable selenium compounds have been described above, these are not intended to be limiting. Those skilled in the art understand that when it comes to unstable selenium compounds used as sensitizers in photographic emulsions, the structure of the compound is not particularly important as long as selenium is unstable; It is generally understood that the moiety has no role other than to support the selenium and allow it to exist in an unstable form in the emulsion. In the present invention, unstable selenium compounds having such a broad concept are advantageously used. The non-unstable selenium compound used in the present invention is
No. 4553, Special Publication No. 52-34492 and Special Publication No. 5
The compound described in No. 2-34491 is used. Non-labile selenium compounds include, for example, selenite, potassium selenocyanide, selenazole compounds, quaternary salts of selenazole compounds, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, Examples include 2-selenoxazolidinethione and derivatives thereof. Among these selenium compounds, the following general formulas (IV) and (V) are preferable.
can be given. General formula (IV)

[0035]

[Chemical formula 17]

In the formula, Z1 and Z2 may be the same or different and represent an alkyl group (for example, methyl, ethyl, t-butyl, adamantyl, t-octyl)
, alkenyl groups (e.g. vinyl, propenyl), aralkyl groups (e.g. benzyl, phenethyl), aryl groups (e.g. phenyl, pentafluorophenyl, 4-
chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic groups (e.g. pyridyl, chenyl, furyl, imidazolyl),
-NR1 (R2), -OR3 or -SR4. R1, R2, R3 and R4 may each be the same or different and represent an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group include the same examples as Z1. However, R1 and R2 are hydrogen atoms or acyl groups (e.g., acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4
-trifluoromethylbenzoyl).

In the general formula (IV), preferably Z1 represents an alkyl group, an aryl group or -NR1 (R2), and Z2 represents -NR5 (R6). R1, R
2, R5 and R6 may each be the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In general formula (IV), more preferably N
, N-dialkylselenourea, N,N,N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N,N-dialkyl-arylselenoamide, N
-Alkyl-N-aryl-arylselenoamide. General formula (V)

[0038]

[Chemical formula 18]

In the formula, Z3, Z4 and Z5 may be the same or different, and are an aliphatic group, an aromatic group, a heterocyclic group, -OR7, -NR8 (R9), -S
Represents R10, -SeR11, -X or a hydrogen atom. R
7, R10 and R11 represent an aliphatic group, aromatic group, heterocyclic group, hydrogen atom or cation;
9 represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom, and X represents a halogen atom. In general formula (V), Z3, Z4, Z5, R7, R8, R9,
The aliphatic group represented by R10 and R11 is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group,
Aralkyl groups (e.g. methyl, ethyl, n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl,
cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl). In general formula (V), Z3, Z4
, Z5 , R7 , R8 , R9 , R10 and R1
The aromatic group represented by 1 is a monocyclic or condensed aryl group (
For example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-
methylphenyl).

In the general formula (V), Z3, Z4,
Z5, R7, R8, R9, R10 and R11
The heterocyclic group represented by is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom, or a sulfur atom (e.g., pyridyl, chenyl,
(furyl, thiazolyl, imidazolyl, benzimidazolyl). In the general formula (V), the cations represented by R7, R10 and R11 represent an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In general formula (V), preferably Z3, Z4 or Z5 represents an aliphatic group, an aromatic group or -OR7, and R7 represents an aliphatic group or an aromatic group. In general formula (V), more preferably represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of compounds represented by formulas (IV) and (V) are shown below, but the present invention is not limited thereto.

[0041]

[Chemical formula 19]

[0042]

[C20]

[0043]

[C21]

[0044]

[C22]

[0045]

[C23]

[0046]

[C24]

[0047]

[C25]

[0048]

[C26]

The amount of selenium sensitizer used depends on the selenium compound used, the silver halide grains (the type and content of halogen,
Although it varies depending on grain size, crystal shape, etc.), chemical ripening conditions, etc., it is generally 10-8 to 10-4 per mole of silver halide.
The amount used is preferably about 10-7 to 10-5 moles. The conditions for chemical sensitization in the present invention are not particularly limited, but the pAg is generally 5 to 10, preferably 5.
5 to 8, more preferably 6 to 7.5, and the temperature is generally 30 to 80°C, preferably 40 to 70°C. The pH is generally 4-10, preferably 5-8. The temperature is generally 30 to 80°C, preferably 40 to 70°C.
It is ℃. In the present invention, it is preferable to sensitize the surface to selenium after forming a localized phase with a high silver bromide content. As chemical sensitization other than selenium sensitization, it is preferable to use sulfur sensitization in combination, but it is also preferable to use gold sensitization, reduction sensitization, etc. in combination. The chemical sensitization with sulfur used in the present invention is carried out using a sulfur-containing compound (eg, thiosulfate, thioureas, mercapto compounds, rhodanine) that can react with active gelatin or silver. Specific examples of these are U.S. Pat. Nos. 1,574,944, 2,278,
No. 947, No. 2,410,689, No. 2,728
, No. 668 and No. 3,656,955.

In the photosensitive material of the present invention, a hydrophilic colloid layer which can be decolorized by treatment as described on pages 27 to 76 of European Patent EP 0,337,490A2 is added for the purpose of improving image sharpness, etc. Dyes (especially oxonol dyes) are added to the sensitive material so that the optical reflection density at 680 nm is 0.70 or more, and di- to tetrahydric alcohols (among others) are added to the water-resistant resin layer of the support. For example, titanium oxide surface-treated with trimethylolethane)
The content is preferably 2% by weight or more (more preferably 14% by weight or more).

Photographic additives such as cyan, magenta and yellow couplers that can be used in the present invention are preferably used after being dissolved in a high boiling point organic solvent, and the high boiling point organic solvent has a melting point of 100°C or less and a boiling point of 140°C. Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher,
More preferably, the temperature is 170°C or higher. Details of these high boiling point organic solvents are described in the lower right column on page 137 to the upper right column on page 144 of the specification of JP-A-62-215272. Cyan, magenta, or yellow couplers may also be impregnated into loadable latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents mentioned above, or water-insoluble and organic It can be dissolved together with a solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution. Preferably columns 7 to 15 of U.S. Pat. No. 4,857,449.
Column and No. 12 of International Publication No. WO88/00723 Specification
Homopolymers or copolymers described on pages 30 to 30 are used, and methacrylate or acrylamide polymers, particularly acrylamide polymers, are preferably used from the viewpoint of color image stabilization.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277,589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler. That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent the generation of stains and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

[0053] The photosensitive material according to the present invention is also treated with anti-mildew agents as described in JP-A No. 63-271247 in order to prevent various types of mold and bacteria that grow in the hydrophilic colloid layer and degrade images. It is preferable to add an agent.

[0054] The support used in the photosensitive material according to the present invention may be a white polyester support for display purposes or a support on the side having a silver halide emulsion layer on which a layer containing a white pigment is provided. A support may also be used. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support. In particular, the transmission density of the support was set to 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferable to set it in the range of 5 to 0.8.

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

[0056] Also, upon exposure, US Pat. No. 4,88
Preferably, a band stop filter as described in US Pat. No. 0,726 is used. This removes light color mixing,
Color reproducibility is significantly improved.

The exposed light-sensitive material may be subjected to conventional black-and-white or color development processing, but in the case of color light-sensitive materials, for the purpose of rapid processing, it is preferable to carry out bleach-fixing processing after color development. In particular, when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fix solution is approximately 6.5 for the purpose of promoting desilvering.
The following is preferable, and about 6 or less is more preferable.

Silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied to process this light-sensitive material As processing additives, the following patent publications, especially European Patent EP 0,355,660A2 (
Those described in JP-A-2-139544) are preferably used.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

[0064] Also, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan coupler described in No. 33144, European Patent EP 0,333,185A2
3-hydroxypyridine cyan coupler (
Among them, 4 of couplers (42) listed as specific examples
Particularly preferred are equivalent couplers with a chlorine leaving group to make them di-equivalent, couplers (6) and (9), and cyclic active methylene cyan couplers described in JP-A No. 64-32260 (especially preferred). Particular preference is given to the couplers examples 3, 8, 34 listed by way of example).

As a method for processing color photosensitive materials, the methods described in JP-A-2-207250, page 27, upper left column to page 34, upper right column, are particularly preferably applied.

[0066]

EXAMPLES The present invention will be explained in detail below according to Examples, but the present invention is not limited thereto. Example 1 32g of lime-treated gelatin was added to 800cc of distilled water,
After dissolving at 40°C, 5.76g of sodium chloride was added and the temperature was raised to 75°C. Add 1% N,N'-dimethylimidazolidine-2-thione (1% aqueous solution) to this solution.
．． 8cc was added. Next, add 100g of silver nitrate to 40g of distilled water.
A solution containing 0 cc of sodium chloride and a solution of 34.4 g of sodium chloride dissolved in 400 cc of distilled water were heated for 5 minutes while maintaining the temperature at 75°C.
The mixture was added to the above solution and mixed for 3 minutes. Next, silver nitrate 60
g dissolved in 200 cc of distilled water and 1 ml of sodium chloride.
Dissolve 7.4g in 200cc of distilled water and heat at 75°C.
The mixture was added and mixed for 18 minutes while maintaining the temperature. After desalting and washing with water at 40°C, 90 g of lime-treated gelatin was added, and the pAg was adjusted to 7.5 and the pH to 6.5 with sodium chloride and sodium hydroxide. After raising the temperature to 58°C, a blue-sensitive sensitizing dye shown below was added at 3 x 10-4 mol per mol of silver halide, and triethylthiourea was added at 6 x 10-6 mol per mol of silver halide. Optimal sulfur sensitization was carried out using The silver chloride emulsion thus obtained was designated as Emulsion A.

Emulsion A is made by changing the pH adjusted to 5.8 before adding a blue-sensitive sensitizing dye, and instead of optimally sulfur sensitizing using triethylthiourea, dimethylselenourea is mixed with a halogen. A silver chloride emulsion was prepared which differed only in that it was optimally sensitized with selenium using 6 x 10 -6 mol per mol of silver chloride, and this was designated as emulsion B. 32g lime-processed gelatin
was added to 800 cc of distilled water and dissolved at 40°C, then 5.76 g of sodium chloride was added and the temperature was raised to 75°C. Add N,N'-dimethylimidazolidine to this solution.
1.8 cc of 2-thione (1% aqueous solution) was added. Subsequently, a solution in which 100 g of silver nitrate was dissolved in 400 cc of distilled water and a solution in which 34.4 g of sodium chloride was dissolved in 400 cc of distilled water were added to and mixed with the above solution over 53 minutes while maintaining the temperature at 75°C. Next, add 59.2 g of silver nitrate to 200 c of distilled water.
Add the solution dissolved in c and 17.1 g of sodium chloride to 2 ml of distilled water.
00 cc was added and mixed over 18 minutes while maintaining the temperature at 75°C. After lowering the temperature to 40°C, add the blue-sensitive sensitizing dye shown below at 3 x 10-4 per mole of silver halide.
Then add 0.8 g of silver nitrate in 100 cc of distilled water and 0.56 g of potassium bromide in 100 cc of distilled water.
The solution dissolved in c was added and mixed over 8 minutes while maintaining the temperature at 40°C. After desalting and washing with water, 90 g of lime-treated gelatin was added, and the pAg and pH were adjusted to 7.5 and 6.5 with sodium chloride and sodium hydroxide, respectively. After raising the temperature to 58° C., sulfur sensitization was optimally performed using the same amount of triethylthiourea as in Emulsion A. Silver chlorobromide emulsion thus obtained (containing 0.5 mol% silver bromide)
was designated as emulsion C.

Emulsion C is made by changing the pH adjusted to 5.8 before adding a blue-sensitive sensitizing dye, and instead of optimally sulfur sensitizing using triethylthiourea, the same amount as Emulsion B is used. A silver chlorobromide emulsion was prepared which differed only in that it was optimally sensitized to selenium using dimethylselenourea, and this was designated as emulsion D. Emulsions A, B, C and D thus prepared
The particle shape, particle size, and particle size distribution were determined from electron micrographs. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was calculated by dividing the standard deviation of the particle size by the average particle size. Emulsions A, B, C and D all had cubic grains with a grain size of 0.82 μm and a grain size distribution of 0.10. The electron micrographs of emulsions C and D are
Compared to emulsions A and B, the corners of the cube had a more pointed shape. In addition, X-ray diffraction of Emulsions C and D showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol % to 30 mol %. From the above, emulsions C and D are
It can be said that a localized phase having a silver bromide content of 10 mol % to 30 mol % is epitaxially grown at the corners of the cubic silver chloride matrix grains.

After corona discharge treatment was applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was applied, and various photographic constituent layers were further coated to obtain the layer structure shown below. A multilayer color photographic paper (Sample A) was prepared. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (ExY) 19.1g, color image stabilizer (
Cpd-1) 4.1g and color image stabilizer (Cpd-7)
To 0.7 g, add 27.2 cc of ethyl acetate and solvent (So
4. lv-3) and solvent (Solv-7), respectively.
1 g of sodium dodecylbenzene sulfonate was added and dissolved, and this solution was mixed with 18 ml of a 10% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate.
After adding it to 5 cc, it was emulsified and dispersed using an ultrasonic homogenizer. The obtained dispersion was mixed and dissolved with the silver chloride emulsion A described above to prepare a first layer coating solution. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, the total amount of Cpd-10 and Cpd-11 was 25% each in each layer.
．． It was added at a concentration of 0 mg/m2 and 50.0 mg/m2. The following spectral sensitizing dyes were used in each layer.

[0070]

[C27]

[0071]

[C28]

[0072]

[C29]

The following compound was added to the red-sensitive emulsion layer in an amount of 2.6×10 −3 mol per mol of silver halide.

[0074]

[C30]

In addition, the following dyes (the coating amount is shown in parentheses) were added to the emulsion layer to prevent irradiation.

[0076]

[Chemical formula 31]

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver. Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)] First layer (blue-sensitive yellow coloring layer) Said silver chloride emulsion A

0.30 Gelatin

1.22
Yellow coupler (ExY)

0.82 Color image stabilizer (Cpd-1)

0.19 Solvent (Solv-3)

0.18 Solvent (So
lv-7)
0.1
8 Color image stabilizer (Cpd-7)

0.06

Second layer (color mixing prevention layer) Gelatin

0.64 Color mixing prevention agent (Cpd
-5)
0.10 Solvent (
Solv-1)
0
．． 16 Solvent (Solv-4)

0.08 Third layer (green-sensitive magenta coloring layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of large emulsion B with an average grain size of 0.55 μm and small emulsion B with an average grain size of 0.39 μm) Ag molar ratio).The coefficient of variation of grain size distribution is 0.10 and 0.08, respectively, and each size emulsion is A
0.12 gelatin (gBr0.8 mol% was locally contained on a part of the particle surface)


1.28 magenta coupler (ExM)

0.23 color image stabilizer (Cpd-2)

0.03 color image stabilizer (Cpd-3)

0.16 color image stabilizer (Cpd-
4)
0.02 Color image stabilizer (Cpd-9)
0.02
Solvent (Solv-2)

0.40 Fourth layer (ultraviolet absorption layer) Gelatin

1.41 Ultraviolet absorber (UV-1)

0.47 Color mixing prevention agent (Cpd
-5)
0.05 solvent (So
lv-5)
0.2
4

Fifth layer (red-sensitive cyan coloring layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of large emulsion C with an average grain size of 0.58 μm and small emulsion C with an average grain size of 0.45 μm) (Ag molar ratio).The coefficient of variation of the grain size distribution is 0.09 and 0.11, and each size emulsion has AgBr0
．． (6 mol% was locally contained on a part of the particle surface)
0.23 gelatin

1.04 Cyan coupler (ExC)

0.32 color image stabilizer (Cpd-2)

0.03 color image stabilizer (Cpd
-4)
0.02 color image stabilizer (Cpd-6)
0.18 color image stabilizer (Cpd-7)
0
．． 40 color image stabilizer (Cpd-8)

0.05 solvent (Solv-6)

0.14 Sixth layer (ultraviolet absorption layer) Gelatin

0.48 Ultraviolet absorber (UV-1)

0.16 Color mixing prevention agent (Cpd
-5)
0.02 solvent (So
lv-5)
0.0
8 Seventh layer (protective layer) Gelatin

1.10 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17
liquid paraffin

0.03

[0080]

[C32]

[0081]

[Chemical formula 33]

[0082]

[C34]

[0083]

[C35]

[0084]

[C36]

[0085]

[C37]

[0086]

[C38]

[0087]

[C39]

[0088]

[C40]

For Sample A obtained as above, the emulsion of the first layer (blue-sensitive layer) was replaced as shown in Table 6,
Further, photosensitive materials were prepared that differed only in that the compounds shown in Table 6 were added to the first layer coating solution, and these were designated as Samples B to W. In order to investigate the sensitivity of the photosensitive material and the fluctuation range of photographic sensitivity due to changes in humidity during exposure,
and keeping the photosensitive material in an atmosphere of 25°C-85%RH,
Exposure for 0.1 seconds was applied through an optical wedge and a blue filter, and color development processing was performed using the processing steps and processing solution shown below. Sensitivity (S) is calculated by calculating the reciprocal of the exposure amount required to give a density 0.5 higher than the fog density when exposed at 25°C and 55% RH, and is expressed as a relative value with the sensitivity of sample A as 100. did. The sensitivity change (ΔS humidity) was expressed as the difference in the logarithm of the exposure amount required to give a density 0.5 higher than the fog density. Negative values represent desensitization under high humidity exposure. To evaluate changes in photographic performance due to long-term storage of photosensitive materials, samples were stored in an atmosphere of 60°C and 40% RH for 2 days, then exposed and processed as described above, and compared with samples that were not stored in the above atmosphere. Changes in fog density (△D storage) were measured. The above results are shown in Table 7.

[0090]

[Table 6]

[0091]

[Table 7]

(Development Processing) The exposed sample was subjected to continuous processing (running) using a paper processing machine until twice the capacity of the color development tank was replenished in the next processing step, and then used. Treatment process temperature
Time Replenisher* Tank capacity
Color development 35℃ 4
5 seconds 161 ml 17 liters Bleach-fixing 30-35℃
45 seconds 215 ml 17
Liter rinse■ 30-35℃
20 seconds -
10 liter rinse■ 30-35
℃ 20 seconds -
10 liter rinse ■ 30~
35℃ 20 seconds 350ml
10 liters dry
70-80° C. 60 seconds * The replenishment amount was per 1 m 2 of the photosensitive material (3 tank countercurrent system from rinsing ■ to ■ was used.) The composition of each processing solution was as follows.

Color developer
tank liquid
replenisher water

800ml 800ml Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid
1.5g 2.0g Potassium bromide
0.015g
- Triethanolamine
8.0g
12.0g Sodium chloride
1.4g
− Potassium carbonate

25g 25g
N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-amino aniline sulfate
5.0g 7.0g
N,N-bis(carboxymethyl)hydrazine
4.0g 5.0g N,N-di(sulfoethyl)hydroxylamine・1Na

4.0g 5.0g Fluorescent brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.
0g 2.0g Add water

1000ml 1000ml
pH (25℃)
10.05 10
．． 45

Bleach-fix solution (tank solution and replenisher solution are the same) Water


400ml ammonium thiosulfate (7
00g/liter)
100ml sodium sulfite

17g ethylenediaminetetraacetic acid iron(III) ammonium
55g Disodium ethylenediaminetetraacetate
5g
ammonium bromide

Add 40g water

1000ml
pH (25℃)

6.0 Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium and magnesium are each 3
ppm or less)

As is clear from the results in Table 7, selenium sensitization is effective in increasing the sensitivity of high-silver chloride emulsions, but the desensitization is large when exposed to light under high humidity, and the fog density during long-term storage is low. There is also a problem that the increase is large (sample E). Samples containing selenium-sensitized high silver chloride emulsions and compounds of the present invention (F, G, H, N
-W) have the characteristics of high sensitivity but little desensitization during exposure under high humidity and little sensitization during long-term storage. Furthermore, these effects were more pronounced in the samples (N to W) used in combination with emulsions having localized phases with high silver bromide content near the surface of silver halide grains than in the samples without localized phases (F). -H) It can be seen that this is more remarkable compared to H). Example 2 32g of lime-treated gelatin was added to 1000cc of distilled water and dissolved at 40°C, then 3.3g of sodium chloride was added and the temperature was raised to 70°C. Add 1% N,N'-dimethylimidazolidine-2-thione (1% aqueous solution) to this solution.
．． 8cc was added. Next, add 32.0g of silver nitrate to 22.0g of distilled water.
A solution obtained by dissolving 11.0 g of sodium chloride in 200 cc of distilled water was added to and mixed with the above solution over 14 minutes while maintaining the temperature at 70°C. Furthermore, silver nitrate 1
A solution in which 28.0 g of sodium chloride was dissolved in 560 cc of distilled water and a solution in which 44.0 g of sodium chloride was dissolved in 560 cc of distilled water were added and mixed over 40 minutes while maintaining the temperature at 70°C. 4
After desalting and washing with water at 0°C, 90.0 g of lime-treated gelatin was added, and the pAg was adjusted to 7.5 and the pH to 5.8 with sodium chloride and sodium hydroxide. Subsequently, a blue-sensitive sensitizing dye similar to that used in Example 1 was added at 4×10 −4 mol per mol of silver halide, and then 6×10 −4 mol was added per 1 mol of silver halide, and then 6
Selenium sensitization was optimally performed at 0°C. The silver chloride emulsion thus obtained was designated as Emulsion E. 32 g of lime-treated gelatin was added to 1000 cc of distilled water and dissolved at 40°C, then 3.3 g of sodium chloride was added and the temperature was raised to 70°C. 2.0 cc of N,N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added to this solution. Next, a solution of 32.0 g of silver nitrate dissolved in 200 cc of distilled water, 10.9 g of sodium chloride, and 0 potassium bromide were added.
．． Dissolve 22g in 200cc of distilled water and heat at 70°C.
The mixture was added to and mixed with the above solution over a period of 15 minutes while maintaining the temperature. Furthermore, a solution of 128.0 g of silver nitrate dissolved in 560 cc of distilled water, 43.6 g of sodium chloride, and 0.0 g of potassium bromide were added.
A solution obtained by dissolving 90 g in 560 cc of distilled water was added and mixed over 40 minutes while maintaining the temperature at 70°C. After desalting and washing at 40°C, 90.0 g of lime-treated gelatin
was added, and the pAg was adjusted to 7.5 and the pH to 5.8 with sodium chloride and sodium hydroxide. Subsequently, a blue-sensitive sensitizing dye similar to that used in Example 1 was added at 4 x 10-4 mol per mol of silver halide, and the mixture was heated to 60°C using the same amount of dimethylselenourea as in Example 1. The selenium sensitization was performed optimally. The silver chlorobromide emulsion thus obtained (containing 1 mol % of silver bromide) was designated as Emulsion F. Emulsion G is a silver bromide ultrafine grain emulsion (grain size 0.05 μm, potassium hexachloroiridate (IV) 7.0× per mole of silver bromide at 60°C before selenium sensitization).
After adding 0.4 mol% of silver bromide to silver chloride (containing 10-6 mol) and aging for 15 minutes, a silver chlorobromide emulsion was prepared with the only difference being that selenium sensitization was optimized. This was designated as Emulsion G. For the three types of emulsions E, F, and G thus prepared, the grain shape, grain size, and grain size distribution were determined from electron micrographs. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was calculated by dividing the standard deviation of the particle size by the average particle size. E, F and G 3
All types of emulsions had cubic grains with a grain size of 0.69 μm and a grain size distribution of 0.09. A photosensitive material that differs from Sample A obtained in Example 1 only in that the emulsion in the first layer (blue-sensitive layer) was replaced as shown in Table 8, and the compounds shown in Table 8 were further added to the first layer coating solution. Materials were prepared and designated as samples a to i. Regarding these samples, as in Example 1, the effect of humidity during exposure and changes in fog density due to long-term storage of the photosensitive material were investigated. The results are shown in Table 8.

[0096]

[Table 8]

As is clear from the results in Table 8, the effects of the present invention are particularly remarkable in emulsions having a localized phase with a high silver bromide content near the surface of the silver halide grains.

[0098]

[Effects of the Invention] The present invention provides excellent rapid processing properties, high sensitivity, and less fluctuation in sensitivity due to changes in humidity during exposure.
Furthermore, a silver halide photographic material is obtained in which an increase in fog density is suppressed even when the material is stored for a long period of time.

Claims (2)

[Claims] Claim 1: A silver halide photographic material having at least one light-sensitive emulsion layer containing a silver halide emulsion on a support, wherein the light-sensitive emulsion layer contains a compound represented by the general formula (I).
, containing at least one compound represented by the general formula (II) or the general formula (III) and silver halide grains having a silver chloride content of 90 mol% or more, and chemically sensitized using a selenium compound. A silver halide photographic material characterized by containing a silver halide emulsion. General formula (I)
embedded image In the formula, X1 is -NR15R16 or -NHSO2
R17 represents a hydroxyl group or a group having the same meaning as X1. R11, R12, R13, and R14 each represent a hydrogen atom or an arbitrary substituent, and R11 and R1
2. R13 and R14 may jointly form a carbon ring. R15 and R16 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R15 and R16
may jointly form a nitrogen-containing heterocycle. R17
represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (II) [Formula 2] In the formula, X2 and Y2 are each a hydroxyl group, -NR23R
24 or -NHSO2 R25. R21, R
22 each represents a hydrogen atom or an arbitrary substituent,
R21 and R22 may jointly form a carbocycle or a heterocycle. R23 and R24 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R23
and R24 may jointly form a nitrogen-containing heterocycle. R25 represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (III) [Formula 3] In the formula, X3 represents a hydroxyl group or -NR32R33, and Y3 represents -CO- or -SO2 -. R3
1 represents a hydrogen atom or an arbitrary substituent, and n is 0 or 1. R32 and R33 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R31, R32, and R3
2 and R33 may jointly form a nitrogen-containing heterocycle. 2. Substances in which 95 mol % or more of silver chloride contains a localized silver bromide phase with a silver bromide content of at least 10 mol % in the vicinity of the surface of silver halide grains contained in a silver halide emulsion. 2. The silver halide photographic material according to claim 1, which is a silver chlorobromide emulsion which does not contain silver iodide.