JP2006284939A - Silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material which suppresses remaining of a sensitizing dye after development, ensures improved stability in film production by coating, and has high sensitivity and excellent unexposed film storage stability of the sensitive material. <P>SOLUTION: The silver halide color photosensitive material contains at least one compound represented by formula (I) or (IV) in at least one layer in the silver halide color photosensitive material. In the formula (I), Ar represents an aromatic group; R<SP>1</SP>and R<SP>2</SP>each independently represent H, alkyl or an aromatic group; G<SP>1</SP>represents carbonyl, sulfonyl, sulfinyl, phosphoryl, oxalyl or iminomethylene; Het<SP>1</SP>represents a heterocyclic group; and R<SP>3</SP>-R<SP>5</SP>each independently represent H, alkyl, aralkyl or an aromatic group. In the formula (IV), Ar and R<SP>1</SP>-R<SP>5</SP>each do not contain a polyhydroxy-aromatic ring as its partial structure, and when R<SP>5</SP>is aryl, both R<SP>3</SP>and R<SP>4</SP>represent H. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, to improve the residual color of a white background after color development and to improve the change in color of the white background during long-term storage of a color image. The present invention relates to a silver color photographic light-sensitive material.

In a silver halide color photographic light-sensitive material, a sensitizing dye is added to a photosensitive silver halide emulsion grain and spectrally sensitized to a desired wavelength region including blue, green, red or infrared.
The sensitizing dye added here is usually unnecessary for the image after the development processing, and it is preferable that all of the sensitizing dye is originally discharged or decolored from the photosensitive material in the development processing step. In silver halide color photographic light-sensitive materials, some sensitizing dyes may remain until after the development processing step.
For example, in the color reversal film photographic material, when such sensitizing dye remains, the coloring of the sensitizing dye tends to be noticeable on the white background of the image, and the color of the white background changes due to the fading of the sensitizing dye caused by the observation light. Therefore, it is desirable that the remaining of the sensitizing dye is kept small as a color film design.
On the other hand, in recent color films, there are many means to increase the surface area by using silver halide emulsion grains to be used as tabular grains and to add more sensitizing dyes to the increased surface to improve the sensitivity. It has become. Naturally, this increases the residual amount of the sensitizing dye after the development processing and impairs the quality of the color film. Therefore, a technique for reducing the residual amount of the sensitizing dye has been demanded. Further, such a technique for reducing the residual amount of the sensitizing dye has been particularly important in recent technological trends that increase the aspect ratio of tabular silver halide grains and serve as a resource for improving sensitivity.

  In addition, a silver halide color photographic light-sensitive material having a non-color-sensitive photosensitive emulsion layer for the purpose of increasing the multi-layer effect has been developed to improve color reproducibility, but it was added to the non-color-sensitive photosensitive emulsion layer. Since the oxidized form of the color developing agent generated from the silver halide diffuses to other image forming layers, the amount of the color turbidity inhibitor added is increased. As a result, the stability of the silver halide color photographic light-sensitive material during raw storage and the stability of the coated surface during coating film formation began to appear. These performances are also important qualities, and imparting this stability was a new issue.

On the other hand, hydrazine compounds typified by hydrazides are known as anti-turbidity agents (for example, Patent Document 1) in silver halide color photographic light-sensitive materials, and are also known to have an effect on image storability (for example, Patent Document 2) has not been known at all to be effective in reducing the residual sensitizing dye, and it has not always been satisfactory with respect to the coated surface.
Further, hydrazides whose acyl part is a heterocyclic ring are used as a thickening agent for black-and-white silver halide light-sensitive materials for printing (for example, Patent Documents 3 to 6), and a direct positive for surface development in the presence of a nucleating agent. Although it has been proposed to use it as a nucleating agent for a silver halide photographic light-sensitive material (for example, Patent Document 5 and Patent Document 6), there is no description of prevention of color turbidity or improvement of residual color due to the remaining of a sensitizing dye.
JP-A-1-147455 (pages 26-34) JP2003-43647A (page 57) Japanese Patent Publication No. 3-75850 US Pat. No. 4,816,373 JP-A-2-196234 JP-A-2-196235

  The object of the present invention is to reduce the residual of sensitizing dye after development processing in the field of silver halide color photographic light-sensitive materials, and to improve the stability at the time of coating film formation. It is to provide a silver halide color photographic light-sensitive material having excellent properties.

As a result of intensive studies on the residual reduction of the sensitizing dye in the color film and the stability during raw storage and coating film formation, the present inventors have prevented color turbidity between the spectrally sensitized color-sensitive layers. As a result, we have found that when a specific anti-turbidity agent is used as an inhibitor for this, not only the stability during raw storage and coating film formation, but also the residual amount of sensitizing dye is reduced, and further investigation The present invention has been reached.
The object of the present invention has been achieved by the following constitution.

(1) In a silver halide color photographic material having at least one photosensitive silver halide emulsion layer on a support, at least one layer of the silver halide color photographic material has the following general formula (I) A silver halide color photographic light-sensitive material comprising at least one compound represented by the formula:

In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group or Represents an iminomethylene group, and Het ¹ represents a heterocyclic group. )

(2) The silver halide color photographic light-sensitive material as described in (1), wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).

In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group or Represents an iminomethylene group, and Het ² represents a nitrogen-containing hetero 6-membered ring group.

(3) The silver halide color photographic light-sensitive material as described in (2), wherein the compound represented by the general formula (II) is a compound represented by the following general formula (III).

In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group or Represents an iminomethylene group. R ^a represents ^a substituent, and n represents 0 or an integer of 1 to 4.

(4) In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one hydrophilic layer other than the light-sensitive layer in the silver halide color photographic light-sensitive material. The silver halide color photographic light-sensitive material as described in (3), wherein the colloid layer contains at least one compound represented by the general formula (III).

(5) In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one hydrophilic layer other than the light-sensitive layer in the silver halide color photographic light-sensitive material. A silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula (IV) in a colloid layer.

In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group or Represents an iminomethylene group, and R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aromatic group. However, each group of Ar and R ^{1 to} R ⁵ does not contain a polyhydroxy aromatic ring as a partial structure thereof, and when R ⁵ is an aryl group, R ³ and R ⁴ both represent a hydrogen atom.

(6) The silver halide color photographic material as described in (1), wherein the compound represented by the general formula (I) is a color turbidity inhibitor.

(7) The silver halide color photographic light-sensitive material as described in (5), wherein the compound represented by the general formula (IV) is a color turbidity inhibitor.

(8) In at least one silver halide emulsion forming the silver halide emulsion layer, 70% or more of the total projected area of silver halide grains contained in the silver halide emulsion is a flat plate having an average aspect ratio of 2 or more. The silver halide color photographic light-sensitive material as described in any one of (1) to (7), which is a silver halide grain.

(9) The silver halide color photographic light-sensitive material as described in (8), wherein the tabular silver halide grains have a {111} plane as the main plane.

(10) The silver halide color photographic material as described in (8) or (9), wherein the silver iodide content of the tabular silver halide grains is 0.5 to 20 mol%.

  The present invention improves the residual color due to the residual reduction of the sensitizing dye after the development processing of the silver halide color photographic light-sensitive material, improves the stability at the time of coating film formation, and has high sensitivity and stable storage of the light-sensitive material. A silver halide color photographic light-sensitive material having excellent properties can be provided.

The present invention is described in detail below.
First, the compound represented by the general formula (I) will be described in detail.
The aromatic group represented by Ar represents an aryl group or a heteroaromatic group. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples thereof include phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, and the like, and may be further condensed to form a heteroaromatic ring as a whole. The heteroaromatic group contains, for example, a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, and may be condensed with an aromatic carbocycle, specifically, for example, imidazolyl, pyridyl, pyrazyl, pyrimidyl, quinolyl, Examples include isoquinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, oxadiazolyl, thiadiazolyl, benzthiazolyl, carbazolyl, azepinyl and the like.

  Ar may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms; For example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc., alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably carbon numbers) 2 to 20, particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, Particularly preferred are those having 2 to 10 carbon atoms, such as propargyl, 3-pentynyl, etc., and aryl groups (preferably having 6 to 30 carbon atoms, more preferred). Or having 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, etc., an amino group (preferably having 0 to 30 carbon atoms, more preferably Has 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc., an alkoxy group (preferably having 1 to 30 carbon atoms). More preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc., aryloxy groups (preferably having 6 to 30 carbon atoms, more preferably Has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms. , 1-naphthyloxy, 2-naphthyloxy, etc.),

Heteroaromatic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyl group (preferably Has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, More preferably, it has 5 to 30 carbon atoms, particularly preferably 10 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably 7 to 30 carbon atoms, more preferably 10 to 30 carbon atoms). Particularly preferably having 15 to 30 carbon atoms, such as phenyloxycarboni Etc.), acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, particularly preferably 15 to 30 carbon atoms such as acetoxy, benzoyloxy, etc.), acylamino groups (preferably having 2 carbon atoms) -30, more preferably 5-30 carbon atoms, particularly preferably 10-30 carbon atoms, such as acetylamino, benzoylamino, etc., alkoxycarbonylamino groups (preferably 2-30 carbon atoms, more preferably carbon atoms). 5 to 30, particularly preferably 10 to 30 carbon atoms, for example, methoxycarbonylamino and the like, aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 10 to 30 carbon atoms, particularly preferably carbon number) 15 to 30, for example, phenyloxycarbonylamino and the like, sulfonylamino group (preferably Alternatively, it has 1 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, and particularly preferably 10 to 30 carbon atoms. For example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably 0 to 30 carbon atoms, More preferably, it has 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms. For example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc.), a carbamoyl group (preferably 1-30 carbon atoms). More preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc., alkylthio groups (preferably having 1 to 30 carbon atoms, more preferably carbon atoms). 1 to 20, particularly preferably 1 to 12 carbon atoms, for example Methylthio, ethylthio, etc.),

An arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio), a heteroaromatic thio group (preferably having 1 to 30 carbon atoms, More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms. For example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio, etc.), a sulfonyl group (preferably Has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), a sulfinyl group (preferably 1 to 30 carbon atoms, more preferably carbon atoms). 1 to 20, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably carbon 1-30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, such as ureido, methylureido, phenylureido, etc., phosphoric acid amide groups (preferably having 1-30 carbon atoms, more preferably Has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, Iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms). Examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. Specific examples include imidazolyl and pyridyl. Quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, for example, trimethylsilyl, triphenylsilyl, etc., urethane group (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, still more preferably 2 to 24 carbon atoms, Methoxycarbonylamino, ethoxycarbonylamino, n-octadecyloxycarbonylamino, etc.), an aralkyl group (preferably having 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, still more preferably 7 to 24 carbon atoms, Benzyl, phenethyl, naphthylmethyl, etc.) It is.

  These substituents may be further substituted.

  The aromatic group represented by Ar is particularly preferably an aryl group. More preferable substituents include alkyl groups, aralkyl groups, alkoxy groups, aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, hydroxy groups. A halogen atom, a cyano group, a sulfo group or a carboxyl group, particularly preferably an acylamino group, a sulfonylamino group, a ureido group or a urethane group.

The alkyl group represented by R ¹ and R ² in the general formula (I) is preferably one having 1 to 30 carbon atoms and may be linear, branched or cyclic. Specific examples include methyl, ethyl, butyl, t-butyl, cyclohexyl, octyl, dodecyl, octadecyl and the like.
The aralkyl group represented by R ¹ and R ² is preferably one having 7 to 30 carbon atoms, and specifically includes benzyl, phenethyl, naphthylmethyl and the like.
The aromatic group represented by R ¹ and R ² is an aryl group or heteroaromatic group shown in the example of Ar, preferably an aryl group, and the aryl group preferably has 6 carbon atoms. ˜30, specifically phenyl, naphthyl and the like.

R ¹ and R ² are particularly preferably a hydrogen atom.

G ¹ in the general formula (I) represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group, or an iminomethylene group, and particularly preferably a carbonyl group.

Het ¹ in formula (I) represents a heterocyclic group, preferably a 5- to 7-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom. For example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, Benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadia Ropirijin, dibenzazepines, tri benzazepine, furan, benzofuran, thiophene, benzothiophene, and the like, these rings are benzo-fused, may form a heterocyclic ring condensed ring.
Here, Het ¹ may have a substituent, and specific examples thereof include the same as those described above as the substituent for Ar.

Among the compounds represented by the general formula (I), preferred are the compounds represented by the general formula (II).
^{Here, Ar, R 1, R 2} , and G ¹ is Ar in the general formula ^{(I), R 1, R} 2, and G ¹ and respectively the same.
Het ² in the general formula (II) represents a nitrogen-containing hetero 6-membered ring, such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline. is there.

Among the compounds represented by the general formula (II), more preferable are compounds represented by the general formula (III), and the pyridine ring group to which G ¹ is bonded is 2-pyridyl, 3-pyridyl, 4-pyridyl. Represents one of the following. R ^a represents ^a substituent, and specific examples include those listed as the substituent for Ar. n represents an integer of 0, 1 to 4, and is preferably 0.

Next, the compound represented by formula (IV) will be described.
Wherein, Ar, R ^1, R ² and G ¹ is Ar in the general formula ^{(I), R 1, R} 2 and G ¹ and respectively the same.
R ³ , R ⁴ and R ⁵ in the general formula (IV) each independently represent a hydrogen atom, an alkyl group, an aralkyl group or an aromatic group, and the alkyl group is preferably a straight chain having 1 to 30 carbon atoms. However, it may be branched or cyclic. Specific examples include methyl, ethyl, butyl, t-butyl, cyclohexyl, octyl, dodecyl, octadecyl and the like. The aralkyl group preferably has 7 to 30 carbon atoms, and specifically includes benzyl, phenethyl, naphthylmethyl and the like. The aromatic group has the same meaning as the aryl group and heteroaromatic group described for Ar.
R ³ , R ⁴ and R ⁵ may further have a substituent, and the substituent is the same as the example of the substituent for Ar.

R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
R ⁵ is preferably an alkyl group or an aryl group, and particularly preferably an aryl group or an alkyl group having 10 or less carbon atoms. Further, when R ⁵ is an aryl group, R ³ and R ⁴ both represent a hydrogen atom.

In the general formula (IV), each of Ar and R ¹ to R ⁵ is, does not contain a polyhydroxy aromatic ring as a partial structure.

  When the compound represented by the general formula (I) or the general formula (IV) of the present invention is too hydrophobic, it cannot be released from the oil droplets, so that the activity as an anti-turbidity agent is lowered. Diffusion causes side effects such as color development inhibition during development. Accordingly, it is required to have appropriate hydrophilicity / hydrophobicity. In the present invention, the color turbidity preventing agent refers to a color mixing preventing agent for preventing color mixing caused by an oxidized form of a developing agent generated in another layer, and is represented by the general formula (I) or the general formula (IV). The compound is preferably a color turbidity inhibitor.

  In general, the hydrophilicity / hydrophobicity of a compound is often expressed by the logarithm of the distribution coefficient to 1-octanol / water (log P), and can be easily determined from the retention time in high performance liquid chromatography using a reverse phase column. Recently, a program for estimating a logP value from a two-dimensional structural formula of a compound has been sold, and a value calculated using this program (referred to as a ClogP value) has become a standard for molecular design.

In the present invention, the ClogP value calculated by Hansch-Leo's “ClogP Tool” (algorithm version = 4.01, fragment database = 17) sold by Daylight Chemical Information Systems, USA is used as the hydrophilicity / hydrophobicity parameter.
The ClogP value of the compound represented by the general formula (III) is preferably 5 or more and 10 or less, more preferably 6 or more and 9 or less, and particularly preferably 7 or more and 8 or less.

  In order to obtain such moderate hydrophilicity / hydrophobicity, it is preferable to incorporate a “ballast group” commonly used in an immobile photographic additive such as a coupler as a substituent of the aromatic group represented by Ar. The ballast group is usually a group having a carbon number of 8 or more and relatively inert to photographic properties. For example, an alkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group, ether group, amide A group, a ureido group, a urethane group, a sulfonamide group, a thioether group, and the like, and combinations of these groups can be selected.

For the purpose of reducing stains due to residual sensitizing dye after processing, the compound represented by formula (I) or formula (IV) is a group that dissociates during development processing (specifically, pKa value in solution). Preferably has no more than 11 groups (for example, sulfo group, carboxyl group, phenolic OH group, sulfonamide group). In the case of having a sulfonamide group (—NHSO ₂ R) as a substituent for Ar, a group capable of forming a hydrogen bond at an appropriate site in the molecule (alkoxy group, carbonyl group, etc.) in order to suppress dissociation of NH protons ) Is a preferred design.

  Specific examples of the compound represented by the general formula (I) or the general formula (IV) are described below. However, the present invention is not limited to the following compounds.

  The compound represented by the general formula (I) or (IV) of the present invention can be easily synthesized according to the method described in US Pat. No. 4,816,373 or Japanese Patent Publication No. 3-75850.

  The compound represented by the general formula (I) or (IV) of the present invention is particularly preferably diffusion-resistant, and the molecular weight per> N—N <is preferably 300 or more and 20,000 or less, and 400 or more. 1,200 or less is more preferable, and 450 or more and 800 or less are more preferable.

  In the present invention, a known antioxidant or the like may be added to the same layer or another layer in combination with the compound represented by the general formula (I) or (IV) of the present invention. When these are used in combination, the content ratio of the compound represented by the general formula (I) or (IV) of the present invention is more preferably 50 mol% or more in terms of the total molar ratio of the anti-turbidity agent and the antioxidant. Is 70 mol% or more. As the compound to be used in combination, a hydroquinone derivative is preferable, and a compound represented by the general formula (II) described in JP-A-3-248152 is preferably used.

  The compound represented by the general formula (I) or (IV) of the present invention is at least one layer such as a protective layer, a photosensitive silver halide layer, an intermediate layer, a filter layer, an undercoat layer and an antihalation layer in the photosensitive material. It can be contained and used. Preferably, it is contained in at least one hydrophilic colloid layer other than the photosensitive layer, and most preferably, a layer adjacent to the photosensitive emulsion layer and / or two photosensitive emulsion layers (the color sensitivity is This may be the same or different) in the intermediate layer.

  In order to add the compound represented by the general formula (I) or (IV) of the present invention to these layers, the coating solution is used as it is or in a silver halide color photographic material such as alcohol (for example, methyl alcohol). It can be added by dissolving in a low-boiling organic solvent that does not affect. Further, it can be dispersed and impregnated in a polymer such as latex, or it can be dissolved in a high boiling point organic solvent and emulsified and dispersed in an aqueous gelatin solution. Alternatively, as a solid dispersion method, the powder can be used by dispersing it in water with a ball mill, a colloid mill, or ultrasonic waves.

Examples of the high boiling point organic solvent that can be used include the following.
Phthalates (eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) ) Phthalate etc.),

Esters of phosphoric acid or phosphonic acid (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di- 2-ethylhexylphenyl phosphate, etc.)

Benzoic acid esters (for example, 2-ethylhexylbenzoate, 2,4-dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecanamide, N, N-diethyl) Laurylamide, N, N, N ′, N′-tetrakis (2-ethylhexyl) isophthalic acid amide, N, N, N ′, N′-tetrakiscyclohexylisophthalic acid amide, ortho-hexadecyloxybenzamide, or the like No. 2000-29159, JP-A No. 2001-281821, JP-A No. 2002-40606, JP-A No. 8-110624, etc., alcohols (for example, isostearyl alcohol, oleyl alcohol, etc.),

Aliphatic esters (eg, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl sylate), aniline derivatives ( For example, N, N-dibutyl-2-butoxy-5-tert-octylaniline)

Chlorinated paraffins (paraffins having a chlorine content of 10% to 80%),
Trimesic acid esters (for example, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene,

Phenols (for example, 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol),

Carboxylic acids (for example, 2- (2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid, etc.),

And alkylphosphoric acids (for example, di- (2-ethylhexyl) phosphoric acid, diphenylphosphoric acid).

  In addition to the above high-boiling solvents, it is also preferable to use compounds described in JP-A-6-258803 as high-boiling solvents.

  In addition, specific examples of latex dispersion method steps, effects, and impregnation latex as one of polymer dispersion methods include US Pat. No. 4,199,363, West German Patent Application (OLS) 2,541,274, No. 2,541,230, Japanese Examined Patent Publication No. 53-41091, and European Patent Publication No. 029104, and dispersion by an organic solvent-soluble polymer is described in PCT International Publication No. WO 88/00723 pamphlet. Yes.

  As an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or more and about 160 ° C. or less (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, methanol, ethanol) is used in combination. May be.

  When the compound represented by formula (I) or (IV) according to the present invention is added to the non-photosensitive layer, the gelatin coating amount of the non-photosensitive layer is suitably 0.2 to 2.0 g per square meter. Yes, it is preferably 0.3 to 1.2 g.

The total amount of the compound represented by formula (I) or (IV) according to the present invention is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 3 per square meter. × 10 ^-3 mol.
In addition, when adding the compound represented by general formula (I) or (IV) to a photosensitive layer, the compound represented by general formula (I) or (IV) is 1 * 10 <^-9> per square meter. ˜1 × 10 ⁻⁵ mol is preferably added, more preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol. If the compound represented by formula (I) or (IV) is added to the photosensitive layer beyond the above range, the sensitivity may be lowered, which is not preferable.
On the other hand, the general formula (I) or when added to a non-photosensitive layer a compound represented by (IV) of the general formula (I) or per square meter of the compound represented by (IV) 1 × 10 ^- It is preferable to add ⁷ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol.

Next, the silver halide grains preferably used in the silver halide color photographic light-sensitive material of the present invention will be described.
The silver halide emulsion used in the present invention may be either a surface latent image type that mainly forms a latent image on the surface, an internal latent image type that is formed inside the grain, or a type that has a latent image on both the surface and inside. Is preferably a negative silver halide emulsion. Among the internal latent image types, a core / shell internal latent image type emulsion described in JP-A-63-264740 may be used. A method for preparing this core / shell internal latent image type emulsion is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development process or the like, it is preferably 3 to 40 nm, more preferably 5 to 30 nm.

The silver halide color photographic light-sensitive material of the present invention preferably contains tabular grains having an average equivalent sphere diameter of 0.2 or more and an average aspect ratio of 0.55 μm or less and an average aspect ratio of 2 or more. It is particularly preferable to contain tabular grains or grains having an average aspect ratio of 8 or more.
In the case of tabular silver halide grains having an average aspect ratio of 2 or more, the silver halide grains preferably occupy 70% or more of the total projected area.
When tabular grains having an average aspect ratio of 8 or more are included, there is no limitation on the equivalent sphere diameter of the grains, but preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.15 μm or more and 2.0 μm or less. is there. The average aspect ratio is preferably 10 or more, more preferably 15 or more.
When tabular grains having an average sphere equivalent diameter of 0.55 μm or less and an average aspect ratio of 2 or more are included, preferably particles having an average aspect ratio of 3 or more (more preferably 4 or more) and an average sphere equivalent diameter of 0.55 μm or less are included. More preferably, it is preferable to include particles having an average aspect ratio of 3 or more (more preferably 4 or more) and an average sphere equivalent diameter of 0.5 μm or less.

The tabular silver halide grains of the present invention may contain any silver halide, but are preferably silver iodobromide or silver iodochlorobromide, more preferably 0.5 mol% to 20 mol of silver iodide. Silver iodobromide and silver iodochlorobromide containing mol%.
The coefficient of variation of the silver iodide content distribution between grains is preferably 20% or less. More preferably, it is 15% or less, and particularly preferably 10% or less. If the coefficient of variation is greater than 20%, the contrast is not high, and the decrease in sensitivity when a pressure is applied increases, which is not preferable. The silver iodide content of each grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The variation coefficient of the distribution of silver iodide content between grains is the standard deviation of the silver iodide content when the silver iodide content of at least 100, more preferably 200, particularly preferably 300 or more emulsion grains is measured. And the average silver iodide content, the relational expression (standard deviation / average silver iodide content) × 100 = a value defined by the coefficient of variation. The measurement of the silver iodide content of individual grains is described, for example, in EP 147,868. There may or may not be a correlation between the silver iodide content Yi (mol%) of each grain and the sphere equivalent diameter Xi (μm) of each grain, but it is desirable that there is no correlation.

  The silver halide emulsion of the present invention may have a multiple structure with respect to the halogen composition in the grains. For example, it may have a quintuple structure. Here, the structure means that the structure has a distribution of silver iodide, and means that the silver iodide content differs between each structure by 1 mol% or more. The structure regarding the silver iodide distribution can be basically obtained by calculation from the prescription value in the grain preparation process. The change in the silver iodide content at the interface between the structures can be abrupt or gentle. In order to confirm these, it is necessary to consider the measurement accuracy in analysis, but the EPMA method (Electron Probe Micro Analyzer method) is usually effective. Prepare a sample in which emulsion grains are dispersed so that they do not come into contact with each other, and analyze the X-rays emitted when the sample is irradiated with an electron beam, thereby performing elemental analysis of the extremely small region irradiated with the electron beam. Can do. The measurement at this time is preferably performed by cooling to a low temperature in order to prevent sample damage due to the electron beam. The silver iodide distribution in the grains when the tabular grains are viewed from the direction perpendicular to the main surface can be analyzed by the same method, but the cross section of the tabular grains can be obtained by solidifying the specimen and using a sample cut into ultrathin sections with a microtome. Intragranular silver iodide distribution in can also be analyzed.

  The tabular silver halide grain is a general term for silver halide grains having one twin plane or two or more parallel twin planes. The twin plane means the {111} plane when ions of all lattice points are in a mirror image relation on both sides of the {111} plane. This tabular grain is composed of two main surfaces parallel to each other and side surfaces connecting these main surfaces. When the tabular grains are viewed from above with respect to the main surface, the main surface has a triangular shape, a hexagonal shape, or a round shape in which these are rounded. A hexagonal, circular shape has circular main surfaces parallel to each other.

The aspect ratio of tabular grains refers to a value obtained by dividing grain diameter by thickness. The particle thickness is measured by depositing metal from the diagonal direction of the particle together with the reference latex, measuring the shadow length on an electron micrograph, and calculating with reference to the latex shadow length. Easy to do. The particle diameter is the diameter of a circle having an area equal to the projected area of the parallel main surface of the particle. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.
For the purpose of obtaining monodispersed tabular grains having a large aspect ratio, gelatin may be additionally added during grain formation. At this time, the gelatin to be used is preferably a chemically modified gelatin described in JP-A-10-148897 and JP-A-11-143002, or gelatin having a low methionine content described in US47131320 and US4942120. In particular, the former chemically modified gelatin is gelatin characterized in that at least two carboxyl groups are newly introduced when the amino group in the gelatin is chemically modified, but succinylated gelatin or trimellitated gelatin is used. It is preferable to use it. The chemically modified gelatin is preferably added before the growth step, more preferably immediately after nucleation. The addition amount is 50% or more, preferably 70% or more based on the weight of the total dispersion medium during particle formation.

Examples of the silver halide solvent that can be used in the present invention include U.S. Pat. Nos. 3,271,157, 3,531,286, 3,574,628, and JP-A-54-1019. (A) organic thioethers described in JP-A-54-158917, etc., (b) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, JP-A-55-2982, etc. (C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319, and (d) imidazole described in JP-A-54-100717 (E) sulfite, (f) ammonia, (g) thiocyanate and the like. Particularly preferred silver halide solvents include thiocyanate, ammonia and tetramethylthiourea. The amount of the silver halide solvent used varies depending on the type. For example, in the case of thiocyanate, the preferred amount used is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide. Regardless of which solvent is used, it is basically possible to remove the solvent by providing a water washing step after forming the first shell as described above.

One preferred form of tabular grains in the present invention includes tabular grains having dislocations.
First, tabular grains having dislocations will be described.
The dislocations of tabular grains are described in, for example, J. F. Hamilton, Photo. Sci. Eng. 11, 57, (1967) and T.W. Shiozawa, J. et al. Soc. Photo. Sci. Japan. 35, 213, (1972), and can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out with care so as not to apply a pressure that causes dislocations to the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed to prevent damage (printout, etc.) due to electron beams. Observation is performed by the transmission method in a cooled state. In this case, the thicker the particle is, the more difficult it is to transmit an electron beam. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position of the dislocation for each particle when viewed from the direction perpendicular to the main plane can be obtained.

  The position of dislocations in the tabular grains used in the present invention is generated from the distance of x% of the length from the center to the side to the side in the major axis direction of the tabular grain. The value of x is preferably 10 ≦ x <100, more preferably 30 ≦ x <98, and even more preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where this dislocation starts is similar to the particle shape, but it may be distorted rather than a perfect shape. The direction of the dislocation line is roughly from the center to the side, but it is often meandering.

  Regarding the number of dislocations in the tabular grains used in the present invention, it is preferable that 50% (number) or more of grains containing 10 or more dislocations are present. More preferably, particles containing 10 or more dislocations are 80% (number) or more, particularly preferably particles containing 20 or more dislocations are 80% (number) or more.

  When the silver halide grains of the present invention are tabular grains having dislocations, the aspect ratio is 2 or more, preferably 3 or more, more preferably 4 or more and 20 or less.

The dislocations of tabular grains used in the present invention are introduced by providing a high iodine phase inside the grains. The high iodine phase is a silver halide solid solution containing iodine. In this case, the silver halide is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but silver iodide or iodobromide. Silver is preferable, and silver iodide is particularly preferable.
The amount of silver halide forming the high iodine phase is 30 mol% or less, more preferably 10 mol% or less of the total silver amount in terms of silver amount.

  The phase grown outside of the high iodine phase must be lower than the iodine content of the high iodine phase, with a preferred iodine content of 0-12 mol%, more preferably 0-6 mol%, most preferably 0. ~ 3 mol%.

  As a preferable method for forming the high iodine layer, there is a method in which a silver iodobromide or silver iodide fine grain emulsion is added. As these fine particles, fine particles prepared in advance can be used, and more preferably, fine particles immediately after preparation can be used.

First, the case of using fine particles prepared in advance will be described. In this case, there is a method in which fine particles prepared in advance are added, ripened and dissolved. As a more preferable method, there is a method in which a silver iodide fine grain emulsion is added, and then an aqueous silver nitrate solution, or an aqueous silver nitrate solution and an aqueous halogen solution are added. In this case, dissolution of the silver iodide fine grain emulsion is promoted by addition of an aqueous silver nitrate solution. The silver iodide fine grain emulsion is preferably added rapidly.
The rapid addition of the silver iodide fine grain emulsion means that the silver iodide fine grain emulsion is preferably added within 10 minutes. More preferably, it means adding within 7 minutes. This condition may vary depending on the temperature of the system to be added, pBr, pH, type and concentration of protective colloid agent such as gelatin, presence / absence of silver halide solvent, type and concentration, etc. However, as described above, the shorter one is preferable. At the time of addition, it is preferable not to substantially add an aqueous silver salt solution such as silver nitrate. The temperature of the system at the time of addition is preferably 40 ° C. or higher and 90 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.
The silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Details will be described later.

  Another preferred embodiment of the tabular grains of the present invention is a tabular silver halide host grain having two main planes parallel to each other and having an aspect ratio of 2 or more (hereinafter referred to as “host tabular grain” or “host grain”), And silver halide grains (hereinafter referred to as “epitaxial junction tabular grains”) composed of silver halide protrusions (hereinafter referred to as “silver halide protrusions” or “protrusions”) epitaxially bonded on the surface of the host grains. "). Here, the protruding portion is a portion raised with respect to the host particle, and can be confirmed by observation with an electron microscope.

  The host tabular grains in the present invention are composed of two main planes parallel to each other and side surfaces connecting these main planes. The shape of the main plane may be any polygon surrounded by a straight line, a shape surrounded by an indefinite curve such as a circle or an ellipse, or a shape surrounded by a combination of a straight line and a curve, but at least one vertex It is preferable to have one. Furthermore, a triangle having three vertices, a quadrilateral having four vertices, a pentagon having five vertices, a hexagon having six vertices, or a combination thereof is more preferable. Here, the vertex means a non-rounded corner formed by two adjacent sides. When the corner is rounded, it means that the length of the rounded curved portion is divided into two equal parts.

  The main plane of the host tabular grains in the epitaxially bonded tabular grains may have any kind of crystal structure. That is, the crystal structure of the main plane may be {111} plane, {100} plane or {110} plane, and may be a higher order plane, but a more preferable mode is that the main plane is {111} plane or {100} plane. It is a tabular grain, and most preferably a tabular grain having a {111} plane as the main plane. In the case of a tabular grain having a {111} plane as a main plane, a mode in which grains having a hexagonal shape having six vertices occupy 70% or more of the total projected area is preferable. Further, in the case of a tabular grain having a {100} plane as a main plane, it is preferable that a quadrangle having four vertices occupy 70% or more of the total projected area.

  The host tabular grains in the epitaxially bonded tabular grains preferably have an aspect ratio of 2 or more, more preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less, by dividing the equivalent circle diameter of the grains by the grain thickness. Is more preferable, and most preferably 15 or more and 200 or less. Here, the equivalent circle diameter of the particle is the diameter of a circle having an area equal to the projected area of the main plane.

  The equivalent circle diameter of the host tabular grains can be obtained by, for example, taking a transmission electron micrograph by the replica method, obtaining the projected area of each grain by correcting the photographing magnification, and converting it to the equivalent circle diameter. . Although the grain thickness may not be calculated simply from the length of the shadow of the replica due to epitaxial deposition, it can be calculated by measuring the length of the shadow of the replica before epitaxial deposition. . Or it can obtain | require easily by cut | disconnecting the sample which apply | coated the emulsion even after epitaxial deposition, and taking the electron micrograph of the cross section.

  The equivalent circle diameter of the host tabular grains in the epitaxially bonded tabular grains is preferably 0.5 to 10.0 μm, and more preferably 0.7 to 10.0 μm. The particle thickness is preferably 0.02 μm to 0.5 μm, more preferably 0.02 to 0.2 μm, and most preferably 0.03 to 0.15 μm.

  The host tabular grains in the epitaxially bonded tabular grains preferably have an equivalent grain variation coefficient of 40% or less, more preferably 30% or less, and particularly preferably 25% or less. Here, the inter-particle variation coefficient of the equivalent circle diameter is a value obtained by dividing the standard deviation of the equivalent circle diameter distribution of each particle by the average equivalent circle diameter and multiplying by 100.

  In an epitaxially bonded tabular grain, the silver halide protrusion is formed by epitaxial bonding at an arbitrary position on the surface of the host tabular grain. The formation position is on the main plane of the host tabular grain, or at the apex, or other than the apex. The most preferable formation position is the apex portion. Here, the apex portion means a portion in a circle having a radius of 1/3 of the length of the shorter side of the two sides adjacent to the apex when the tabular grain is viewed from the main plane in the vertical direction. Specifically, an aspect in which the silver halide grains in which the protrusions are present at all apexes on the main plane of the host tabular grain occupy 70% or more of the total projected area is preferable, and an aspect occupying 80% or more is more preferable. An embodiment occupying 90% or more is more preferable.

  The silver amount of the silver halide protrusions of the epitaxially bonded tabular grains is characterized by a ratio of 12% or less with respect to the silver amount of the host tabular grains. The ratio of the silver amount is more preferably 0.5% or more and 10% or less, and further preferably 1% or more and 8% or less. If the amount of silver is too small, the reproducibility of epitaxial formation becomes poor, and if it is too large, problems such as a decrease in sensitivity and deterioration in graininess are caused. Alternatively, the ratio of the silver halide protrusions to the grain surface is preferably 50% or less of the surface of the host tabular grain, and more preferably 20% or less.

The silver halide protrusions of the epitaxial tabular grains preferably contain pseudohalides. As described in JP-A-7-72569, the term “pseudohalide” is close to the properties of a halide (that is, a sufficiently electronegative monovalent anionic group, at least a halide and Known as CN ⁻ , OCN ⁻ , SCN ⁻ , SeCN ⁻ , TeCN ⁻ , N ³⁻ , C (CN) ³⁻ , and CH ⁻ , representing the same positive Hammett sigma value) Refers to a group of compounds. The preferable content of the pseudohalide in the protruding portion is 0.01 to 10 mol%, more preferably 0.1 to 7 mol%, based on the silver amount in the protruding portion.

  Epitaxial tabular grains are composed of pure silver bromide, silver iodobromide, silver chlorobromide, or silver chloroiodobromide having a halogen composition of host grains and protrusions of 70 mol% or more. is there. When the amount is less than 70 mol%, there is a problem that the increase in fog after storage becomes large. The silver bromide content is more preferably 80 mol% or more, and most preferably 90 mol% or more.

  In the epitaxial tabular grains, the average silver iodide content of all grains is preferably 20 mol% or less, more preferably 15 mol% or less, and most preferably 10 mol% or less. If the silver iodide content exceeds 20 mol%, sufficient high sensitivity cannot be obtained. In addition, an embodiment in which the average silver iodide content of the protrusions is lower than the average silver iodide content of the host grain outer shell 8% (amount of host grain silver) is preferable. Here, the outer shell 8% of the host particles refers to a region in which the amount of silver in the layered region from the surface of the host particles toward the center of the particle occupies 8% of the total amount of silver in the host particles.

  In the epitaxial tabular grains, the silver chloride content of the host grains and the protrusions is preferably 8 mol% or less, more preferably 4 mol% or less, and most preferably 1 mol% or less. preferable.

  The epitaxial tabular grains preferably have a monodisperse distribution of silver iodide content between grains. More specifically, when the average silver iodide content of all grains is I mol%, silver halide grains having a silver iodide content in the range of 0.6I to 1.4I are 70% of the total projected area. The aspect which occupies% or more is preferable. Furthermore, it is preferable that the silver halide grains having a silver iodide content of 0.7I to 1.3I occupy 70% or more of the total projected area.

  Epitaxial tabular grains are composed of silver salts other than silver chloride, silver bromide, silver iodide, such as silver rhodane, silver selenocyanate, silver tellurocyanate, silver sulfide, on host grains or projections or both of host grains and projections. , Silver selenide, silver telluride, silver carbonate, silver phosphate, organic acid silver, etc. may be included as part of the silver halide, or a silver salt other than silver halide may be used as a separate grain. It may be contained in the emulsion.

  The host particles used in the present invention may have a multiple structure of a double structure or more with respect to the halogen composition distribution in the particles. For example, it may have a quintuple structure. Here, the term “structure” means that the silver iodide has a structure in the grain distribution, and that the silver iodide content differs by 1 mol% or more between the structures. The structure of the intragranular distribution of silver iodide can basically be obtained by calculation from the prescription value in the grain preparation process. The change in the silver iodide content at the interface between the structures can be abrupt or gentle. In order to confirm these, it is necessary to consider the measurement accuracy in analysis, but the EPMA method (Electron Probe Micro Analyzer method) is usually effective. Prepare a sample in which emulsion grains are dispersed so that they do not come into contact with each other, and analyze the X-rays emitted when the sample is irradiated with an electron beam, thereby performing elemental analysis of the extremely small region irradiated with the electron beam. Can do. The measurement at this time is preferably performed by cooling to a low temperature in order to prevent sample damage due to the electron beam. The silver iodide distribution in the grains when the tabular grains are viewed from the direction perpendicular to the main plane can be analyzed by the same method, but the cross section of the tabular grains can be obtained by solidifying the specimen and cutting it into ultrathin sections using a microtome. Intragranular silver iodide distribution in can also be analyzed.

  In the silver halide emulsion of the present invention, it is preferable that the silver halide grains having no dislocation lines other than the epitaxial junction occupy 70% or more of the total projected area. Furthermore, it is more preferable that the silver halide grains having no dislocation lines in any region of the grains including the epitaxial junction occupy 70% or more of the total projected area.

  Next, a method for producing tabular grains having a {111} face as a main plane (hereinafter referred to as “{111} tabular grains”), which is one of preferred embodiments of the host tabular grains in the present invention, will be described. {111} tabular grains used in the present invention are "Theory and Practice of Photography" by Cleeve (Cleve, Photography Theory and Practice (1930)), page 13; Gatoff, Photographic Science and Engineering (Gutuff, Photographic Science and Technology). Engineering, 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439. 520 and British Patent No. 2,112,157 and the like.

  The preparation of {111} tabular grains usually consists of a combination of three steps of nucleation, ripening and growth. In the nucleation step, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used, and a high pBr described in US Pat. No. 4,914,014 is used. The nucleation in a short time as described in JP-A-2-222940 is extremely effective in the nucleation step of the particles used in the present invention. In the present invention, the silver nitrate aqueous solution, the halogen aqueous solution and the low molecular weight oxidized gelatin are preferably added within one minute while stirring in the presence of low molecular weight oxidized gelatin at a temperature of 20 ° C. to 40 ° C. At this time, the pBr of the system is preferably 2 or more, and the pH is preferably 7 or less. The concentration of the aqueous silver nitrate solution is preferably 0.6 mol / liter or less.

  The ripening step is carried out in the presence of a low concentration base as described in US Pat. No. 5,254,453, and at a high pH as described in US Pat. No. 5,013,641. The tabular grain emulsion of the present invention It can be used in the aging step. U.S. Pat. Nos. 5,147,771, 5,147,772, 5,147,773, 5,171,659, 5,210,013, and It is possible to add the polyalkylene oxide compound described in No. 252,453 in the aging step or the subsequent growth step. In the present invention, the aging step is preferably performed at a temperature of 50 ° C. or higher and 80 ° C. or lower. It is preferable to reduce pBr to 2 or less immediately after nucleation or during aging. Further, additional gelatin is preferably added immediately after nucleation until the end of ripening. Particularly preferred gelatin is one in which the amino group is 95% or more modified to be succinylated or trimellitized.

  The growth step is usually performed by a known method in which an aqueous silver nitrate solution and an aqueous halide solution are added simultaneously, and includes the aqueous silver nitrate solution and bromide described in US Pat. Nos. 4,672,027 and 4,693,964. A method of simultaneously adding an emulsion containing an aqueous halogen solution and silver iodide fine grains (hereinafter referred to as “silver iodide fine grain emulsion”) can also be used.

The silver halide grains contained in the silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as a mixed crystal can be formed. 100% silver iodide is preferred. Silver iodide can have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in its crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before the addition described in US Pat. No. 5,004,679 or the like, and may be any one that has undergone a normal water washing step. What passed through this water washing process is used. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution in which the pI value at the time of grain formation is kept constant to form grains is preferable. Where pI is the logarithm of the reciprocal of the I ⁻ ion concentration of the system. The type, concentration, presence / absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, and gelatin are not particularly limited, but the grain size is 0.1 μm or less, more preferably 0.8. A thickness of 07 μm or less is convenient for the present invention. The particle shape cannot be completely specified because it is a fine particle, but the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when it is 20% or less, the effect of the present invention is remarkable.

  Here, the size and size distribution of the silver iodide fine grain emulsion are obtained by placing the silver iodide fine grains on a mesh for observation with an electron microscope and directly observing them by a transmission method instead of the carbon replica method. This is because the measurement error becomes large in the observation by the carbon replica method because the particle size is small. The particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined by using this equivalent projected area circle diameter. The silver iodide fine particles most effective in the present invention have a grain size of 0.06 μm or less and 0.02 μm or more, and a grain size distribution variation coefficient of 18% or less.

  The silver iodide fine grain emulsion is preferably prepared by the usual water washing described in U.S. Pat. No. 2,614,929, etc., the concentration adjustment of protective colloidal agents such as pH, pI, gelatin and the like of silver iodide contained in the silver iodide fine grain emulsion. Density adjustment is performed. The pH is preferably 5 or more and 7 or less. The pI value is preferably set to a pI value that minimizes the solubility of silver iodide or a pI value higher than that value. As the protective colloid agent, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It may be convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver amount in terms of silver atom per kg of the emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver iodide fine grain emulsion is usually added after being dissolved in advance, but it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective for suppressing the generation of bubbles during stirring. Specifically, antifoaming agents described in Examples of US Pat. No. 5,275,929 are used.

  In the growth process of the present invention, an external stirrer described in JP-A-10-043570 can also be used. That is, an emulsion containing silver bromide, silver iodobromide, or silver iodochlorobromide grains (hereinafter also referred to as “ultrafine grain emulsion”) prepared immediately before the addition by the stirring device is continuously added during tabular grain growth. In this method, tabular grains are grown by dissolving the ultrafine grain emulsion. An external mixer for preparing an ultrafine emulsion has a strong stirring ability, and an aqueous silver nitrate solution, an aqueous halogen solution and gelatin are added to the mixer. Gelatin can be mixed with an aqueous silver nitrate solution and / or an aqueous halogen solution in advance or mixed immediately before, or an aqueous gelatin solution alone can be added. The gelatin preferably has an average molecular weight smaller than that of a normal one, and particularly preferably 10,000 to 50,000. Gelatin in which the amino group is modified by 90% or more to phthalation, succination or trimellitization and / or oxidation-treated gelatin with a reduced methionine content is particularly preferably used.

  Next, a method for producing tabular grains having a {100} plane as a main plane (hereinafter referred to as “{100} tabular grains”), which is another preferred embodiment of the host tabular grains in the present invention, will be described. {100} tabular grains are preferably formed in the presence of a polyvinyl alcohol derivative (hereinafter referred to as “polymer (P)”). The polymer (P) strongly adsorbs to the silver halide grains, has a strong protective colloid ability, and inhibits further lamination of silver halide on the adsorption surface.

  Tabular nucleation of {100} tabular grains is caused by adsorption of polymer (P) on a pair of {100} faces that can be the main plane of silver halide grains and adsorption of gelatin on side faces (other faces). Complete. The plate nuclei may be formed by adding (a) Ag + ions and X− ions to an aqueous solution in which the polymer (P) and gelatin are present in advance, or (b) Ag + ions and X in an aqueous solution having only the gelatin. -It can also be formed by adding polymer (P) after adding ions to form microcrystals. If the adsorptive power of the polymer (P) and gelatin can be well controlled in the early stage of more unstable nucleation, it is preferable for monodispersing the thickness to form plate nuclei by the method (a).

  Control of the adsorptive power of polymer (P) and gelatin adjusts the kind of polymer (P) and gelatin to be used (molecular weight, type of substituent, etc.), the amount used, pH during plate nucleation, pAg, etc. Can be done. For example, since the polymer (P) has a stronger adsorption force as the molecular weight increases, in this case, it is necessary to increase the molecular weight of gelatin to balance the adsorption force, or increase the amount of gelatin used to balance the adsorption force. is there. In nucleation, it is the highest priority to achieve a uniform polymer (P) and gelatin adsorption state between particles. At this time, the amount of the polymer (P) used is preferably small, and accordingly, the type of gelatin, It is necessary to select the amount to be used and to select a pH and pAg suitable for it. The adsorptive power depends on the relative relationship between the crystal phase on the AgX particle surface, the polymer (P), and gelatin, and is not uniquely determined.

Even in the process of ripening and growth after nucleation, the balance of adsorption power is required to be changed as necessary. The plate nuclei formed by the methods (a) and (b) are all preferred plate nuclei (the polymer (P) is adsorbed on the pair of {100} faces that can be the main plane described above, and on the side surfaces (other surfaces). It is not necessary when the gelatin is adsorbed), but an aging process is necessary when undesirable nuclear crystals are mixed. At this time, the undesirable nuclear crystals disappear by Ostwald ripening, but the adsorptive power of the polymer (P) having a strong protective colloid ability is weakened to promote ripening. It is also preferable to increase the temperature to create an atmosphere that is easily aged, or to promote aging by adding Ag ⁺ ions and X ⁻ ions.

In the growth process of the {100} tabular grains, possible polymer (P) the state most difference in the adsorption force of the gelatin occurs, i.e. in a state that occurred in the most difference in the solubility of the main plane and side, Ag ⁺ and X ^- in The addition is preferably carried out so as to maintain a state of low supersaturation. In order to make a difference in the adsorption power, it is the simplest and preferable to control the adsorption power of the polymer (P) and gelatin at pH.

  In {100} tabular grain formation, it is preferable that a spectral sensitizing dye is added before the grain formation is completed. Since the polymer (P) strongly adsorbs to the silver halide grains, the surface of the silver halide is kept in a dynamic state (that is, silver ions and halogen ions) to adsorb the spectral sensitizing dye on the main surface having a large surface area. Spectral sensitizing dye and polymer (P) are replaced (allowing new lamination by addition of It is also preferable to add gelatin to relatively reduce the adsorptive power of the polymer (P) to promote substitution.

The kind of spectral sensitizing dye to be used is not particularly limited.
However, in the silver halide photographic light-sensitive material of the present invention, it is suitable for the combination with the compound represented by the general formula (I) or (IV) in the present invention to reduce the residual color due to the residual spectral sensitizing dye. As the spectral sensitizing dye, a sensitizing dye that dissolves in water by 0.05% by mass or more and a hydrophilic sensitizing dye that dissolves at pH 7.5 or more are preferable. More preferably, it is a sensitizing dye that dissolves in an amount of 0.1% by mass or more with respect to water, and a sensitizing dye that dissolves at a pH of 8.0 or more.

Further, it is preferable to use 1 × 10 ⁻² to 2 × 10 ² mol of the compound represented by the general formula (I) or (IV) with respect to 1 mol of the sensitizing dye, more preferably 1 × 10 6. ^{-1 to} 5 x 10 mol.

  Next, in the present invention, a method for forming silver halide protrusions epitaxially bonded onto the surface of the host tabular grain will be described. The formation of the protrusions may be performed immediately after the formation of the host tabular grains, or may be performed after ordinary desalting is performed after the formation of the host tabular grains. Preferably, it is carried out immediately after the formation of the host tabular grains.

  It is preferable to use a site indicator in order to form the protrusion in the present invention. Although various site indicators can be used, it is preferable to use a spectral sensitizing dye. By selecting the amount and type of the dye to be used, the position of the protrusion can be controlled. The spectral sensitizing dye is preferably added in an amount corresponding to 50% to 200% of the saturated coating amount, and more preferably in an amount corresponding to 70% to 150%. The 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 dye. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.

  These spectral sensitizing dyes may be used alone or in combination, and the combination of spectral sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925. Along with the spectral sensitizing dye, a dye that does not itself have a spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization may be added simultaneously or separately.

  Regarding the method of forming the protrusion, an embodiment in which a spectral sensitizing dye is added as a site indicator prior to the formation of the protrusion is preferable, but an aspect in which a spectral sensitizing dye is additionally added after forming the protrusion is also preferable. The added pigment has the effect of keeping the protrusions stable and at the same time has the advantage of higher sensitivity. In this case, the same kind of dye as the spectral sensitizing dye used before the formation of the protrusions may be used, or another kind of dye may be included.

  The silver halide protrusion of the silver halide emulsion of the present invention can be formed by adding a solution containing silver nitrate. At this time, a method of simultaneously adding an aqueous silver nitrate solution and a halide solution is often used, but the silver nitrate solution may be added separately. Further, it may be formed by adding silver bromide fine particles, silver iodide fine particles, silver chloride fine particles having a smaller particle diameter than the thickness of the host tabular grains, or adding fine particles composed of mixed crystals thereof. In the case of adding the silver nitrate aqueous solution and the halide solution at the same time, a method of adding while maintaining the pBr of the system constant is preferable. The addition time of the silver nitrate solution is preferably from 30 seconds to 300 minutes, particularly preferably from 1 minute to 200 minutes. The concentration of the silver nitrate solution is preferably 1.5 mol / liter or less, particularly preferably 1.0 mol / liter or less (hereinafter, the liter is also expressed as “L”). The pBr when forming the silver halide protrusion is preferably 3.5 or more, particularly preferably 4.0 or more. The temperature is preferably 35 ° C. or higher and 45 ° C. or lower. The pH is preferably from 3 to 8, more preferably from 5 to 8.

  It is possible to add a pseudohalide to the protrusions by adding a pseudohalide salt before or during the formation of the protrusions, or by adding it to a halide solution added simultaneously with silver nitrate. For example, it is possible to use KCN, KSCN, KSeCN, or the like.

In the present invention, the content of the pseudo halide in the protruding portion can be measured by the following method. The tabular silver halide grains in the silver halide photographic light-sensitive material are taken out by treating the light-sensitive material with a proteolytic enzyme and centrifuging it. The particles are redispersed and placed on a copper mesh with a support film. The protruding portion of the particles is subjected to point analysis with a spot diameter reduced to 2 nm or less using an analytical electron microscope to measure the content of pseudohalides. The pseudo-halide content can be obtained by processing silver halide grains having a known content as a calibration curve in the same manner, and obtaining the ratio between the Ag intensity and the pseudo-halide intensity in advance. For example, in the case of SCN ⁻ , it can be obtained from the ratio of Ag intensity and S intensity. A field emission type electron gun with a higher electron density than that using thermoelectrons is suitable as an analytical electron source for an analytical electron microscope. Can be analyzed. When the intergranular variation coefficient of the pseudohalide content in the protrusion is 30% or less, usually 20 grains are measured and averaged to obtain the pseudohalide content. When the intergranular variation coefficient of the pseudo halide content of the protrusion is 20% or less, usually 10 particles are measured and averaged to obtain the pseudo halide content. The intergranular variation coefficient of the pseudohalide content in the protrusions is preferably 20% or less.

  The silver halide grain of the present invention preferably has a hole trap zone in the grain. The hole trap zone in the present invention refers to a region having a function of capturing so-called holes, for example, holes generated in pairs with photoelectrons generated by photoexcitation. There are various methods for providing such a hole trap zone, but in the present invention, it is desirable to apply by reduction sensitization.

  In the present invention, the hole trap zone may be present inside the particle, on the particle surface, or both inside and on the surface. When the particle is an epitaxial tabular particle, the host particle, the protrusion, or the host particle It may be present on both of the protrusions. However, since the reduced silver nuclei are easily destroyed by oxygen or moisture in the air, it is preferable that the hole trap zone is present in the grains or in the host grains when the emulsion itself or the photosensitive material is stored for a long period of time.

  The production process of silver halide emulsion is generally roughly divided into processes such as grain formation, desalting and chemical sensitization. Particle formation can be divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeated. The reduction sensitization can be performed on the silver halide emulsion basically in any step during each manufacturing step. Reduction sensitization may be performed during nucleation, physical ripening, or growth, which is the initial stage of particle formation, and may be performed prior to or after chemical sensitization other than reduction sensitization. . In the case of performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. The most preferable method is reduction sensitization during the growth of host particles. The term “growing” as used herein refers to a method in which reduction sensitization is performed while silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. It also means that a method of further growth after reduction sensitization in a state is also included.

  The reduction sensitization of the present invention includes a method of adding a known reducing agent to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere called silver ripening, and a pH of 8 to 8 called high pH ripening. Any of the methods of growing or aging in an atmosphere of 11 high pH can be selected. Two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted. Known reduction sensitizers include primary silver salts, amines and polyamic acids, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, ascorbic acid and derivatives thereof. In this invention, it can select and use from these well-known compounds, and can also use 2 or more types of compounds together. As a reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferable compounds. The addition amount of the reduction sensitizer depends on the type of the reduction sensitizer and the emulsion production conditions. Therefore, it is necessary to select the addition amount, but a range of 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide is appropriate. . However, in the case of an ascorbic acid compound, a range of 5 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol is appropriate.

  The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters, amides, and can be added before or after chemical sensitization during particle formation. Although it may be added at any stage of the emulsion production process, a method of adding during grain growth is particularly preferable. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time of particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also preferable to add the reduction sensitizer solution several times as the particles are formed, or to add it continuously for a long time.

  In order to arrange the hole trap zone only inside the particles, it is effective to contain at least one compound selected from the compounds represented by the following general formula (A), (B) or (C).

General formula (A): G-SO ₂ SM
Formula (B): G-SO ₂ S-G ₁
Formula _{(C): G-SO 2} S- (L) m -SSO 2 -G 2

In the formula, G, G ₁ and G ₂ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, L represents a divalent linking group, m represents 0 or 1;
The compounds represented by the general formulas (A) to (C) may be polymers containing divalent groups derived from the structures represented by (A) to (C) as repeating units. In the general formula (B), G and G ₁ may form a ring, and in the general formula (C), G, G ₂ and L may be bonded to each other to form a ring.

The compounds represented by formulas (A), (B) and (C) will be described in more detail. When G, G ₁ and G ₂ are aliphatic groups, they are saturated or unsaturated, linear, branched or A cyclic aliphatic hydrocarbon group, preferably an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, which may have a substituent. .
Examples of the alkyl group represented by G, G ₁ and G ₂ include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl. Is mentioned.

Examples of the alkenyl group represented by G, G ₁ and G ₂ include allyl and butenyl. Examples of the alkynyl group include propargyl and butynyl.

The aromatic group represented by G, G ₁ and G ₂ includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. It is done. These may be substituted.

The heterocyclic group represented by G, G ₁ and G ₂ is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium. Examples of the ring include pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, and tellurazole. A ring, a triazole ring, a benzotriazole ring, a tetrazole ring, an oxadiazole ring, and a thiadiazole ring.

Examples of the substituent for G, G ₁ and G ₂ include an alkyl group (for example, methyl, ethyl, hexyl), an alkoxy group (for example, methoxy, ethoxy, octyloxy), an aryl group (for example, phenyl, naphthyl, tolyl). ), A hydroxy group, a halogen atom (for example, fluorine, chlorine, bromine, iodine), an aryloxy group (for example, phenoxy), an alkylthio group (for example, methylthio, butylthio), an arylthio group (for example, phenylthio), an acyl group (for example, Acetyl, propionyl, butyryl, valeryl), sulfonyl groups (eg, methylsulfonyl, phenylsulfonyl), acylamino groups (eg, acetylamino, benzamino), sulfonylamino acids (eg, methanesulfonylamino, benzenesulfonylamino), acyloxy groups ( Examples thereof include acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group and the like.

The divalent linking group represented by L in the general formula (C) is an atom or atomic group containing at least one selected from C, N, S and O. Specifically, it is composed of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, —S—, —NH—, —CO—, —SO ₂ — alone or a combination thereof.

L is preferably a divalent aliphatic group or a divalent aromatic group. The divalent aliphatic group of L, _{such, - (CH 2) n- (} n = 1~12), - CH 2 -CH = CH-CH 2 -, - CH 2 C≡CCH 2 -, xylylene Group and the like. Examples of the divalent aromatic group for L include phenylene and naphthylene. These substituents may be further substituted with the substituents described so far.

  M in the general formula (A) is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion, and potassium ion. Examples of the organic cation include ammonium ions (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), guanidine groups, and the like.

  Specific examples of the compound represented by the general formula (A), (B) or (C) are preferably those disclosed in JP-A-10-268456, and preferably incorporated as part of the specification of the present application.

The compound represented by formula (A), (B) or (C) can be easily synthesized by the methods described in JP-A No. 54-1019 and British Patent No. 972,211. The compound represented by formula (A), (B) or (C) is preferably added in an amount of 10 ⁻⁷ to 10 ⁻¹ mol per mol of silver halide. Further, an addition amount of 10 ⁻⁵ to 10 ⁻² , particularly 10 ⁻⁵ to 10 ⁻³ mol / mol Ag is preferable.

  For adding the compounds represented by the general formulas (A) to (C) during the production process, a method usually used when an additive is added to a photographic emulsion can be applied. For example, the water-soluble compound is an aqueous solution having an appropriate concentration, and the water-soluble or sparingly soluble compound is an appropriate organic solvent miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. Among them, it can be dissolved in a solvent that does not adversely affect photographic characteristics and added as a solution.

  The compound represented by the general formula (A), (B) or (C) may be added at any stage during grain formation of the silver halide emulsion, before chemical sensitization or during production. Preferred is a method in which the compound is added before or when reduction sensitization is performed. Particularly preferred is a method of adding during grain growth.

  Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time of particle formation. Alternatively, the compounds represented by the general formulas (A) to (C) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. In addition, it is also preferable to add the solution of the compound represented by the general formulas (A) to (C) several times as the particles are formed, or to add them continuously for a long time.

  Of the compounds represented by the general formulas (A) to (C), the most preferable compound for the present invention is a compound represented by the general formula (A).

As another method for arranging the hole trap zone only inside the particle, there is a method using an oxidizing agent. The oxidizing agent may be inorganic or organic. Examples of inorganic oxidizing agents include ozone, hydrogen peroxide, and adducts thereof (for example, NaBO ₃ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H ₂ O _{2, 2Na 2 SO 4 · H} 2 O 2 · H 2 O), peroxy acid salt _{(e.g., K 2 S 4 O 8,} K 2 C 2 O 6, K 4 P 2 O 8), peroxy complex compounds (e.g. K ₂ [TiO ₂ C ₂ O ₄ ] 3H ₂ O, 4K ₂ SO ₄ · TiO ₂ · OH · 2H ₂ O, Na ₃ [VOO ₂ (C ₂ O ₄ ) ₂ · 6H ₂ O]), permanganese Oxyacid salts such as acid salts (for example, KMnO ₄ ), chromates (for example, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalogenates (for example, potassium periodate), There are salts of high-valent metals (for example, potassium hexacyanoferric acid). Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, chloramine B). ). About the preferable addition amount of these oxidizing agents, addition time, and addition method, it is the same as that of the case of the compound represented by the above-mentioned general formula (A), (B), (C).

  In the present invention, preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonic acids, and quinones, and particularly preferred are thiosulfonic acids represented by the general formulas (A) to (C). Most preferred is a compound represented by formula (A).

  In order to arrange the hole trap zone on the particle surface, the reduction sensitization may be performed after 90% (silver amount) or more of the particles are formed.

  The silver halide grains of the present invention preferably have a temporary electron trap zone. The temporary electron trap zone in the present invention refers to a region having a function of temporarily trapping photoelectrons during the photosensitive process until photoelectrons generated by photoexcitation form a latent image. Such a temporary electron trap zone can be realized by doping a transition metal complex.

In the present invention, specific examples of transition metal complexes suitable as dopants preferably incorporated into the inside and / or surface of silver halide grains are given below. As a metal ion used for the central metal of the transition metal complex, iron, ruthenium, iridium, cobalt, osmium, rhodium, and palladium are preferable. These metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as the ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion More preferably, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thionitrosyl ion are used. The ligand may be coordinated to any of the metal ions, and the same type of ligand may be coordinated to each of the coordinate sites of the metal ion. You may make it coordinate simultaneously. In addition, an organic compound can be used as the ligand. When an organic compound is used as the ligand, a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered ring complex. A ring compound is preferable, and among them, a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to a metal is more preferable, and furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine and pyrazine are particularly preferred. Furthermore, compounds having these compounds as a basic skeleton and having a substituent introduced into the skeleton are also preferred. The transition metal complex is preferably incorporated in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol, per mol of silver.

In the transition metal complex, the metal ion used as the central metal is particularly preferably iron, ruthenium, or iridium. When the central metal is iron or ruthenium, the combination with the ligand is preferably a combination of iron ion and cyanide ion, or ruthenium ion and cyanide ion. In these combinations, it is more preferable that cyanide ions occupy a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites include thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, More preferably, it is occupied by any one of pyridine, pyrazine, and 4,4′-bipyridine. Most preferably, the six coordination sites of the central metal are all occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. Preferred examples when iron or ruthenium is used as the central metal include [Fe (CN) ₆ ] ⁴⁻ , [Fe (CN) ₆ ] ³⁻ , [Ru (CN) ₆ ] ⁴⁻ , [Fe ( Pyrazine) (CN) ₅ ] ^4- , [Fe (CO) (CN) ₅ ] ^3- , [RuF ₂ (CN) ₄ ] ^4- , [Ru (CN) ₅ (OCN)] ^4- , [Ru ( CN) ₅ (N ₃ )] ⁴⁻ , [Fe (CN) ₃ Cl ₃ ] ³⁻ , and [Ru (CO) ₂ (CN) ₄ ] ¹⁻ are preferred. On the other hand, when iridium is used as the central metal, the ligand is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion or thiocyanate ion, and among them, chloride ion or bromide Ions are more preferred. These ligands preferably account for a majority of the coordination number to iridium, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, pyrazine, and 4,4 ′. It is also preferred that it is occupied by any of the bipyridines. Preferred examples of the metal complex using iridium as the central metal include [IrCl ₆ ] ³⁻ , [IrCl ₆ ] ²⁻ , [IrCl ₅ (H ₂ O)] ²⁻ , [IrCl ₅ (H ₂ O)]. _{^{] -, [IrCl 4 (H}} 2 O) 2] -, [IrCl 4 (H 2 O) 2] 0, [IrCl 3 (H 2 O) 3] 0, [IrCl 3 (H 2 O) 3] + [IrBr ₆ ] ³⁻ , [IrBr ₆ ] ²⁻ , [IrBr ₅ (H ₂ O)] ²⁻ , [IrBr ₅ (H ₂ O)] ⁻ , [IrBr ₄ (H ₂ O) ₂ ] ⁻ , [IrBr ₄ (H ₂ O) ₂ ] ⁰ , [IrBr ₃ (H ₂ O) ₃ ] ⁰ , [IrBr ₃ (H ₂ O) ₃ ] ⁺ , [Ir (CN) ₆ ] ³⁻ , [IrBr (CN) ₅ ] ³⁻ , [IrBr ₂ (CN) ₄ ] ³⁻ , [Ir (CN) ₅ (H ₂ O)] ²⁻ , [Ir (CN) ₄ (oxalate)] ³⁻ , [In (NCS) _6] ^3- Preferably they exemplified.

  Next, chemical sensitization of the silver halide grains of the present invention will be described. The chemical sensitization of the present invention may be performed before or after desalting.

One of the chemical sensitizations that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan, 1977, (TH James, The Theory of the Photographic Process, 4th ed, McCillan, 1977) pages 67-76. Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1, 315,755, using pAg 5-10, pH 5-8, and temperature 30-80 ° C. with sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. It can be carried out. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and among them, gold sensitization, palladium sensitization and the combined use of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium auric thiocyanate, gold sulfide, gold selenide, or mesoionic gold compounds described in US Pat. No. 5,220,030 The azole gold compound described in US Pat. No. 5,049,484 can be used. The palladium compound means a palladium divalent salt or a tetravalent salt. A preferable palladium compound is represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom. Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferable. The gold compound and palladium compound are preferably used in combination with thiocyanate or selenocyanate.

In the emulsion of the present invention, a gold sensitizer is preferably used in combination. A preferred amount of the gold sensitizer is 1 × 10 ⁻³ to 1 × 10 ⁻⁷ mole, and more preferably 1 × 10 ^{−4 to} 5 × 10 ⁻⁷ mole, per mole of silver halide. A preferred range for the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ mole per mole of silver halide. A preferable range of the thiocyan compound or selenocyan compound is 5 × 10 ⁻² to 1 × 10 ⁻⁶ mol per mol of silver halide.

Sulfur sensitizers are described in hypo, thiourea compounds, rhodanine compounds and U.S. Pat. Nos. 3,857,711, 4,266,018 and 4,054,457. Sulfur-containing compounds can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned daffine. The book “photographic emulsion chemistry”, pages 138-143. The preferred amount of sulfur sensitizer used in the present invention is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol. It is.

  A preferred sensitizing method for the emulsion of the present invention is selenium sensitization. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. Usually, unstable selenium compounds and / or non-labile selenium compounds are used by adding them and stirring the emulsion for a certain period of time at a high temperature (preferably 40 ° C. or higher). As the unstable selenium compound, compounds described in JP-B Nos. 44-15748, 43-13489, JP-A-4-25832, JP-A-4-109240, and the like are preferably used.

  Specific examples of unstable selenium sensitizers include, for example, isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (for example, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium can give.

  Although preferred types of labile selenium compounds have been described above, these are not limiting. Stable selenium compounds as sensitizers in photographic emulsions are not critical as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule carries selenium and It is generally understood by those skilled in the art that it has no role other than being present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used.

  As the non-labile selenium compound used in the present invention, compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 are used. Non-labile selenium compounds include, for example, selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones. , 2-selenooxazolidinethione and derivatives thereof.

  These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and two or more kinds of the selenium sensitizers can be used in combination. The combined use of labile selenium compounds and non-labile selenium compounds is preferred.

The amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of the silver halide, the ripening temperature and time, etc., but preferably the silver halide 1 It is 1 × 10 ⁻⁸ mol or more per mol. More preferably, it is 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 40 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, with respect to pH, the effects of the present invention can be obtained in a wide range from 4 to 9.

Selenium sensitization is preferably used in combination with sulfur sensitization or noble metal sensitization or both. In the present invention, thiocyanate is preferably added to the silver halide emulsion during chemical sensitization. As thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate or the like is used. Usually, it is dissolved in an aqueous solution or a water-soluble solvent and added. The addition amount is from 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, more preferably from 5 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol, per mol of silver halide.

  The emulsion used in the present invention may be chemically sensitized at the surface or at any position from the surface. For chemical sensitization of the inside, reference can be made to the method described in JP-A No. 63-264740. In addition, the lower the chloride ion content of the epitaxially bonded silver halide protrusions, there is a tendency for chemical sensitization inside, and when the protrusions are formed in the presence of thiocyanate ions, they are more chemically sensitized inside. Tend to.

Next, other preferred embodiments of the silver halide emulsion of the present invention will be described.
The silver halide emulsion of the present invention preferably contains an appropriate amount of calcium ions and / or magnesium ions. As a result, the graininess is improved and the image quality is improved, and the storability is also improved. The appropriate range is 400 to 2500 ppm for calcium and / or 50 to 2500 ppm for magnesium, more preferably 500 to 2000 ppm for calcium and 200 to 2000 ppm for magnesium. Here, 400 to 2500 ppm of calcium and / or 50 to 2500 ppm of magnesium means that at least one of calcium and magnesium is at a concentration within a specified range. If the calcium or magnesium content is higher than these values, the inorganic salt previously retained by the calcium salt, magnesium salt, gelatin or the like is precipitated, which is not preferable because it causes failure during the production of the photosensitive material. Here, the content of calcium or magnesium is expressed by the mass converted to calcium atom or magnesium atom for all compounds containing calcium or magnesium such as calcium ion, magnesium ion, calcium salt, magnesium salt, etc. It is expressed as a concentration per unit mass.

Calcium added to the silver halide emulsion of the present invention can be added at any time during the emulsion production process, but an embodiment in which it is added prior to the formation of the silver halide protrusion is preferred. Furthermore, an aspect in which calcium is added after the formation of the protrusion is also preferable.
Calcium is usually added in the form of a calcium salt. As the calcium salt, calcium nitrate and calcium chloride are preferable, and calcium nitrate is most preferable. Similarly, the magnesium content can be adjusted by adding a magnesium salt during the production of the emulsion. As the magnesium salt, magnesium nitrate, magnesium sulfate and magnesium chloride are preferable, and magnesium nitrate is most preferable. The quantitative method of calcium or magnesium can be determined by ICP emission spectroscopic analysis. Calcium and magnesium may be used alone or in combination. It is more preferable to contain calcium.

  As a particularly useful compound for the purpose of reducing the fog of the silver halide emulsion and suppressing the fog increase during storage, a mercaptotetrazole compound having a water-soluble group described in JP-A-4-16838 can be mentioned. Further, the above-mentioned published patent publication discloses that preservability is enhanced by using a combination of a mercaptotetrazole compound and a mercaptothiadiazole compound.

  The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles (eg, benzothiazolium salts); nitroimidazoles; nitrobenzimidazoles; chlorobenzimidazoles; bromobenzimidazoles; mercaptothiazoles; mercaptobenzothiazoles; mercaptobenzimidazoles; Benzotriazoles; nitrobenzotriazoles; mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; For example, triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindene It can be added a number of compounds known as antifoggants or stabilizers, such as classes. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, in the water washing process, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. Besides adding the original fog prevention and stabilizing effect during emulsion preparation, control grain habit, reduce grain size, decrease grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

  It is advantageous to use gelatin as the protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers. However, other hydrophilic colloids can be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers; proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic properties, such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, homopolymers or copolymers such as polyvinyl pyrazole; A polymer material can be used.

  Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bull. Soc. Sci. Photo. Japan, no. 16, 30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or enzyme-decomposed product of gelatin can also be used.

  The emulsion of the present invention is preferably washed with water for desalting and made into a protective colloid dispersion using a newly prepared protective colloid dispersion. Although the temperature of water washing can be selected according to the objective, it is preferable to select in the range of 5-50 degreeC. Although pH at the time of water washing can also be chosen according to the objective, it is preferred to choose between 2-10. More preferably, it is the range of 3-8. Although pAg at the time of water washing can also be selected according to the objective, it is preferable to select between 5-10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. The coagulation sedimentation method can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like.

Hereinafter, the silver halide color photographic light-sensitive material (color reversal film or color negative film) which is a preferred embodiment of the present invention will be described in detail.
The color photographic light-sensitive material of the present invention comprises a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler on a transparent support, a magenta dye-forming coupler, a green-sensitive silver halide emulsion layer, and a red-sensitive halogen containing a cyan dye-forming coupler. It is sufficient that at least one silver halide emulsion layer is provided, but each color-sensitive emulsion layer is preferably a color-sensitive unit in which two or more photosensitive emulsion layers having different sensitivities are combined. These color-sensitive emulsion layers or color-sensitive units are composed of a red-sensitive silver halide emulsion layer (or red-sensitive unit), a green-sensitive silver halide emulsion layer (or green-sensitive unit), and a blue-sensitive material from the side close to the support. It is preferable to install the silver halide emulsion layers (or blue-sensitive units) in this order. When the structure of the color-sensitive unit is kept, it is preferable that each unit has a three-layer unit structure composed of three photosensitive emulsion layers of a low-sensitivity layer, a medium-sensitivity layer, and a high-sensitivity layer from the side close to the support. These are described in JP-B-49-15495, JP-A-59-202464, and the like.

  In one preferred embodiment of the present invention, an undercoat layer / antihalation layer / first intermediate layer / red sensitive emulsion layer unit (low sensitivity red sensitive layer / medium sensitive red from the side close to the support) is provided on the support. Sensitive layer / high-sensitivity red-sensitive layer is preferred) / second intermediate layer / green-sensitive emulsion layer unit (low-sensitive green-sensitive layer / medium-sensitive green-sensitive layer / high-sensitivity green from the side close to the support) 3 layers of sensitive layer) / third intermediate layer / yellow filter layer / blue sensitive emulsion layer unit (from the side close to the support, low sensitivity blue sensitive layer / high sensitive blue sensitive layer) or low sensitivity It is preferable that the photosensitive element is composed of three layers of blue sensitive layer / medium sensitive blue sensitive layer / high sensitive blue sensitive layer) / first protective layer / second protective layer.

  Each of the first, second, and third intermediate layers may be a single layer or may have two or more layers. The intermediate layer includes couplers, DIR compounds, and the like described in JP-A-61-43748, 59-113438, 59-113440, 61-20037, and 61-20038. May be included, and a color mixing inhibitor may be included as normally used.

  It is also preferable that the protective layer has a three-layer configuration of a first protective layer to a third protective layer. When the protective layer has two or three layers, the second protective layer preferably contains fine grain silver halide having a sphere equivalent average particle size of 0.10 μm or less. The silver halide is preferably silver bromide or silver iodobromide.

The photosensitive silver halide grains used in the present invention may be used in combination with photosensitive silver halide grains having a shape other than the range of the tabular grains of the present invention, but the average aspect ratio is 8 or more (more preferably 10 or more). ) Is used in an amount of 30% or more (more preferably 60% or more) in terms of a mass ratio in terms of silver with respect to the total amount of photosensitive silver halide grains contained in the photosensitive material, or a sphere equivalent average diameter of 0.55 μm. Or less (more preferably 0.5 μm or less) and grains having an average aspect ratio of 2 or more (more preferably 3 or more) in a mass ratio of 30% or more based on the total amount of photosensitive silver halide grains contained in the photosensitive material ( More preferably, it is preferably 60% or more).
Alternatively, particles having an average aspect ratio of 8 or more (more preferably 10 or more) and particles having an average sphere equivalent diameter of 0.55 μm or less (more preferably 0.5 μm or less) and an average aspect ratio of 2 or more (more preferably 3 or more). The silver equivalent mass of the combined grains is preferably 50% or more (more preferably 70% or more) with respect to the total amount of photosensitive silver halide grains contained in the photosensitive material.

  The silver halide color photographic light-sensitive material may have a light-sensitive emulsion layer other than those listed here. In particular, it is preferable from the viewpoint of color reproducibility that a light-sensitive emulsion layer spectrally sensitized in the cyan light region is provided to give a multilayer effect to the red-sensitive emulsion layer. The layer imparting the multi-layer effect may be blue sensitivity, green sensitivity, or red sensitivity. BL, as described in U.S. Pat. Nos. 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, and 63-89850. It is also possible to dispose a donor layer having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as GL, RL, or the like adjacent to or close to the main photosensitive layer.

The silver halide photographic light-sensitive material of the present invention is characterized by containing a hydrazine compound represented by the above general formula (I) or (IV), but typically contains a yellow color-forming coupler. A silver halide color photographic light-sensitive material having at least one emulsion layer, a green-sensitive emulsion layer containing a magenta color-forming coupler, and a red-sensitive emulsion layer containing a cyan color-forming coupler.
In particular, the effect of the present invention is important in a silver halide color photographic light-sensitive material for photographing use such as a color negative film and a color reversal film, and it is preferably applied to these color films. In the present invention, it is particularly preferable to apply to a color reversal film in which an image is directly used for viewing.

  When the present invention is applied to a silver halide color photographic light-sensitive material, examples of the image forming coupler used include the following.

Yellow coupler;
A coupler represented by the formula (I) or (II) described in the specification of EP502,424A;
A coupler represented by the formulas (1) and (2) described in the specification of EP513,496A (for example, Y-28 (18 pages));
A coupler represented by formula (I) of claim 1 of EP 568,037A;
A coupler represented by the general formula (I) on lines 45 to 55 of column 1 of US Pat. No. 5,066,576;
A coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425;
A coupler according to claim 1 on page 40 of EP 498,381 A1 (for example D-35);
A coupler represented by the formula (Y) on page 4 of EP447,969A1 (for example, Y-1, Y-54);
Couplers represented by formulas (II) to (IV) of column 7, lines 36 to 58 of US Pat. No. 4,476,219;
A coupler represented by formula (I) in JP-A No. 2002-318442;
Couplers represented by general formulas (I) to (IV) of JP-A-2003-50449;
A coupler represented by the formula (I) in EP 1,246,006 A2;
Such.

Magenta coupler;
Couplers described in JP-A-3-39737 (for example, L-57, L-68, L-77);
Couplers described in EP456,257A (for example, A-4-63, A-4-73, A-4-75);
Couplers described in the specification of EP486,965A (for example, M-4, M-6, M-7)
A coupler described in the specification of EP571,959A (for example, M-45)
A coupler (for example, M-1) described in JP-A-5-204106;
A coupler (for example, M-22) described in JP-A-4-362631
Couplers represented by the general formula (MC-1) described in JP-A-11-119393 (for example, CA-4, CA-7, CA-12, CA-15, CA-16, CA-18);
A coupler represented by the formula (M-I) (M-II) described in US Pat. No. 6,492,100B2;
A coupler represented by the formula (I) described in US Pat. No. 6,468,729B2;
Such.

Cyan coupler;
Couplers described in JP-A-4-204843 (for example, CX-1,3,4,5,11,12,14,15);
Couplers described in JP-A-4-43345 (for example, C-7, 10, 34, 35 and (I-1), (I-17));
A coupler represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385;
Couplers represented by the general formula (PC-1) described in JP-A-11-119393 (for example, CB-1, CB-4, CB-5, CB-9, CB-34, CB-44, CB- 49, CB-51);
Couplers represented by the general formula (NC-1) described in JP-A-11-119393 (for example, CC-1, CC-17);
A coupler represented by formula (I) in JP-A No. 2002-162717;
Such.

  For various techniques and inorganic / organic materials that can be used for silver halide photographic emulsions and silver halide photographic light-sensitive materials using the same, generally, Research Disclosure No. 1 is used. Those described in 308119 (1989), 37038 (1995), and 40145 (1997) can be used.

  In addition to this, more specifically, for example, technologies and inorganic / organic materials that can be used for color photographic light-sensitive materials to which silver halide photographic emulsions can be applied are described in the following locations of European Patent No. 436,938A2. And in the patents cited in Table 1 below.

(Item) (Applicable part)
1) Layer structure: page 146, line 34 to page 147, line 25) 2) silver halide emulsion that can be used together: page 147, line 26 to page 148, line 12) 3) yellow coupler that can be used together: Page 137, line 35 to page 146, line 33, page 149, line 21 to line 23) magenta coupler that can be used in combination: page 149, line 24 to line 28; European Patent No. 421,453A1 Page 3 line 5 to page 25 line 55

5) Cyan couplers that can be used in combination: page 149, lines 29 to 33; European Patent No. 432,804A2, page 3, line 28 to page 40, line 2 6) Polymer coupler: page 149, line 34 7th to 38th lines; European Patent No. 435,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler: page 53, line 42 to page 137, line 34, page 149, page 39 Lines 45 to 45 8) Functional couplers that can be used in combination: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; European Patent No. 435,334A2 3rd page, 1st line to 29th page, 50th line 9) Antiseptic / antifungal agent: 15th page, 25th line to 28th line 10) Formalin scavenger: 15th page, 15th line to 17th line 11) Combined use Other possible additives: page 153, lines 38-47 Eye; European Patent No. 421,453A1, page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40) 12) Dispersion method: page 150, line 4 to 24 Line 13) Support: page 150, lines 32 to 34 14) Film thickness and film properties: page 150, lines 35 to 49 15) Color development step: page 150, lines 50 to 151 Page 47, line 16) Desilvering process: page 151, line 48 to page 152, line 53 17) Automatic developing machine: page 152, line 54 to page 153, line 2 18) Water washing and stabilization process: Page 153, line 3 to line 37

Hereinafter, the present invention will be specifically described by way of examples, but is not limited thereto.
[Example 1]
Preparation of sample 101 (1) Preparation of triacetylcellulose film Triacetylcellulose was dissolved in dichloromethane / methanol = 92/8 (mass ratio) by a normal solution casting method (13% by mass), and plasticized. The agent, triphenyl phosphate and biphenyl diphenyl phosphate, added at a mass ratio of 2: 1 so that the total was 14% with respect to triacetyl cellulose, was prepared by the band method. The thickness of the support after drying was 97 μm.

(2) Contents of undercoat layer The following undercoat was applied to both surfaces of the triacetylcellulose film. The numbers represent the mass contained per 1.0 liter of undercoat liquid.
Gelatin 10.0g
Salicylic acid 0.5g
Glycerin 4.0g
700 ml of acetone
200 ml of methanol
Dichloromethane 80ml
Formaldehyde 0.1mg
Add water and add 1.0 liter

(3) Application of Back Layer The following back layer was applied to one side of the support that had been primed as described above.
1st layer binder: acid-treated gelatin (isoelectric point 9.0) 1.00 g
Polymer latex P-2 (average particle size 0.1 μm) 0.13 g
Polymer latex: P-4 (average particle size 0.2 μm) 0.23 g
UV absorber U-1 0.030g
UV absorber U-2 0.010g
UV absorber U-3 0.010g

UV absorber U-4 0.020g
High boiling point organic solvent Oil-2 0.030g
Surfactant W-2 0.010g
Surfactant W-4 3.0mg
The pH of the first layer coating solution was 8.2.

Second layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.10 g
Polymer latex: P-4 (average particle size 0.2 μm) 0.11 g
UV absorber U-1 0.030g
UV absorber U-3 0.010g
UV absorber U-4 0.020g
High boiling point organic solvent Oil-2 0.030g
Surfactant W-2 0.010g
Surfactant W-4 3.0mg
Dye D-2 0.10 g
Dye D-10 0.12 g
Potassium sulfate 0.25g
Calcium chloride 0.5mg
Sodium hydroxide 0.03g
The pH of the second layer coating solution was 6.7.

Third layer binder: acid-treated gelatin (isoelectric point 9.0) 3.30 g
Surfactant W-2 0.020g
Potassium sulfate 0.30g
Sodium hydroxide 0.03g
The pH of the third layer coating solution was 6.7.

Fourth layer Binder: Lime-treated gelatin (isoelectric point 5.4) 1.15 g
1: 9 copolymer of methacrylic acid and methyl methacrylate (average particle size 2.0 μm) 0.040 g
6: 4 copolymer of methacrylic acid and methyl methacrylate (average particle size 2.0 μm) 0.030 g
Surfactant W-2 0.060g
Surfactant W-1 7.0mg
Curing agent H-1 0.23g
The pH of the fourth layer coating solution was 5.2.

  The film surface pH of the back layer total coating film was 6.7.

(4) Application of photosensitive emulsion layer (1) Preparation of emulsion D (1-1) Host particle formation step 0.75 g of potassium bromide and oxidized low molecular weight gelatin 2 having an average molecular weight of 1 to 20,000 in a reaction vessel While stirring and maintaining 1000 ml of an aqueous solution containing 0.5 g (hereinafter also referred to as “mL”) at 35 ° C., 25 mL of an aqueous solution containing 0.8 g of silver nitrate and 40 mL of an aqueous solution containing 0.6 g of potassium bromide are added for 45 seconds. Over a double jet process. Thereafter, the temperature was raised to 70 ° C., 23 g of succinated gelatin was added, and thiourea dioxide was added in an amount of 2.0 × 10 ⁻⁵ mol per mol of the host grain silver in order to introduce a hole trap zone.
Next, 38 mL of use stations containing 6.13 g of silver nitrate were added by the double jet method over 23 minutes. At this time, the silver potential was kept at -10 mV with respect to the saturated calomel electrode.
Further, the silver iodide content was measured by an external stirrer described in JP-A-10-43570 using 600 mL of an aqueous solution containing 97 g of silver nitrate, 74 g of potassium bromide, 7.2 g of potassium iodide, and 700 mL of a solution containing 120 g of low molecular weight gelatin. A silver iodobromide fine grain emulsion (average size: 0.09 μm) was prepared, and this silver iodobromide fine grain emulsion was continuously added to the reaction vessel to dissolve the fine grains, and the host grains were put over 60 minutes. I grew up. At this time, an aqueous potassium bromide solution was added separately to keep the silver potential at ± 0 mV with respect to the saturated calomel electrode.
After the temperature was lowered to 40 ° C., while maintaining the temperature, 100 mL of an aqueous solution containing 16.3 g of silver nitrate and an aqueous solution of potassium bromide containing 4 mol% of potassium iodide were added to silver potential to −5 mV by the double jet method over 25 minutes. Added while keeping.

(1-2) Epitaxial Deposition Step Following the host particle formation step, the following step operation was performed to carry out epitaxial deposition. The silver potential was adjusted to +50 mV while maintaining 40 ° C.
After adding 2.3 × 10 ⁻⁴ mol of compound F-12 and 3.2 × 10 ⁻⁵ mol of compound F-7 as stabilizers, 1.5 × 10 ^{−3 of} spectral sensitizing dye S-1 was added. After adding 0.1 mol of an aqueous solution of calcium nitrate, the temperature was once raised to 70 ° C. and again lowered to 40 ° C., and then the spectral sensitizing dye S-3 was added at 2.0 × 10 ⁻⁴ mol. Then, 1.45 × 10 ⁻³ mol of potassium thiocyanate, 5.8 × 10 ⁻⁶ mol of potassium ferrocyanide, and 2.0 × 10 ⁻⁷ mol of K ₂ [IrCl ₆ ] were added.
Subsequently, 140 mL of an aqueous solution containing 17 g of silver nitrate and 100 mL of an aqueous solution containing 10.8 g of potassium bromide were added at a constant flow rate over 60 minutes by the double jet method to perform epitaxial deposition. At this time, the silver potential was kept at +120 mV with respect to the saturated calomel electrode. The amount of silver used for epitaxial deposition was 12.4% of the host grains.
After completion of the addition, the silver potential was adjusted to +120 mV with respect to the saturated calomel potential with silver nitrate, and then 200 mL of an aqueous solution containing 24 g of gelatin was added.

(1-3) Desalting / dispersing step After desalting by a known flocculation method at 35 ° C., 44 g of gelatin, 2.5 × 10 ⁻⁵ mol of compound F-12 as a stabilizer, compound F After adding 1.2 × 10 ⁻⁴ mol of -13 and adding 4.4 mL of phenoxyethanol as a preservative, the pH was adjusted to 5.9 and pAg 8.0 at 50 ° C.

(1-4) Chemical Sensitization Step While maintaining the above emulsion at 40 ° C., 6.7 × 10 ⁻⁶ mol of compound F-14 and 8.1 × 10 ⁻⁶ mol of sodium thiosulfate are used as chemical sensitizers. Then, 2.2 × 10 ⁻⁶ mol of N, N-dimethylselenourea was added, and the mixture was heated to 50 ° C. and aged for 100 minutes, and then 5.2 × 10 ⁻⁴ mol of compound F-11 was added. The chemical sensitization process was completed by adding 2.5 mol of potassium bromide.

The emulsion thus obtained had an average equivalent circle diameter of 1.5 μm, a coefficient of variation of equivalent circle diameter of 28%, an average thickness of 0.054 μm, and an average aspect ratio of 28. The silver iodobromide tabular grains having a silver content of 4.8 mol% were used as host grains, and silver halide grains having protrusions formed mainly at the apexes of the host tabular grains accounted for 88% of the total projected area. The average halogen composition of the protrusions was silver iodide content: silver bromide content: silver chloride content = 1.5: 98.5: 0 (mol%).
Further, when the respective sensitivities of the emulsion were determined based on the definition of surface sensitivity / total development sensitivity in the text, the total development sensitivity was higher than the surface sensitivity.

(2) Preparation of Emulsion F (2-1) Grain Formation In a reaction vessel, 1200 mL of an aqueous solution containing 0.9 g of potassium bromide and 3.7 g of oxidized low molecular weight gelatin having an average molecular weight of 1 to 20,000 was maintained at 35 ° C. While stirring, 31 mL of an aqueous solution containing 1.0 g of silver nitrate and 35 mL of an aqueous solution containing 0.9 g of potassium bromide were added by a double jet method over 50 seconds. Thereafter, the temperature was raised to 75 ° C., 17 g of succinated gelatin was added, and thiourea dioxide was added in an amount of 8 × 10 ⁻⁶ mol per 1 mol of silver of the host particles in order to introduce a hole trap zone.

Next, 59 mL of an aqueous solution containing 8.7 g of silver nitrate and 71 mL of an aqueous solution containing 6.2 g of potassium bromide were added over 13 minutes by the double jet method. At this time, the silver potential was kept at +4 mV with respect to the saturated calomel electrode. After completion of addition, 2.0 × 10 ⁻⁵ mol of Compound F-12 was added.
Further, silver bromoiodide fine particles (average size: 0.09 μm) using an external stirrer described in JP-A-10-43570 using 690 mL of an aqueous solution containing 110 g of silver nitrate, 74 g of a solution containing 74 g of potassium bromide and 73 g of low molecular weight gelatin. The silver bromide fine grain emulsion was continuously added to the reaction vessel to dissolve the fine grains, and the host grains were grown for 52 minutes. After the temperature of this solution was lowered to 50 ° C., while maintaining the temperature, 112 mL of an aqueous solution containing 45 g of silver nitrate and 101 mL of an aqueous solution containing 28.3 g of potassium bromide were maintained for 48 minutes while maintaining the silver potential at +110 mV by the double jet method. Added. After the addition was completed, an aqueous potassium bromide solution was added to adjust the silver potential to -65 mV.
Subsequently, using an aqueous solution containing 48 g of an aqueous solution containing 3.5 g of silver nitrate, 3.5 g of potassium iodide and 3.5 g of low molecular weight gelatin, a silver iodide fine grain emulsion (average size: 0.09 μm) by an external stirrer as described above. The silver bromide fine grain emulsion was continuously added to the reaction vessel over 1 minute. At this time, 20 mL of an aqueous solution containing 8.1 g of silver nitrate and 15 mL of an aqueous solution containing 4.2 g of silver bromide were added to the reaction vessel at the same time as the addition of the fine grain emulsion was started over 3 minutes.

After the temperature of this solution was lowered again to 40 ° C., 118 mL of an aqueous solution containing 47 g of silver nitrate and 68 mL of an aqueous solution containing 19 g of potassium bromide were added over 38 minutes while maintaining the silver potential at +30 mV. During this addition, 3.0 × 10 ⁻⁶ mol of potassium ferrocyanide and 1.0 × 10 ⁻⁷ mol of K ₂ [IrCl ₆ ] were added.

(2-2) Desalting / dispersing step After desalting at 35 ° C. by a known flocculation method, 52 g of gelatin, 7.8 × 10 ⁻³ mol of calcium nitrate, and 1.3 of compound F-13 were added. × 10 ⁻³ mol was added, 8.0 mL of phenoxyethanol was added as a preservative, and the pH was adjusted to 5.9 and pAg 8.2 at 50 ° C.

(2-3) Chemical Sensitization Step While maintaining the above emulsion at 56 ° C., 1.0 × 10 ⁻³ mol of spectral sensitizing dye S-1 and 2.2 × 10 3 of spectral sensitizing dye S-3 were obtained. ^-4 mol, potassium thiocyanate 6.5 × 10 ^-4 mol, chloroauric acid 2.5 × 10 ^-6 mol, sodium thiosulfate 4.6 × 10 ^-6 mol and N, N-dimethyl After adding 1.1 × 10 ⁻⁶ mol of selenourea, the mixture was heated to 50 ° C. and ripened for 90 minutes, and then a silver iodobromide fine grain emulsion corresponding to 2 g of silver nitrate (average grain size 0.05 μm, silver iodide) (1 mol% content) was added, and after aging for another 20 minutes, 5.2 × 10 ⁻⁴ mol of compound F-11 was added to complete the chemical sensitization step.

(Evaluation of dislocation lines)
For the above emulsions D and F, dislocation lines were directly observed using a transmission electron microscope by the method described in Example 1- (2) of JP-A-62-220238. As a result, in Emulsion D, dislocation lines were not observed for grains exceeding 80% of the number of grains, whereas in Emulsion F, many dislocation lines were observed for grains exceeding 80% of the number of grains (10 or more). ) Observed.

Based on Emulsion D, Emulsion C was prepared by changing the size and silver iodide content of the emulsion by a known method.
Further, based on the emulsion D, H, I, J, L, M, N, and R were prepared by changing the size and sensitizing dye by a known method.
Based on Emulsion F, Emulsions A, B and E were prepared by changing the size and silver iodide content of the emulsion in a well-known manner. Further, G, K, O, P, Q, S, T, U, and V were prepared based on Emulsion F by changing the size and sensitizing dye by a known method.
The characteristics of emulsions A to V are shown in Tables 1 and 2, and the types of spectral sensitizing dyes used are shown in Tables 3 to 5.

A photosensitive emulsion layer shown below was coated on the side opposite to the coated back layer to prepare Sample 101. The number represents the amount added per m ² . The effect of the added compound is not limited to the described use.
The gelatin shown below had a molecular weight (mass average molecular weight) of 100,000 to 200,000. The content of main metal ions was 2500 to 3000 ppm calcium, 1 to 7 ppm iron, and 1500 to 3000 ppm sodium.
Gelatin having a calcium content of 1000 ppm or less was also used in combination.
Each layer is prepared as an emulsified dispersion containing gelatin as an organic compound (W-2 and W-3 are used as surfactants), and a photosensitive emulsion and yellow colloidal silver are also prepared as gelatin dispersions. A coating solution was prepared by mixing these so as to obtain the described addition amount, and was used for coating. Cpd-H, O, P, Q, dye D-1, 2, 3, 5, 6, 8, 9, 10, 11, 12, H-1, P-3, F-1 to 9 are water or methanol , Dimethylformamide, ethanol, dimethylacetamide and the like were dissolved in an appropriate water-miscible organic solvent and added to the coating solution of each layer.
The gelatin concentration (mass content of gelatin solid / volume of coating solution) of each layer thus adjusted is in the range of 2.5% to 15.0%, and the pH of each coating solution is 5.0 to 8.5. In a coating solution for a layer containing a silver halide emulsion, the pAg value was 7.0 to 9.5 when adjusted to pH 6.0 and a temperature of 40 ° C.
After coating, the sample was dried by a multi-stage drying process maintained at a temperature in the range of 10 ° C to 45 ° C.

First layer: Antihalation layer Black colloidal silver 0.20g
Gelatin 2.20g
Compound Cpd-B 0.010 g
UV absorber U-1 0.050 g
UV absorber U-2 0.030g
UV absorber U-3 0.020g
UV absorber U-4 0.020g
UV absorber U-5 0.010g
Compound Cpd-F 0.20 g
Compound Cpd-R 0.020 g
Compound Cpd-S 0.020 g
High-boiling organic solvent Oil-2 0.020g
High boiling point organic solvent Oil-6 0.030g
High boiling point organic solvent Oil-8 0.020g
Dye D-4 1.0mg
Dye D-8 1.0mg
0.05 g microcrystalline solid dispersion of dye E-1
W-3 0.030g

Second layer: Intermediate layer 0.4 g of gelatin
Compound Cpd-F 0.050 g
Compound Cpd-R 0.020 g
Compound Cpd-S 0.020 g
High-boiling organic solvent Oil-6 0.020g
High boiling point organic solvent Oil-7 5.0mg
High boiling point organic solvent Oil-8 0.020g
Dye D-11 2.0mg
Dye D-7 4.0 mg
W-3 0.010g

3rd layer: Intermediate layer 0.4g of gelatin

Fourth layer: photosensitive emulsion layer Emulsion R Silver amount 0.02 g
Emulsion S Silver amount 0.05g
Emulsion T Silver amount 0.24g
Fine grain silver iodide (average sphere equivalent diameter 0.05μm)
0.005g silver
Gelatin 0.5g
Compound Cpd-F 0.030 g
High boiling point organic solvent Oil-6 0.010g
High boiling point organic solvent Oil-7 5.0mg
Dye D-7 4.0 mg
W-3 0.015g

5th layer: photosensitive emulsion layer Emulsion U Silver amount 0.14g
Gelatin 0.25g
Compound Cpd-M 0.010 g
High boiling point organic solvent Oil-6 0.010g
High-boiling organic solvent Oil-7 1.7mg

Layer 6: Intermediate layer Gelatin 1.50g
Compound Cpd-M 0.20 g
Compound Cpd-F 0.030 g
Compound Cpd-D 0.010 g
Compound Cpd-K 3.0 mg
UV absorber U-6 0.010g
High-boiling organic solvent Oil-6 0.15g
High boiling point organic solvent Oil-3 0.010g
High boiling point organic solvent Oil-4 0.010g

Seventh layer: Low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.05 g
Emulsion B Silver amount 0.40g
Emulsion C Silver amount 0.15g
Yellow colloidal silver Silver amount 0.1mg
1.00g gelatin
Coupler C-1 0.10g
Coupler C-2 4.0mg
UV absorber U-2 3.0mg
Compound Cpd-D 1.0 mg
Compound Cpd-J 2.0mg
High boiling point organic solvent Oil-5 0.050 g
High-boiling organic solvent Oil-10 0.010g
W-3 4.0mg
W-6 6.0mg

Eighth layer: Medium sensitivity red-sensitive emulsion layer Emulsion C Silver amount 0.12 g
Emulsion D Silver amount 0.12g
Silver bromide emulsion covered inside (average sphere equivalent diameter 0.11μm cubic grains)
0.01g of silver
Gelatin 0.50g
Coupler C-1 0.15g
Coupler C-2 7.0mg
Compound Cpd-D 1.5mg
Compound Cpd-T 2.0mg
High boiling point organic solvent Oil-5 0.050 g
High-boiling organic solvent Oil-10 0.010g
W-3 5.0mg
W-6 8.0mg

Ninth layer: High-sensitivity red-sensitive emulsion layer Emulsion E Silver amount 0.32 g
Emulsion F Silver amount 0.14g
Fine-grain silver iodobromide (silver iodide content 0.1 mol%, average sphere equivalent diameter 0.05 μm)
Gelatin 1.20g
Coupler C-1 0.70g
Coupler C-2 0.025g
Coupler C-3 0.020g
Additive P-1 0.010 g
Additive P-3 0.030 g
UV absorber U-1 0.010g
Compound Cpd-D 5.0 mg
Compound Cpd-L 1.0 mg
Compound Cpd-T 0.020 g
High boiling point organic solvent Oil-5 0.25g
High boiling point organic solvent Oil-9 0.05g
High boiling point organic solvent Oil-10 0.10g
W-3 0.013g
W-6 0.025g

Layer 10: Intermediate layer Gelatin 0.50g
Additive P-2 0.10 g
Dye D-5 0.020g
Dye D-9 6.0 mg
Compound Cpd-I 0.020 g
Compound Cpd-O 3.0mg
Compound Cpd-P 5.0 mg
High-boiling organic solvent Oil-6 0.020g

11th layer: Intermediate layer Yellow colloidal silver Silver amount 3.0mg
1.00g gelatin
Additive P-2 0.05g
Compound Cpd-A 0.05 g
Compound Cpd-D 0.030 g
Compound Cpd-M 0.30 g
High boiling point organic solvent Oil-3 0.010g
High boiling point organic solvent Oil-6 0.20g
W-3 0.020g

Layer 12: Low-sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.07 g
Emulsion H Silver amount 0.31g
Emulsion I Silver amount 0.31g
1.00g gelatin
Coupler C-4 0.045g
Coupler C-5 0.030g
Coupler C-6 5.0mg
Compound Cpd-B 0.012 g
Compound Cpd-G 3.0mg
Compound Cpd-K 2.4 mg
High-boiling organic solvent Oil-2 0.024g
High boiling point organic solvent Oil-5 0.024g
Additive P-1 5.0mg
W-2 6.0mg
W-3 4.0mg

13th layer: Medium sensitivity green sensitive emulsion layer Emulsion I Silver amount 0.15 g
Emulsion J Silver amount 0.28g
Gelatin 0.60g
Coupler C-4 0.10g
Coupler C-5 0.070g
Coupler C-6 0.010g
Additive P-1 0.010 g
Compound Cpd-B 0.030 g
Compound Cpd-U 9.0 mg
High boiling point organic solvent Oil-2 0.015g
High boiling point organic solvent Oil-5 0.030g
W-2 0.020g
W-3 8.0mg

14th layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver amount 0.30 g
Silver bromide emulsion coated inside (average sphere equivalent diameter 0.11 μm cube)
Silver amount 3.0mg
Gelatin 1.0g
Coupler C-4 0.40g
Coupler C-5 0.30g
Coupler C-7 0.05g
Compound Cpd-B 0.030 g
Compound Cpd-U 0.030 g
Additive P-1 0.10 g
W-2 0.070g
W-3 0.030g

15th layer: Yellow filter layer Yellow colloidal silver Silver amount 2.0mg
Gelatin 1.0g
Compound Cpd-C 0.010 g
Compound Cpd-M 0.10 g
High-boiling organic solvent Oil-1 0.020g
High-boiling organic solvent Oil-6 0.020g
0.40 g of microcrystalline solid dispersion of dye E-2
W-3 0.010g

16th layer: Photosensitive emulsion layer Emulsion V Silver amount 0.15 g
Gelatin 0.40g
High boiling point organic solvent Oil-5 2.0mg
Compound Cpd-Q 0.20 g
Dye D-6 2.0mg

17th layer: Low-sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.07 g
Emulsion M Silver amount 0.05g
Emulsion N Silver amount 0.09g
Gelatin 0.80g
Coupler C-9 0.10g
Coupler C-10 0.50g
UV absorber U-5 0.035g
Additive P-1 0.020 g
Compound Cpd-B 0.020 g
Compound Cpd-I 10.0 mg
Compound Cpd-K 1.5mg
W-3 0.030g
W-6 0.030g

18th layer: High-sensitivity blue-sensitive emulsion layer Emulsion O Silver amount 0.08 g
Emulsion P Silver amount 0.12g
Emulsion Q Silver amount 0.19g
2.00 g of gelatin
Coupler C-8 0.15g
Coupler C-10 0.80g
Coupler C-6 0.010g
UV absorber U-5 0.060g
Additive P-1 0.010 g
Compound Cpd-B 0.060 g
Compound Cpd-D 3.0mg
Compound Cpd-E 0.020 g
Compound Cpd-F 0.020 g
Compound Cpd-N 5.0 mg
High boiling point organic solvent Oil-5 0.020g
W-3 0.060g
W-6 0.060g

19th layer: 1st protective layer gelatin 0.70 g
UV absorber U-1 0.20g
UV absorber U-2 0.10g
UV absorber U-5 0.10g
Compound Cpd-B 0.030 g
Compound Cpd-O 5.0 mg
Compound Cpd-A 0.030 g
Compound Cpd-H 0.10 g
Dye D-1 1.0 mg
Dye D-3 1.0 mg
Dye D-6 0.015g
Dye D-12 4.0 mg
High boiling point organic solvent Oil-3 0.040g
W-3 0.015g

20th layer: 2nd protective layer Colloidal silver Silver amount 2.5mg
Fine-grain silver iodobromide emulsion (average sphere equivalent diameter 0.06 μm, silver iodide content 1 mol%)
Silver amount 0.15g
Gelatin 0.80g
UV absorber U-1 0.15g
UV absorber U-2 0.070g
UV absorber U-5 0.090g
High boiling point organic solvent Oil-3 0.010g
W-3 6.0mg

21st layer: 3rd protective layer gelatin 1.00g
Polymethylmethacrylate (average particle size 1.5μm)
0.10 g
6: 4 copolymer of methyl methacrylate and methacrylic acid (average particle size 1.5 μm) 0.15 g
Silicone oil SO-1 0.10g
Surfactant W-1 5.0mg
Surfactant W-2 0.040g
In addition to the above composition, additives F-1 to F-11 were added to all the emulsion layers. Further, gelatin hardener H-1 and coating and emulsifying surfactants W-2, W-3, and W-4 were added to each layer in addition to the above composition.
Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.
The coating film thickness in the dry state of the sample 101 produced as described above was 26.5 μm, and the swelling ratio when swollen with distilled water at a temperature of 25 ° C. was 1.88 times.

<Preparation of organic solid disperse dye>
(Preparation of microcrystalline solid dispersion of dye E-1)
15 g of W-5 and water were added to a wet cake of dye E-1 (270 g as the net amount of E-1) and stirred to make 4000 g. Next, 1700 ml of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultraviscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec through the slurry at a discharge rate of 0.51 / min for 2 hours. Crushed. The beads were removed by filtration, water was added to dilute to a dye concentration of 3% by weight, and then heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained dye fine particles was 0.30 μm, and the breadth of the particle size distribution (particle size standard deviation × 100 / average particle size) was 20%.

(Preparation of microcrystalline solid dispersion of dye E-2)
270 g of water and W-3 were added to 1400 g of E-2 wet cake containing 30% by mass of water and stirred to obtain a slurry having an E-2 concentration of 40% by mass. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm are filled into a crusher, Ultra Viscomill (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed is about 10 m / sec and the discharge rate is 0.5 liter / min through the slurry. For 8 hours. This was diluted with ion-exchanged water to 20% by mass to obtain a microcrystalline solid dispersion of E-2. The average particle size was 0.15 μm.
Next, changes as shown in Table 6 were made based on the sample 101 to prepare samples 102 to 110. In Table 6, the compound number indicated by “the compound of the present invention” indicates that shown in the specific example of the compound represented by formula (I) or (IV).

  The development process shown below was defined as (development process A). In the evaluation, samples 101 and 104 that were not exposed and those that were completely exposed to light were used at a ratio of 1: 1 after running processing until the replenishment amount was four times the tank capacity.

(Development A)
In the evaluation, the sample 101 that had been completely exposed to the unexposed light was used at a ratio of 1: 1 after running processing until the replenishment amount was four times the tank capacity. The conditions for the treatment process are shown in Table 7 below.

The composition of each treatment solution was as follows.
[First developer] [Tank solution] [Replenisher]
Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 1.5 g 1.5 g
Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g
Sodium sulfite 30g 30g
Hydroquinone potassium monosulfonate 20g 20g
Potassium carbonate 15g 20g
Potassium bicarbonate 12g 15g
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g
Potassium bromide 2.5g 1.4g
Potassium thiocyanate 1.2g 1.2g
Potassium iodide 2.0mg −
Diethylene glycol 13g 15g
Add water 1000ml 1000ml pH 9.65 9.65
The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversing liquid] [Tank liquid] [Replenisher]
Nitrilo-N, N, N-trimethylenephosphonic acid tank solution ・ Same as 3.0 g of sodium salt, stannous chloride and dihydrate 1.0 g 〃
Sodium hydroxide 8g 〃
Glacial acetic acid 15ml 〃
1000ml with water
pH 6.00 〃
The pH was adjusted with acetic acid or sodium hydroxide.

[Color developer] [Tank solution] [Replenisher]
Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g
Sodium sulfite 7.0 g 7.0 g
Trisodium phosphate, 12 hydrate 25g 25g
Potassium bromide 1.0 g −
Potassium iodide 50mg −
Sodium hydroxide 10.0g 10.0g
Citrazic acid 0.5g 0.5g
N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline, 3/2 sulfuric acid, monohydrate
9.0g 9.0g
3,6-dithiaoctane-1,8-diol 0.6 g 0.7 g
Add water 1000ml 1000ml pH 11.85 12.00
The pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] [Tank liquid] [Replenisher]
Ethylenediaminetetraacetic acid, disodium salt, dihydrate 8.0 g 8.0 g
Sodium sulfite 6.0g 8.0g
1-thioglycerol 0.4 g 0.4 g
Formaldehyde sodium bisulfite adduct 25g 25g
Add water 1000ml 1000ml pH 6.30 6.10
The pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher solution]
Ethylenediaminetetraacetic acid, disodium salt, dihydrate 2.0 g 4.0 g
Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / Dihydrate
120g 240g
Potassium bromide 100g 200g
Ammonium nitrate 10g 20g
Add water 1000ml 1000ml pH 5.70 5.50
The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher solution]
Ammonium thiosulfate 80g Same as tank solution Sodium sulfite 5.0g 〃
Sodium bisulfite 5.0g 〃
1000ml with water
pH 6.60 〃
The pH was adjusted with acetic acid or aqueous ammonia.

[Stabilizer] [Tank fluid] [Replenisher]
1,2-Benzisothiazolin-3-one 0.02 g 0.03 g
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 0.3 g
Polymaleic acid (average molecular weight 2,000) 0.1 g 0.15 g
Add water 1000ml 1000ml pH 7.0 7.0

(Sample evaluation)
The above-mentioned samples 101 to 110 were cut into strips, and sensitometry was performed by the following method.

(Evaluation of color turbidity)
Two sets of samples 101 to 110 were prepared, and one set was subjected to monochromatic exposure so as to give the lowest density of the cyan image with red monochromatic light (exposed through a filter having a shorter wavelength than 600 nm). The exposed sample was developed by the development process A. The “analysis density” is calculated from the obtained result, the lowest density of the cyan analysis density is obtained, and this value is set as the A density.
Next, the second set of samples is exposed to white light having a color temperature of 4800 degrees, and the same development processing as described above is performed to obtain the cyan density of each sample. This value is used as the B density.
By calculating the difference between the A density and the B density thus obtained, the degree of color turbidity in the cyan color red-sensitive emulsion layer was evaluated. The larger this value, the worse the color turbidity.
The “analytical density” means a color density obtained by subtracting the density due to the secondary absorption of the color material of the color sensitive layer other than the relevant color sensitive layer. For example, the analysis density of the red color-sensitive layer is a value obtained by subtracting the cyan density due to the secondary absorption of each color material of the blue-sensitive emulsion layer and the green color-sensitive layer from the measured cyan density.

(Evaluation of remaining color)
Two sets of samples 101 to 110 were prepared. One set was exposed to white light so that the minimum density of each sample was obtained, and development was performed in the same manner except that the temperature of the second washing was set to 15 ° C. in the development process A. Treatment B was applied.
The other set was exposed under the same conditions that resulted in the lowest density, and then subjected to development processing-C in development processing-A, in which the second water washing was extended at 40 ° C. for 20 minutes.
Thereafter, the concentration (550 nm) of both was measured, and the difference was taken as the characteristic value. The larger the value, the more sensitizing dye remains in Development Processing-B, which is not preferable.

(Evaluation of storage stability)
Two sets of samples 101 to 110 were prepared, one set was stored for 14 days under the condition of 55 ° C. and 55% RH, and the other set was stored frozen for the same period. Thereafter, the two were exposed to white light having a color temperature of 4800 K through an optical wedge whose density was continuously changed, and processed by the development process A described above, and the respective densities of yellow, magenta, and cyan were measured. In particular, for a cyan density with a large change, the exposure value giving a cyan density of 0.7 was used as a characteristic value, and the difference between the exposure value of the one stored frozen and the exposure value stored for 3 days at 60 ° C. and 55% RH was taken. Table 12 shows the results. The larger the value, the greater the sensitivity change and the poorer storage stability.

(Surface condition evaluation of coating film)
Samples 101 to 110 were exposed with a light-adjusting exposure device so that the density of the cyan image, magenta image, and yellow image was around 1.0, and the above-described development processing A was performed. The number of foreign matters having a size of 100 μm or more was counted in an area of 10 cm square using a microscope with a magnification of 50 times. This operation was randomly selected at five points to determine the average number. The numbers after the decimal point are rounded down. The larger the number, the worse the coated surface shape.
Table 8 shows the obtained results.

Sample 102 in which the compound of Cpd-M is replaced with comparative compound X-1 in comparison with sample 101 is improved in storage stability, but the effect of improving other performance is small. Similarly, the sample 103 replaced with the comparative compound X-2 was improved in the residual color and storage stability, but rather the coated surface condition was deteriorated. On the other hand, Samples 103 to 110 replaced with the compound of the present invention have obtained favorable results for the problem which is the subject of the present invention. In particular, the sample 104 and the sample 110 using the compound of the general formula (I) of the present invention are more preferable in the present invention. In addition, a preferable result is obtained in the sample 109 in which the anti-turbidity agent other than the present invention is mixed to such an extent that the effects of the present invention are not impaired.

[Example 2]
Based on the samples 104 and 106 of the present invention of Example 1, the changes as shown in Table 9 were made, and samples 204 and 206 were produced. In Table 9, the compound number indicated by “the compound of the present invention” indicates that shown in the specific example of the compound represented by formula (I) or (IV).

(Sample evaluation)
Samples 104, 204, 106, and 206 were cut into strips, and sensitometry was performed by the following method.

(Evaluation of color turbidity)
Evaluation was performed in the same manner as in Example 1.

(Evaluation of sensitivity and color density)
The sample of Example 2 was exposed to white light having a color temperature of 4800 K through an optical wedge having a continuously changing density, processed by the above-described development process-A, and each density of yellow, magenta, and cyan. Was measured. In Example 2, the exposure amount giving a magenta density of 0.7 in Example 2 was used as a characteristic value, and the difference in exposure amount with respect to the samples 104 and 106 was expressed in logarithm in Table 9. + Indicates that the sensitivity is high, and-indicates that the sensitivity is low. The maximum color density also showed magenta density.
Table 10 shows the obtained results.

From the sample 104 of the present invention, the compound NO. Sample 204 in which 3 is added to the eleventh layer of the low-sensitivity green-sensitive emulsion layer is in a preferable direction because the color turbidity is further reduced.
Similarly, from the sample 106, the compound NO. Sample 206 in which No. 19 was added to the eleventh layer of the low-sensitivity green-sensitive emulsion layer obtained the effect of color turbidity. The effect of adding 19 is not so great. On the other hand, since the color density was lowered, it can be seen that addition of a large amount of the compound represented by the general formula (I) or (IV) according to the present invention is not preferable.

Claims (10)

In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one layer in the silver halide color photographic light-sensitive material is represented by the following general formula (I). A silver halide color photographic material comprising at least one compound.

[In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group. Represents a group or an iminomethylene group, and Het ¹ represents a heterocyclic group. ] 2. The silver halide color photographic material according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II).

[In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group. Represents a group or an iminomethylene group, and Het ² represents a nitrogen-containing hetero 6-membered ring group. ] 3. The silver halide color photographic material according to claim 2, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (III).

[In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group. Represents a group or an iminomethylene group. R ^a represents ^a substituent, and n represents 0 or an integer of 1 to 4. ]   In a silver halide color photographic material having at least one photosensitive silver halide emulsion layer on a support, at least one hydrophilic colloid layer other than the photosensitive layer in the silver halide color photographic material is provided. 4. The silver halide color photographic material according to claim 3, comprising at least one compound represented by the general formula (III). In a silver halide color photographic material having at least one photosensitive silver halide emulsion layer on a support, at least one hydrophilic colloid layer other than the photosensitive layer in the silver halide color photographic material is provided. A silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula (IV):

[In the formula, Ar represents an aromatic group, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aromatic group, and G ¹ represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphoryl group, an oxalyl group. Represents a group or an iminomethylene group, and R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aromatic group. However, each group of Ar and R ^{1 to} R ⁵ does not contain a polyhydroxy aromatic ring as a partial structure thereof, and when R ⁵ is an aryl group, both R ³ and R ⁴ represent a hydrogen atom. ]   2. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (I) is a color turbidity preventing agent.   6. The silver halide color photographic light-sensitive material according to claim 5, wherein the compound represented by the general formula (IV) is a color turbidity inhibitor.   In at least one silver halide emulsion forming the silver halide emulsion layer, a tabular halide having an average aspect ratio of 2 or more of 70% or more of the total projected area of silver halide grains contained in the silver halide emulsion The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material is a silver particle.   9. The silver halide color photographic light-sensitive material according to claim 8, wherein the tabular silver halide grains have a {111} plane as a main plane.   10. The silver halide color photographic light-sensitive material according to claim 8, wherein the silver iodide content of the tabular silver halide grains is 0.5 to 20 mol%.