JPH10254084A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material small in residual dye stains even after rapid processing and appropriate in spectral maximum wavelength and high in sensitivity by incorporating a specified compound. SOLUTION: This silver halide photographic sensitive material contains at least one of the compounds represented by the formula in which Z<1> is an atomic group necessary to complete a naphthothiazole ring, Z<2> is an atomic group necessary to complete a 5-membered N-containing hetero ring; V<1> is an cyano group; each of R<1> and R<2> is an alkyl group; L<1> is a methine group; X<1> is acounter ion necessary to neutralize an intramolecular charge; and n<1> is a number of >=0 necessary to neutralize the intramolecular charge. This photosensitive material attains both of high sensitivity and low residual dye stains and it is small in change of sensitivity and pressure susceptibility when it is stored in an unexposed state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having suitability for rapid processing and short-time exposure and having little residual color after processing. .

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials which have become widespread today have progressed more and more quickly and easily at various places due to advances in light-sensitive materials themselves and development processing techniques. Taking color printing as an example of silver halide photographic light-sensitive materials, a centralized system with a production base equipped with high-speed printers and large-scale processing equipment for mass production, and a small print processor called a minilab installed in stores Due to the development of a distributed processing method using a large number of prints, mass production for various purposes is performed, and it is desired to produce many prints quickly and easily.

[0003] For rapid processing, see US Pat.
No. 0,878 discloses a technique for processing a color photographic light-sensitive material using a silver halide emulsion having a high silver chloride content with a color developing solution substantially free of sulfite ions and benzyl alcohol. However, pursuing such a reduction in processing time also shortens the time required for dissolving the dyes and sensitization contained in the photosensitive material, so that if the processing time is further reduced in the future, color residue will occur in the past. Even for those which did not exist, there is a possibility that a problem that color residue derived from these dyes and pigments becomes remarkable may occur.

As a silver halide photographic light-sensitive material suitable for such rapid processing, for example, most of currently manufactured photographic printing papers for color photography can be processed more rapidly than silver bromide emulsions. Silver halide emulsions with a high possible silver chloride content have been used. It is known that a silver chloride emulsion has a structure in which a spectral sensitizing dye is less likely to be adsorbed than a silver bromide emulsion, and as a spectral sensitizing dye for avoiding such a property, For example, JP-A-8
A monomethine cyanine dye having a naphthothiazole structure described as a sensitizing dye A in JP-114888 is known. Although this dye shows satisfactory sensitivity by being well adsorbed on a silver chloride emulsion, color remnants after processing may become a problem if processing is further accelerated in the future.

As a means for reducing the color residue after the treatment, a dye in which a naphthothiazole ring is replaced by a benzothiazole ring having a halogen atom or the like as a substituent (for example, described in JP-B 8-33610, page 21). Blue-sensitive dyes) or dyes in which a naphthothiazole ring is replaced by a benzothiazole ring having a cyano group or the like as a substituent (for example, a blue-sensitive dye described on page 4 of JP-A-8-297341). I have. Depending on the form of use, these are effective as a dye with little color retention, but the exposure conditions are different because the absorption maximum wavelength is shorter than the dye having a naphthothiazole ring,
There is a problem that the sensitivity is low due to insufficient adsorption to the silver chloride emulsion. As means for achieving both high sensitivity and reduction of color residue after processing, US Pat.
Nos. 45, 3,044,875, 2,304,112 and 2,278,461 disclose dyes in which a heterocyclic structure is substituted with a benzothiazole ring via a linking group. -179744 and JP-A-8-50
No. 341, a dye having a benzothiazole ring substituted with a heterocyclic group is disclosed. However, these dyes have a shorter absorption maximum wavelength than intended in the use form of the present invention, and a degree of color retention. Is not sufficiently reduced.

As is apparent from the above description, even when rapid processing is performed, a silver halide photograph containing a spectral sensitizing dye that has a small color residue after processing and provides an appropriate spectral maximum wavelength and sensitivity. It is desired to provide a photosensitive material.

[0007]

The problem to be solved by the present invention is that a silver halide photograph which gives less color residue even after rapid processing and which gives an appropriate spectral maximum wavelength and sensitivity. It is to provide a photosensitive material.

[0008]

As a result of intensive studies, the objects of the present invention have been achieved by the following silver halide photographic materials. That is,

(1) A silver halide photographic material comprising at least one compound represented by formula (I). General formula (I)

[0010]

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In the formula, Z ¹ represents an atomic group necessary for completing a naphthothiazole ring. Z ² represents an atom group necessary for completing a nitrogen-containing 5-membered heterocyclic ring. V ¹ represents a cyano group, and R ¹ and R ² represent an alkyl group. L ¹ represents a methine group, X ¹ represents a counter ion necessary for neutralizing the charge, and n ¹ represents a number of 0 or more required for neutralizing the charge in the molecule. (2) The compound represented by the general formula (I) of (1), wherein the nitrogen-containing 5-membered heterocycle completed with Z ² is a benzothiazole ring or a naphthothiazole ring. The silver halide photographic light-sensitive material as described above. (3) In a silver halide photographic material having at least one silver halide photographic emulsion layer on a support, the silver halide grains of at least one of the silver halide photographic emulsion layers have a silver chloride content. A silver halide photographic material comprising at least 95 mol% of at least one compound represented by the formula (I) in the emulsion layer. (4) In a silver halide photographic material having at least one silver halide photographic emulsion layer on a support, at least one of the emulsion layers comprises at least one compound represented by the general formula (I) and at least one compound represented by the general formula (I) A silver halide photographic material comprising at least one compound represented by II). General formula (II)

[0012]

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In the formula, Z ¹¹ and Z ¹² represent an atomic group necessary for completing a nitrogen-containing 5-membered heterocyclic ring. R ¹¹ and R ¹²
Is the same as R ¹ and R ² , L ¹¹ is the same as L ¹ , X ¹¹ is X
Synonymous with ¹ and n ¹¹ is synonymous with n ¹ .

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds represented by the general formulas (I) and (II) according to the present invention will be described in detail below.

Z ¹ represents an atomic group necessary for completing a naphthothiazole ring, and the naphthothiazole ring represented by Z ¹ is a naphtho [1,2-d] thiazole ring, a naphtho [2,
It may be any of a 1-d] thiazole ring and a naphtho [3,2-d] thiazole ring, and may further have a substituent. Z ² , Z ¹¹ and Z ¹² each represent a nitrogen-containing 5-membered heterocyclic ring which may be condensed, and may further have a substituent. Preferred examples of the nitrogen-containing 5-membered heterocyclic ring represented by Z ² , Z ¹¹ and Z ¹² include a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphtho [1,2-d] thiazole ring and a naphtho [2,1- d] thiazole ring, naphtho [3,2-d] thiazole ring, oxazoline ring, oxazole ring, benzoxazole ring, naphtho [1,2-
d) oxazole ring, naphtho [2,1-d] oxazole ring, naphtho [3,2-d] oxazole ring, indolenine ring, imidazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, naphtho [1, 2-
d] selenazole ring, naphtho [2,1-d] selenazole ring, naphtho [3,2-d] selenazole ring, tellurazole ring, benzotellurazole ring, naphtho [1,2-d]
Tellurazole ring, naphtho [2,1-d] tellurazole ring, naphtho [3,2-d] tellurazole ring, indoline ring, quinoline ring, oxadiazole ring, imidazo [4
5-b] quinoxaline ring and the like,
More preferred are a thiazole ring, a benzothiazole ring, a naphtho [1,2-d] thiazole ring and a naphtho [2,1-
d] thiazole ring, naphtho [3,2-d] thiazole ring, oxazole ring, benzoxazole ring, naphtho [1,2-d] oxazole ring, naphtho [2,1-d]
Oxazole ring and naphtho [3,2-d] oxazole ring, particularly preferred are benzothiazole ring, naphtho [1,2-d] thiazole ring and naphtho [2,1-d]
A thiazole ring and a naphtho [3,2-d] thiazole ring.

Z¹ , Z¹¹And Z¹²Yes as a substituent of
May have a good thing, Z ^Two As a substituent of
Is V¹ May have another substituent. Z¹ , Z
^Two , Z¹¹And Z¹²The following are preferred as substituents
Is mentioned. An unsubstituted alkyl group having 1 to 35 carbon atoms (eg,
For example, methyl group, ethyl group, propyl group, isopropyl
Group, butyl group, isobutyl group, hexyl group, octyl
Group, dodecyl group, octadecyl group, cyclopentyl group,
Cyclopropyl group, cyclohexyl group), substituted alkyl
When the substituent is V, the substituent represented by V is
Is not limited, for example, carboxy group, sulfo group,
Group, halogen atom (for example, fluorine atom, chlorine atom, odor
Atom, iodine atom), hydroxy group, having 1 to 35 carbon atoms
Alkoxycarbonyl group (for example, methoxycarbonyl
Group, ethoxycarbonyl group, phenoxycarbonyl group,
Benzyloxycarbonyl group), alkyl having 1 to 35 carbon atoms
Coxy groups (eg methoxy, ethoxy, benzyl
Xyl group, phenethyloxy group),

An aryloxy group having 6 to 35 carbon atoms (for example, phenoxy group, 4-methylphenoxy group, α-naphthoxy group), an acyloxy group having 1 to 35 carbon atoms (for example, acetyloxy group, propionyloxy group), 1 to
35 acyl groups (for example, acetyl, propionyl,
Benzoyl group, mesyl group), carbamoyl group having 1 to 35 carbon atoms (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), and sulfamoyl group having 0 to 35 carbon atoms (for example, Sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl group having 6 to 35 carbon atoms (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α
-Naphthyl group),

A heterocyclic group having 4 to 35 carbon atoms (for example, 2-
Pyridyl group, tetrahydrofurfuryl group, morpholino group, 2-thienyl group), amino group having 0 to 35 carbon atoms (for example, amino group, dimethylamino group, anilino group, diphenylamino group), alkylthio group having 1 to 35 carbon atoms Group (eg, methylthio group, ethylthio group), having 1 to 3 carbon atoms
5 alkylsulfonyl groups (eg, methylsulfonyl group, propylsulfonyl group), alkylsulfinyl groups having 1 to 35 carbon atoms (eg, methylsulfinyl group), nitro groups, phosphoric acid groups, and acylamino groups having 1 to 35 carbon atoms (eg, An acetylamino group), an ammonium group having 1 to 35 carbon atoms (eg, trimethylammonium group, tributylammonium group), a mercapto group, a hydrazino group having 1 to 35 carbon atoms (eg, trimethylhydrazino group), and a ureido having 1 to 35 carbon atoms Groups (eg ureido groups, N, N-
A dimethylureido group), an imide group having 1 to 35 carbon atoms, an unsaturated hydrocarbon group having 1 to 35 carbon atoms (for example, a vinyl group,
Ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group). V may be further substituted on these substituents. ｝,

An unsubstituted aryl group having 6 to 35 carbon atoms (for example, phenyl group and 1-naphthyl group), a substituted aryl group having 6 to 45 carbon atoms (the above-mentioned V is mentioned as a substituent), and a carbon number 4 to 35 unsubstituted heterocyclic groups (e.g., 2
-Pyridyl group, 2-thiazolyl group, morpholino group, 2-
A thienyl group), a substituted heterocyclic group having 4 to 45 carbon atoms (the aforementioned V is mentioned as the substituent), or a substituent represented by the aforementioned V is preferably used.

More specifically, alkyl groups (for example, methyl group, ethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, sulfomethyl group, 2-sulfoethyl group, −
Sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-
Cyanoethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, hydroxymethyl group, 2-hydroxyethyl group,
4-hydroxybutyl group, 2,4-dihydroxybutyl group, 2-methoxyethyl group, 2-ethoxyethyl group, methoxymethyl group, 2-ethoxycarbonylethyl group, methoxycarbonylmethyl group, 2-methoxyethyl group, 2
-Ethoxyethyl group, 2-phenoxyethyl group, 2-
(4-phenyl-phenoxy) ethyl group, 2-naphthoxyethyl group, 2-acetyloxyethyl group, 2-propionyloxyethyl group, 2-acetylethyl group,

3-benzoylpropyl group, 2-carbamoylethyl group, 2-morpholinocarbonylethyl group, sulfamoylmethyl group, 2- (N, N-dimethylsulfamoyl) ethyl group, benzyl group, 2-naphthylethyl Group, 2- (2-pyridyl) ethyl group, allyl group, 3-aminopropyl group, dimethylaminomethyl group, 3-ditylaminopropyl group, methylthiomethyl group, 2-methylsulfonylethyl group, methylsulfinylmethyl group, 2 −
Acetylaminoethyl group, acetylaminomethyl group, trimethylammoniummethyl group, 2-mercaptoethyl group, 2-trimethylhydrazinoethyl group, methylsulfonylcarbamoylmethyl group, (2-methoxy) ethoxymethyl group, and the like. Aryl group (for example, phenyl group, 1-naphthyl group, p-phenylphenyl group,
p-chlorophenyl group), heterocyclic group (for example, 2-pyridyl group, 2-thiazolyl group, 4-phenyl-2-thiazolyl group),

Carboxy, chloro, bromo, formyl, acetyl, benzoyl, 3-carboxypropanoyl, 3-hydroxypropanoyl, chlorine, N-phenylcarbamoyl, N-butylcarbamoyl, A boric acid group, a sulfo group, a hydroxy group, a methoxy group, a methoxycarbonyl group, an acetyloxy group, and a dimethylamino group are preferred.

V ¹ represents a cyano group, which may be bonded to the ring at any position on the ring represented by Z ² . When Z ² is benzothiazole, substitution with a 5- or 6-position cyano group is preferred.

R ¹ , R ² , R ¹¹ and R ¹² represent an alkyl group. Examples of the alkyl group include those having 1 to 1 carbon atoms.
2, preferably an unsubstituted alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), a substituted alkyl group {for example, a carboxy group, a sulfo group, Cyano group, halogen atom (for example, fluorine, chlorine, bromine), hydroxy group, alkoxycarbonyl group having 1 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), alkoxy group having 1 to 8 carbon atoms (Eg, methoxy, ethoxy, benzyloxy, phenethyloxy),
A monocyclic aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-tolyloxy), an acyloxy group having 1 to 3 carbon atoms (eg, acetyloxy, propionyloxy), an acyl group having 1 to 8 carbon atoms (eg, acetyl , Propionyl, benzoyl, mesyl), a carbamoyl group having 1 to 8 carbon atoms (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group having 1 to 8 carbon atoms (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), having 6 to 6 carbon atoms
And an alkyl group having 1 to 18 carbon atoms で substituted with 10 aryl groups (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl).

More preferably, it is an unsubstituted alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), and 1 to 6 carbon atoms. 6 carboxyalkyl groups (eg 2
-Carboxyethyl group, carboxymethyl group), a sulfoalkyl group having 1 to 6 carbon atoms (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-
Sulfobutyl group) and methanesulfonylcarbamoylmethyl group, and particularly preferred are 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, and 4-sulfobutyl group.
A sulfobutyl group and a methanesulfonylcarbamoylmethyl group.

L ¹ and L ¹¹ represent a substituted or unsubstituted methine group. Examples of the substituted ring group include a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, cyclopropyl), and 6 to 15 carbon atoms, preferably A substituted or unsubstituted aryl group having 6 to 10 carbon atoms (eg, phenyl, tolyl, o-carboxyphenyl, o-methoxyphenyl), a heterocyclic group (eg, pyridyl, thienyl, furyl, pyrazyl, thiazolyl, morpholyl); A halogen atom (eg, methoxy group, ethoxy group), an amino group having 1 to 12, preferably 1 to 8 carbon atoms (eg, amino group, dimethylamino group, methylphenylamino group, 4-acetylpiperazin-1-yl group) And the like, and particularly preferably a hydrogen atom, a methyl group or an ethyl group.

X ¹ and X ¹¹ are included in the formula to indicate the presence or absence of a cation or an anion when a counter ion is required to neutralize the ionic charge in the molecule of the compound. I have. Whether a compound is a cation, anion, or a compound having no net ionic charge depends on its molecular structure and substituents. Typical cations as counterions include inorganic or organic ammonium ions (eg, triethylammonium ion, pyridinium ion), alkali metal ions (eg, sodium ion, potassium ion), and alkaline earth metal ions (eg, calcium ion) , Magnesium ion).

Typical anions as counterions include halide ions (eg, fluoride ions, chloride ions, bromide ions, iodide ions), and arylsulfonic acid ions (eg, p-toluenesulfonic acid). Ion, p-chlorobenzenesulfonic acid ion), alkylsulfonic acid ion (for example, methanesulfonic acid ion), aryldisulfonic acid ion (for example, 1,3
-Benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion, ethyl sulfate ion), sulfate ion, thiocyanate ion, perchloric acid Ion, tetrafluoroboric acid, pyrophosphate ion, acetate ion, trifluoromethanesulfonic acid ion, hexafluorophosphate ion and the like. The counter ion may be an ionic polymer, another organic compound having a reverse charge, or a metal complex ion (for example, bis (1,2-benzenedithiolato) nickel (III) ion). Preferred are sodium ion, potassium ion, triethylammonium ion and pyridinium ion, and more preferred are sodium ion, potassium ion and triethylammonium ion. n ¹ , n ¹¹ and n ²¹ represent a number of 0 or more necessary for neutralizing the electric charge.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the scope of the compounds used in the present invention is not limited thereto. Specific examples of the compound represented by the general formula (I)

[0030]

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[0031]

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[0032]

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[0033]

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Specific examples of the compound represented by the general formula (II)

[0035]

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In the present invention, the compounds represented by the general formulas (I) and (II)
The synthesis of the compound represented by, with reference to the following literature and the synthesis examples described in the literature cited therein,
Those skilled in the art can easily synthesize. a) Heterocyclic Compounds-Cyanine Die and & Co. by FM Harmer
Related Compounds (Heterocyclic compound
s-Cyanine dyes and related compounds-) ”(John Wiley & Sons),
New York London, 1964). b) Tea Haiti James (TH James)
`` The Theory of Photographic Process (T
he Theory of Photographic Process) ", (Macmillan
(Macmillan), New York, 1977). Hereinafter, specific synthesis examples will be described, but the synthesis method of the methine compound of the present invention is not limited thereto. Other dyes of the present invention can be synthesized according to the following synthesis method. Scheme 1

[0037]

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Synthesis of Exemplified Compound I-1 Intermediate III-1 1.5 g, Intermediate III-2 2.3 g
Was added to 20 ml of acetonitrile at room temperature, and 2 g of triethylamine was added dropwise with stirring at room temperature. The reaction mixture once became a homogeneous solution 20 minutes after the start of dropping,
After 0 min, a yellow dye gradually precipitated. After reacting at room temperature for 1.5 hours, the precipitated dye was filtered and ethanol 50
Washed with ml. Purification by recrystallization from a mixed solvent of methanol and acetonitrile gave 1.2 g of the target compound. λmax 443 nm.

The compounds represented by formulas (I) and (II) of the present invention can be present in any layer in a silver halide photographic material. It is preferable that the compound be present in a state in which the photosensitive colloid layer is adsorbed on the photosensitive silver halide grains.

In order to incorporate the sensitizing dyes represented by formulas (I) and (II) in the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion.
Alternatively, water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1 -Butanol, 1-methoxy-2-propanol,
It may be dissolved in a solvent such as N, N-dimethylformamide alone or in a mixed solvent and added to the emulsion. Further, as described in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24,185, etc.
A method in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving, and this dispersion is added to an emulsion.
No. 23,389, JP-B-44-27,555, JP-B-57-22,091, etc., the dye is dissolved in an acid, and the solution is added to an emulsion. Or a method in which a base is coexisted to form an aqueous solution and added to the emulsion,
U.S. Pat. No. 3,822,135, U.S. Pat.
No. 026, JP-A-53-102733, and JP-A-58-105, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion. A method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, as described in JP-A-51-141, and a compound which causes red shift as described in JP-A-51-74,624. Dissolve the dye using
A method of adding the solution to the emulsion may be used.
Also, ultrasonic waves can be used for dissolution.

The sensitizing dye of the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful.
For example, US Pat. No. 2,735,766, US Pat.
No. 628,960; U.S. Pat. No. 4,183,756; U.S. Pat. No. 4,225,666;
No. 42, JP-A-60-196,749, etc., the stage before silver halide grain formation and / or desalination, during and / or after desalination. To the time before the start of chemical ripening, see JP-A-58-113,
As disclosed in the specification such as No. 920, etc., at any time before the emulsion is coated, just before chemical ripening or during the process, or before chemical ripening and before coating. good. No. 4,225,666.
As disclosed in the specification of Japanese Patent Application Laid-Open No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step and during the chemical ripening step. Separately after completion of chemical ripening, or before and after chemical ripening or during and after the process may be divided and added, and the type of compound and compound combination to be divided and added may also be changed. It may be added.

The amount of the compound represented by the general formulas (I) and (II) of the present invention varies depending on the shape and size of the silver halide grains.
The amount is 1 to 4 mmol, preferably 0.1 to 2.5 mmol, and may be used in combination with another sensitizing dye.

In the silver halide photographic light-sensitive material of the present invention, silver chlorobromide emulsion grains, silver chloride emulsion grains or silver chloroiodobromide having a silver chloride content of at least 95 mol% are contained in at least one of the silver halide emulsion layers. It preferably contains silver emulsion grains. Further, 95 mol% in the silver halide emulsion grains of not only this single layer but also all of the photosensitive silver halide emulsion layers.
It is preferable to use silver chloride or silver chlorobromide having the above-mentioned silver chloride. It is more preferable to use silver chloride or silver chlorobromide in which 98 mol% or more is silver chloride. In particular, in the present invention, silver bromochloride or silver chloride substantially free of silver iodide can be preferably used in order to speed up the development processing time. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or equal between the grains, but when an emulsion having the same halogen composition between the grains is used, it is easy to make the properties of each grain uniform. In the case where a high silver chloride emulsion is used in the present invention, a structure having a silver bromide localized phase in a layered or non-layered form inside and / or on the surface of silver halide grains is preferable. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%.
The silver bromide content of the silver bromide localized phase is determined by X-ray diffraction (for example,
"The Chemical Society of Japan, New Experimental Chemistry, 6, Structural Analysis" Maruzen,
It is described in. ) And the like. And these localized phases can be on the inside of the particle, on the edge, corner or plane of the particle surface,
As one preferable example, a material obtained by epitaxial growth at a corner portion of a particle can be cited.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also preferably used. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain and the number average is taken) is 0.1 to 2 μm. Is preferred. In addition, their particle size distribution is represented by a coefficient of variation (standard deviation of particle size distribution divided by average particle size) 2.
0% or less, preferably 15% or less, more preferably 1% or less.
What is called monodispersion of 0% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or irregular shapes such as spherical or tabular. Those having an irregular crystal form or those having a complex form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, 50% or more, preferably 7%, of the particles having the above-mentioned regular crystal form are contained.
The content is preferably 0% or more, more preferably 90% or more. In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

As the silver halide photographic light-sensitive material according to the present invention, other conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmissive support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening material, preferably, benzoxazole-based, coumarin-based,
A pyrazoline-based fluorescent whitening material is more preferable, and a benzoxazolylnaphthalene-based and benzooxazolylstilbene-based fluorescent whitening material is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio in the case of mixing with the water-resistant resin is preferably 0.0005 to 3% by weight with respect to the resin, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

The above-mentioned reflective support comprises a silver halide emulsion,
Silver halide emulsion storage stabilizer or antifoggant, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservation As for the improver (anti-stain agent and anti-fading agent), dye (colored layer), gelatin type, layer composition of photosensitive material and coating pH of photosensitive material, those described in the patents in Table 1 are preferably applied to the present invention. it can.

[0049]

[Table 1]

The cyan, magenta and yellow couplers which can be used in the present invention include those described in JP-A-62-21.
No. 5272, page 91, upper right column, line 4 to page 121, upper left column 6
Line, page 14 upper right column, line 14 to page 18 upper left column last line, page 30 upper right column, line 6 to page 35 lower right column, line 11 of JP-A-2-33144 and EP 0355,660A2. Page 4, lines 15 to 27, page 30, line 30 to end of page 28, 4
Page 5, lines 29 to 31, page 47, lines 23 to 63, page 50
The couplers described in the line are also useful. As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.

The photosensitive material according to the present invention is suitable for a scanning exposure method using a cathode ray (CRT), in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser.
Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is the above red,
The phosphor is not limited to green and blue, and a phosphor that emits light in a yellow, orange, violet, or infrared region may be used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used. If the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode ray tube also has a phosphor that emits light in a plurality of spectral regions, multiple colors are exposed at once,
That is, a plurality of color image signals may be input to the cathode ray tube to emit light from the tube surface. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for high image quality.

The photosensitive material according to the present invention is a gas laser.
ー, light emitting diode, semiconductor laser, semiconductor laser
Alternatively, a solid-state laser using a semiconductor laser as the excitation light source
-Second harmonic generation light source combining a laser and a nonlinear optical crystal
Digital scanning exposure using monochromatic high density light such as (SHG)
It is preferably used for the system. The system is compact,
Semiconductor lasers, semiconductor lasers to make them cheap
-Or a combination of solid-state laser and nonlinear optical crystal
It is preferable to use a second harmonic generation light source (SHG)
No. Especially compact, inexpensive, long life and stable
The use of semiconductor lasers is preferred for designing expensive equipment.
Preferably, at least one of the exposure light sources is a semiconductor laser.
It is preferred to use. Using such a scanning exposure light source
When used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention is used.
Arbitrarily set according to the wavelength of the scanning exposure light source used
Can be. Solid-state laser using semiconductor laser as excitation light source
Laser or semiconductor laser and nonlinear optical crystal
In the SHG light source obtained by
And blue light and green light can be obtained. Therefore,
The spectral sensitivity maximum of the light-sensitive material has three normal blue, green, and red waves.
It is possible to have it in a long area. Such scanning dew
The exposure time in the light was set to a pixel density of 400 dpi.
It is good to define the pixel size of the case as the exposure time.
A good exposure time is 10 ^-FourSeconds or less, more preferably
10^-6Seconds or less.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. For processing the photosensitive material according to the present invention,
JP-A-2-207250, page 26, lower right column, lines 1 to 3
Page 4, upper right column, ninth line, and JP-A-4-97355 No. 5
The processing materials and processing methods described in the upper left column of the page, line 17 to the lower right column of page 18, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

As the method of developing the photosensitive material used in the present invention after exposure, there are a conventional method of developing with a developing solution containing an alkali agent and a developing agent, and a developing method in which the developing agent is incorporated in the photosensitive material and the developing agent is not contained. In addition to a wet method such as a method of developing with an activator liquid such as a liquid, a thermal developing method using no processing liquid can be used. Wet development methods for photosensitive materials include the conventional method of developing with a developer containing an alkaline developing agent, and an activator that incorporates the developing agent into the photosensitive material and develops with an activator solution such as an alkaline solution that does not contain the developing agent. There are methods. In particular, since the activator method does not include a developing agent in the processing solution,
This is a preferable method from the viewpoint of easy management and handling of the treatment liquid, and low load on waste liquid treatment, and also from the viewpoint of environmental conservation. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, Japanese Patent Application Nos. 7-63572, 7-334190, and 7-3.
No. 34192, No. 7-334197, No. 7-3443
The hydrazine-type compound described in No. 96 is preferred.

Further, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Hei 7
Image forming methods using an activator solution containing hydrogen peroxide described in JP-A-63587 and JP-A-7-334202 are preferably used. In the activator method,
Desilvering is usually performed after processing with an activator solution.However, in an image amplification processing method using a low silver content photosensitive material, desilvering processing can be omitted and a simple method such as washing or stabilizing processing can be performed. it can. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used. Activator solution, desilvering solution (bleaching / fixing solution) used in the present invention,
Known materials and processing methods for the washing and stabilizing solution can be used. Preferably, Research Disclosure Item 36544 (September 1994) No. 536
Pages 541 to 541 and Japanese Patent Application No. 7-63572 can be used.

Further, in the image forming method of the present invention, as an apparatus for performing exposure and processing from reading of image information, Japanese Patent Application Laid-Open No. Hei.
The digital photographic printer described in No. 2 is preferably used. In particular, in the image recording section, in order to make the pitch of the scanning exposure constant, it is necessary to start the transport of the photosensitive material before the start of the scanning exposure and to make the photosensitive material transport speed constant in advance. The distance conveyed before the start of the scanning exposure varies depending on the performance of the motor for driving the roller, but is preferably 10 mm to 100 mm in the present invention. In this case, every time the scanning exposure is interrupted, a feeding portion of the photosensitive material is generated, causing a loss of the photosensitive material. In order to prevent this loss, it is preferable to provide a step of transporting the photosensitive material by a certain length in the reverse direction when the scanning exposure is stopped. The distance conveyed in the reverse direction is preferably 10 mm to 10 mm in the present invention.
0 mm.

[0057]

【Example】

Example 1 Preparation of emulsion Sodium chloride 6.0 in 3% aqueous solution of lime-processed gelatin
g, and 2.9 ml of N, N-dimethylimidazolidin-2-thione (1% aqueous solution) was added to prepare solution I.
An aqueous solution containing 0.2 mol of silver nitrate (solution I)
I) and an aqueous solution containing 0.01 mol of potassium bromide and 0.19 mol of sodium chloride (solution III) were added and mixed at 50 ° C. with vigorous stirring. Subsequently, silver nitrate was added to 0.
An aqueous solution containing 8 mol (solution IV) and an aqueous solution containing 0.04 mol of potassium bromide and 0.76 mol of sodium chloride (solution V) were added and mixed at 50 ° C. with vigorous stirring. Further, potassium ferrocyanide and potassium hexachloroiridate (IV) were allowed to coexist in the solution III and the solution V, each of which was 6.0 per mol of silver halide.
× 10 ⁻⁵ mol and 5.0 × 10 ⁻⁸ mol were uniformly contained in the emulsion grains. After keeping at 50 ° C for 20 minutes, cool down,
Desalting and washing were performed. Furthermore, lime-processed gelatin 16
After adding 0 g, adjusting the pH and pAg, triethylthiourea was added for optimal sulfur sensitization, and further optimally gold sensitized with potassium hexachloroaurate. Exemplary compound I-1 of the present invention as a photosensitive sensitizing dye
-6 and Comparative Dyes a-1 and a-2 were added in an amount of 3.5 × 10 ^-4 mol per mol of silver halide, and spectral sensitization was performed. The resulting blue-sensitive silver chlorobromide emulsions were designated as Y-1 to Y-8.

Green light-sensitive sensitizing dyes A, B and C were used instead of blue light-sensitive sensitizing dyes for blue light-sensitive emulsions Y-1 to Y-8, respectively, at 2.4 × 10 ^-4 per mol of silver halide. Mole,
By adding 1.2 × 10 ^-4 mol and 1.8 × 10 ^-4 mol, the resulting mixture was spectrally sensitized to give a green light-sensitive emulsion M-1 and a red light-sensitive sensitizing dye D instead of the blue light-sensitive sensitizing dye. ^Was added to 5.0 × 10 ⁻⁵ mol per mol of silver halide to spectrally sensitize to prepare a red-sensitive emulsion C-1.

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Preparation of Samples 101-108 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. . The polyethylene laminated layer on the side of Coating photographic constituent layers was contained K-1 and K-2 one by each ^{3mg / m 2, 12mg / m} 2.

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The following photographic constituent layers were coated to prepare a multilayer silver halide color light-sensitive material (101). Preparation of third layer coating solution 100.0 g of magenta coupler (ExM), 18.8 g of color image stabilizer (Cpd-2), color image stabilizer (Cpd-5)
62.5 g, 6.3 g of color image stabilizer (Cpd-6), 50.0 g of color image stabilizer (Cpd-7), color image stabilizer (Cpd-6)
-8) 6.3 g, ultraviolet absorber (UV-2) 100.0
g of a solvent (Solv-3) and 75.0 g of a solvent (Solv-3).
-4) 243.8 g, solvent (Solv-6) 162.5
g of ethyl acetate and 50 g of ethyl acetate, and this solution is mixed with 20% of sodium dodecylbenzenesulfonate containing 7.0 g.
Emulsified and dispersed in 600 ml of aqueous gelatin solution
Was prepared. The above emulsified dispersion M and silver chlorobromide emulsion M-1
Were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition shown below.

The coating solutions for the first layer, the second layer, and the fourth to seventh layers were prepared in the same manner as the coating solution for the third layer. 1-oxy-3,5-dichloro-s is used as a gelatin hardener in each layer.
-Triazine sodium salt was used. In addition, Cp is added to each layer.
d-12 and Cpd-13 each having a total amount of 25.0 mg /
m ² and 50.0 mg / m ² . The following compound was added to the fifth layer at 3.5 mg / m ² .

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Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × 10 ^-4 mol, 3 mol / mol and 1 mol of silver halide, respectively. 0.0 × 10 ^-3 mol, 2.5 × 1
^0-4 moles were added. Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1 × 10 ^-4 mol and 2 × 10 ^-4 mol of tetrazaindene were added per 1 mol of silver halide. The dye shown below was added to the sixth layer as a water-soluble dye for preventing irradiation.

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion shows a coating amount in terms of silver. Support Titanium oxide (18 wt.) In the polyethylene resin layer on the first layer side
%) And blue dye (ultramarine), K-1 (3 mg / m ² ) and K
-2 (12 mg / m ² ). First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion Y-1 0.27 Gelatin 1.22 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd) -2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.01 Solvent (Solv-1) 0.13 Solvent (Solv-5) 0.13

Second layer (color mixture prevention layer) Gelatin 0.90 Color mixture prevention agent (Cpd-4) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 Solvent (Solv-8) 0.03 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion M-1 0.14 Gelatin 1.45 Magenta coupler (ExM) 0.16 Ultraviolet absorber (UV- 2) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.08 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-3) 0.13 Solvent (Solv-4) 0.39 Solvent (Solv-6) 0.26

Fourth layer (color mixture preventing layer) Gelatin 0.68 Color mixture inhibitor (Cpd-4) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-8) 0.02 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C-1 0.18 Gelatin 0.80 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV- 2) 0.05 color image stabilizer (Cpd-1) 0.05 color image stabilizer (Cpd-2) 0.02 color image stabilizer (Cpd-5) 0.06 color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-14) 0.10 Color image stabilizer (Cpd-15) 0.06 Solvent (Solv-1) 0.15 Solvent ( Solv-10) 0.15

Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.38 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.05 Seventh layer (protective layer) Gelatin 0.90 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-11) ) 0.01

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Sample 101 was mixed with blue-sensitive emulsion Y-1.
Was changed to Y-2 to 8 in the same manner as in Sample 102.
~ 108 were created. Table 2 shows the types of emulsions used for Samples 101 to 108.

[0081]

[Table 2]

The samples 101 to 108 were subjected to the following exposure and treatment after storage for one week at room temperature and normal humidity after coating.
Each sample was passed through a blue filter, a green filter, or a red filter, and a sensitometer (FWH type, manufactured by FUJIFILM Corporation, color temperature of light source: 3200K).
After giving a gradation exposure for sensitometry at an exposure amount of 250 CMS and an exposure time of 1 second, the following processing is carried out, and the color density of the processed sample is measured to obtain a blue, green and red photosensitive emulsion layer. The corresponding sensitometry was obtained. For the high illuminance short-time exposure, the scanning exposure apparatus shown in FIG. 1 of JP-A-8-16238 was used. The exposure part of the scanning exposure apparatus will be described in detail below. Using semiconductor laser as light source 6
A light source (R light) of 88 nm was obtained. SHG for semiconductor laser
532 nm (G light) and 473 nm (B
Light). Laser light of each wavelength was modulated using an external modulator to modulate the amount of light, and reflected by a rotating polyhedron, thereby sequentially scanning and exposing the coated sample moving perpendicularly to the scanning direction. The scanning exposure was performed at 400 dpi, and the average exposure time per pixel was 8 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress a change in light quantity due to temperature. B,
Scanning exposure is performed by modulating the amount of G or R light, the following processing is performed, and the color density of the processed sample is measured to respond to high illuminance short time exposure of the blue, green and red photosensitive emulsion layers. Sensitometry was obtained. Further, using a surface exposure printer (Fuji Film Co., Ltd., Fuji Color Roll Printer 8C6910) and the scanning exposure apparatus, the color density of B, G, and R of each sample was adjusted to be 0.5, Gray exposure was uniform. Gray exposure was performed at the cabinet size, and exposure to the cabinet size was performed continuously. The transport speed of the sample during the scanning exposure was 80 mm / sec. After the exposure, the following treatment was performed to obtain a sample for visual evaluation of pressure property.

Processing Step Temperature Time Replenisher * Tank capacity Color development 38.5 ° C 45 seconds 120ml 500ml Bleaching and fixing 30-35 ° C 45 seconds Rinse (1) 30-35 ° C 20 seconds Rinse (2) 30-35 ° C 20 seconds rinse (3) 30 to 35 ° C. 20 seconds drying 70 to 80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ² (rinse was 3 tank countercurrent system to (3) → (1))

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 2.5g 3.0g 1,2-Dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5g 0.5g Triethanolamine 9.0 g 12.0 g Potassium chloride 5.0 g-Potassium bromide 0.02 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N , N-bis (sulfonatoethyl) hydroxylamine 8.5g 11.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g 9.5g Water is added to 1000ml 1000ml pH (25 ° C) 10.0 11.0

Bleach-fix solution (same as tank solution and replenisher) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 30 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Nitric acid (67 30g Add water to 100ml pH (25 ° C) (with acetic acid and ammonium water) 5.8 Rinse solution (same as tank solution and replenisher) Deionized water (calcium and magnesium are each 3ppm or less)

From the sensitometric curves corresponding to the blue, green and red light-sensitive emulsion layers, the exposure amount giving a density higher than the fog density by 0.5 was read, and the reciprocal of this exposure amount was calculated. The value obtained for sample 107 is 100
In this case, the relative values were defined as sensitivity S (normal surface exposure) and sensitivity S '(high illuminance scanning exposure). Further, an exposure amount giving a density 0.5 higher than the fog density was read by a sensitometry curve, and a color density at an exposure amount 10 times the exposure amount was obtained. The color density (D) in normal surface exposure and the color density (D ') in high-illuminance scanning exposure are obtained,
This ratio (D '/ D) was used as one of the indexes for suitability for high illuminance.
That is, if this value is 1, it indicates that the contrast is high in high-illumination exposure as in normal exposure, and as this value approaches 1 to 0, the tone becomes softer in high-illumination exposure than in normal exposure. . After gray exposure, each processed sample 1
Every 0 sheets (cabinet size) were visually observed, and the pressure-sensitized streaks caused by the photosensitive material transporting roller were evaluated as follows. A: No pressure-sensitized streaks were observed. B: Slight pressure-sensitized streaks were observed in 1 out of 10 sheets
Or two. C: 3 out of 10 stripes with slight pressure-sensitized streaks
10 to 10. D: 1 or 2 out of 10 sheets with clearly visible pressure sensitization streaks. E: 3 to 5 out of 10 sheets with clearly visible pressure sensitizing streaks. F: 6 to 10 out of 10 sheets in which pressure-sensitized streaks are clearly observed.

Evaluation of Residual Color For each of Samples 101 to 108, unexposed samples were treated with different color developers, and the absorption density at 480 nm was measured.

Further, in order to examine the photographic properties after long-term storage, the unexposed sample was aged for one month under conditions of 35 ° C. and 40% RH (corresponding to a forced deterioration test), and evaluated in the same manner as described above. did. To evaluate the change in sensitivity after long-term storage,
The sensitivity difference ΔS (normal surface exposure) and ΔS ′ (high illuminance scanning exposure) after long-term storage with respect to the sensitivity before long-term storage were used. When this value is 0, it indicates that there is no change in sensitivity before and after long-term storage, and when it is greater than 0, it indicates that the increase in sensitivity after long-term storage is large. Table 3 summarizes the evaluation results of the photographic characteristics of each sample.

[0089]

[Table 3]

Table 3 shows the following. Comparative Example 1
In 07, the residual color is large, and the change in sensitivity and pressure is increased by long-term storage. In Comparative Example 108, the residual color was good, but the sensitivity was low. On the other hand, although the samples 101 to 106 of the present invention have high sensitivity, there are few residual colors, and the characteristics that the sensitivity and the pressure property due to long-term storage are small are observed.

Example 2 Exemplified compounds I-1, II-1, and II-2 as blue-sensitive dyes were each added to the blue-sensitive emulsion Y-1 of Example 1 at a ratio of 1.4 per mole of silver halide. A blue-sensitive emulsion Y-11 was prepared by adding × 10 ^-4 mol, and Exemplified Compounds I-3, II-1 and II-2 were each similarly added in an amount of 1.4 × 10 ^-4 per mol of silver halide. The blue-sensitive emulsion Y-12 can be added to the exemplified compounds I-4, II-1, and II-
2 in an amount of 1.4 × 10 ^-4 per mol of silver halide
A blue-sensitive emulsion Y-13 was prepared by adding a mole. In addition, a-1, II-1, and II-2 were used as comparative emulsions.
^Was added in an amount of 1.4 × 10 ^-4 mol per mol of silver halide to prepare a blue-sensitive emulsion Y-14.
The obtained blue-sensitive emulsion Y-11-14 was used in Example 1 together with the green-sensitive emulsion M-1 and the red-sensitive emulsion C-1 of Example 1.
Of the sample 201-
The sample 204 was prepared and processed in the same manner as in Example 1, and the sensitivity of each layer of the sample 204 was evaluated as 100, and evaluated in the same manner as in Example 1.

[0092]

[Table 4]

From Table 4, it can be seen that the silver halide photographic material using the dye of the present invention achieves both high sensitivity and low residual color even in a sample added to an emulsion in combination with another dye. .

[0094]

The silver halide photographic light-sensitive material of the present invention achieves both high sensitivity and low residual color, and has little change in sensitivity and pressure sensitivity when the light-sensitive material is stored unexposed.

Claims (4)

[Claims] 1. A silver halide photographic material comprising at least one compound represented by formula (I). General formula (I) In the formula, Z ¹ represents an atomic group necessary for completing a naphthothiazole ring. Z ² represents an atom group necessary for completing a nitrogen-containing 5-membered heterocyclic ring. V ¹ was a cyano group, R ¹
And R ² represent an alkyl group. L ¹ represents a methine group, X ¹ represents a counter ion necessary for neutralizing the charge,
n ¹ represents a number of 0 or more necessary to neutralize the charge in the molecule. 2. The compound represented by the general formula (I) according to claim 1, wherein the nitrogen-containing 5-membered heterocycle completed with Z ² is a benzothiazole ring or a naphthothiazole ring. 3. The silver halide photographic light-sensitive material described in 1. above. 3. A silver halide photographic material having at least one silver halide photographic emulsion layer on a support, wherein silver halide grains of at least one emulsion layer of the silver halide photographic emulsion layer contain silver chloride. A silver halide photographic light-sensitive material characterized in that the emulsion layer contains at least one compound represented by formula (I) in the emulsion layer. 4. A silver halide photographic material having at least one silver halide photographic emulsion layer on a support, wherein at least one of said emulsion layers contains at least one compound represented by formula (I). A silver halide photographic material comprising at least one compound represented by the formula (II). General formula (II) In the formula, Z ¹¹ and Z ¹² represent an atom group necessary for completing a nitrogen-containing 5-membered heterocyclic ring. R ¹¹ and R ¹² have the same meanings as R ¹ and R ² , L ¹¹ has the same meaning as L ¹ , X ¹¹ has the same meaning as X ¹ , n
¹¹ has the same meaning as n ^1.