JPH09101588A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material high in spectral sensitivity in a red wavelength region and small in residual dye by incorporating a specified spectral sensitizing dye in a silver halide emulsion layer. SOLUTION: One of the silver halide emulsion layers contains the spectral sensitizing dye represented by the formula in which each of Z<1> and Z<2> is, independently, a 5- or 6-membered N-containing heterocyclic group; Z<3> is an a -N(R)- group or an H, O, S, or Te atom; each of R<1> and R<3> is a <=10C aliphatic group; each of R and R<2> is an aliphatic or aryl or heterocyclic group; but at least one of R and R<1> -R<3> is a water-solubilizing group; L<1> is a halogenated methine group; each of L<2> and L<3> is an optionally substituted methine carbon; each of l<1> and l<2> and m<1> is 0 or 1; M<1> is an ion necessary for cancelling the total charge of the molecule; and n<1> is a number necessary for neutralizing it.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high spectral sensitivity in the red light region and less residual color contamination.

[0002]

2. Description of the Related Art A means for expanding the light-sensitive wavelength range of a silver halide emulsion and increasing its sensitivity is well known as a spectral sensitizing technique, and many spectral sensitizing dyes used for this purpose include cyanine dyes and merocyanine dyes. The compound of is known.

These spectral sensitizing dyes must not only expand the photosensitive wavelength range of the silver halide emulsion, but must also satisfy the following conditions.

(1) Appropriate spectral sensitization region and excellent spectral sensitization efficiency (2) No adverse effect of other additives (3) No fog or gamma deterioration during aging of the photosensitive material Stable (4) Not diffusible to other layers (5) Processed photosensitive material is required to have no residual color contamination. However, few satisfy all of these conditions, and particularly in recent years, the processing time has been shortened, and the processing liquid has been recycled by anhydrous washing, and the dye tends to remain. For this reason, dye contamination is likely to remain on the processed light-sensitive material, resulting in a problem that the commercial value is remarkably reduced. Therefore, in the present situation, in the spectral sensitizing dye, improvement of residual color has become an important technical subject.

Conventionally, as a spectral sensitizing dye for sensitizing a red light region, for example, Belgian Patent No. 541,245, US Patent Nos. 2,475,163, 2,493,747, and 2,493,748. No. 2,743,272, No. 3,335,010, No. 3,672,905, No. 3,674,499, French Patent No. 2,113,248.
, German Patents 1,024,800 and 2,153,5
70, 2,300,321, JP-A-54-187.
26, 61-11736, and JP-A-5-13434.
No. 6, No. 5-289222, No. 3-171135 and the like disclose that the complex cyanine and the complex merocyanine are effective. Further, JP-A-49-11121 and 51-33622.
No. 51-115821, No. 51-115822
No. 58-72937, No. 61-203446,
Cyanine described in JP-A-2-256045 and JP-A-3-15042, U.S. Pat. Nos. 2,493,747, 2,493,748, 2,519,001, and JP-A-51-106422. It is known that the merocyanine dyes described in JP-A-59-214030 are effective.

Some of these dyes have been attempted to reduce the residual color contamination by introducing a water-soluble group into the molecule, but they are not sufficient, or the spectral sensitivity decreases and the emulsion coating solution ages. There was a problem that sensitivity fluctuations tended to occur, and it was not satisfactory.

More recently, European Patent 363, disclosed
The dyes described in Nos. 104 and 363,107 show remarkable effects of improving the residual color stain, but the photographic materials containing these dyes have a drawback that the photographic performance varies when stored over time. . Also, JP-A-62-227142
JP-A-4-328542 and JP-A-5-224337 disclose a technique for improving spectral sensitivity and improving the load of residual color contamination by using a dye together with a supersensitizer.

However, these conventional techniques are still at an insufficient level, and further improvement has been required. In addition,
It is well known to use Group VIII complex salts such as iridium and rhodium for the purpose of sensitizing, stabilizing or suppressing irregularities in high illuminance during the physical or chemical ripening process of silver halide emulsions. Particularly, the iridium complex salt is an essential additive for emulsions having a high silver chloride content. However, depending on the type of spectral sensitizing dye used in the emulsion, the combined use of an iridium complex salt has a problem that the emulsion sensitivity is suppressed more than necessary. It has been desired to develop a dye that enhances the spectral sensitivity, has no residual color contamination, and does not deteriorate the photographic performance even when used in combination with an iridium complex salt.

[0009]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a silver halide photographic light-sensitive material having high spectral sensitivity in the red light region and less residual color contamination.
A second object of the present invention is to provide a silver halide photographic light-sensitive material which has high spectral sensitivity in the red light region and which does not deteriorate due to fluctuations in photographic performance during storage over time. A third object of the present invention is to provide a silver halide photographic light-sensitive material having high spectral sensitivity in the red light range and less residual color contamination even when an iridium compound is used.

[0010]

The object of the present invention has been attained by the following.

(1) In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, at least one layer of the silver halide emulsion layer has a spectrum represented by the following general formula [SI]. A silver halide photographic light-sensitive material comprising a sensitizing dye.

[0012]

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In the formula, Z ¹ and Z ² each independently represent a 5- or 6-membered nitrogen-containing heterocyclic group, and Z ³ is --N (R)-.
Represents a group, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom.

R ¹ and R ³ each represent an aliphatic group having 10 or less carbon atoms, and R and R ² each represent an aliphatic group, an aryl group or a heterocyclic group. However, at least one of R, R ¹ , R ² and R ³ represents a group substituting the water-solubilizing group. L ¹
Represents a methine carbon substituted with halogen, L ² and L ³
Each represents an optionally substituted methine carbon.
l ¹ , l ² and m ¹ are integers of 0 or 1. M ¹ represents an ion necessary for canceling the total charge of the molecule, and n ¹ represents the number necessary for neutralizing the total charge of the molecule.

(2) In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a spectrum represented by the following general formula [S-II]. A silver halide photographic light-sensitive material comprising a sensitizing dye.

[0016]

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In the formula, Y ¹¹ , Y ¹² and Y ¹³ each independently represent a —N (R ¹⁰ ) — group, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom.

R ¹¹ and R ¹³ each represent an aliphatic group having 10 or less carbon atoms, and R ¹⁰ and R ¹² each represent an aliphatic group, an aryl group or a heterocyclic group. However, at least one of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represents a group substituting the water-solubilizing group. V
¹ , V ² , V ³ and V ⁴ each represent a hydrogen atom, an alkyl group, an alkoxy group or an aryl group, and V ¹ and V ² or V ³ and V ⁴ are bonded to each other to form a condensed ring together with an azole ring. You may form. L ¹¹ represents a methine carbon substituted with a halogen atom. L ¹² and L ¹³ each represent an optionally substituted methine carbon. m ² represents an integer of 0 or 1, M ¹¹ represents an ion necessary to cancel the total charge of the molecule, and n ² represents a number necessary to neutralize the total charge of the molecule.

(3) The silver halide grains in the silver halide emulsion layer contain at least one iridium compound in an amount of 10 ^-8 mol to 10 ^-4 mol per mol of silver (1) The silver halide photographic light-sensitive material according to the item (2).

The present invention will be described in detail below.

The above general formulas [SI] and [S] according to the present invention are
-II] in the compound represented by R, R ¹ , R ² , R ³ ,
Examples of the water-solubilizing group substituting for R ¹⁰ , R ¹¹ , R ¹² and R ¹³ include acid groups such as sulfo group, carboxy group, phosphono group, sulfate group and sulfino group, and [alkyl group-
CO-NHSO ₂ -] group, [an alkyl group -CO-NHC
O-] group, [an alkyl group -SO ₂ -NHCO-] group,
Examples thereof include an [alkyl group —SO ₂ —NHSO ₂ —] group and a sulfamoyl group that undergo ion dissociation in an alkaline aqueous solution.

The aliphatic group represented by R, R ¹ , R ² , R ³ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is, for example, a branched or straight chain alkyl group having 1 to 10 carbon atoms. (For example, each group of methyl, ethyl, n-propyl, n-pentyl, isobutyl, etc.), an alkenyl group having 3 to 10 atoms (for example,
3-butenyl, 2-propenyl, etc.) or an aralkyl group having 3 to 10 carbon atoms (eg, benzyl, phenethyl, etc.).

Examples of the aryl group represented by R, R ² , R ¹⁰ and R ¹² include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2-, 4-) and a furyl group (2-. ), A thienyl group (2-), a sulforanyl group, a tetrahydrofuryl group, a piperidinyl group and the like.
Each group of R, R ¹ , R ² , R ³ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (eg, methoxy group). , Ethoxy group), aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (eg, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), Sulfamoyl group (eg, sulfamoyl group, N, N-3
-Oxapentamethyleneaminosulfonyl group etc.), methanesulfonyl group, alkoxycarbonyl group (eg ethoxycarbonyl group, butoxycarbonyl group etc.), aryl group (eg phenyl group, carboxyphenyl group etc.), acyl group (eg acetyl) Group, benzoyl group and the like).

Specific examples of the aliphatic group substituted with the water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl, P -Specific examples of aryl groups in which there are groups such as carboxybenzyl, acetylaminosulfonylmethyl, acetylaminocarbonylmethyl, methanesulfonylaminocarbonylmethyl, methanesulfonylaminosulfonylmethyl, and sulfamoylethyl, and the water-solubilizing group is substituted As p There are various groups such as -sulfophenyl group and p-carboxyphenyl group, and specific examples of the heterocyclic group substituted with the water-solubilizing group include 4-sulfothienyl group and 5
There are groups such as a carboxypyridyl group.

In these, R ¹ and R ¹¹ are alkyl groups substituted with a sulfo group, and R, R ² , R ³ , R ¹⁰ ,
It is preferred that at least two of R ¹² and R ¹³ are each a carboxymethyl group.

The 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ¹ and Z ² includes a condensed ring, for example, an oxazole ring (oxazolidine, oxazoline, oxazole, benzoxazole, naphthoxazole, etc.), thiazole ring ( Thiazolidine, thiazoline, thiazole, benzothiazole, naphthothiazole, etc.), imidazole ring (imidazoline, imidazole, benzimidazole, naphthimidazole, etc.), selenazole ring (selenazoline, selenazole benzoselenazole, naphthoselenazole, etc.), tellrazole ring (terrazoline) , Tellurazole, benzotelrazole, naphthoterrazole, etc.), thiadiazole ring, thienothiazole ring, pyridine ring (2-pyridine, 4-pyridine, 2-quinoline, 4
-Quinoline) and the like.

The alkyl group represented by V ¹ , V ² , V ³ and V ⁴ is a linear or branched group (for example, methyl, ethyl, iso-propyl, t-butyl, iso-butyl,
Each group such as t-pentyl and hexyl).
Examples of the alkoxy group represented by V ¹ , V ² , V ³ and V ⁴ include groups such as methoxy, ethoxy and propoxy.

The aryl group represented by V ¹ , V ² , V ³ and V ⁴ may have a substituent at any position, for example, phenyl, p-tolyl, p-hydroxyphenyl, p-. Each group such as methoxyphenyl may be mentioned. V
Examples of the condensed ring in which ¹ and V ² and V ³ and V ⁴ are bonded to each other to form an azole ring include, for example, Cheno [2, 1
-D] oxazole, 4,5,6,7-tetrahydrobenzoxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, naphtho [2.
1-d] imidazole, cheno [1,2-d] thiazole, cheno [2,1-d] 4,5,6,7-tetrahydrobenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,2]. 3-d] thiazole, 4,5,6,7
-Tetrahydrobenzoselenazole, naphtho [1,2-
d] condensed rings such as selenazole and a 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ¹ and Z ² . V ¹ , V ² ,
The above-mentioned substituents represented by V ³ and V ⁴ , and the condensed ring formed may have a substituent at any position,
For example, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), trifluoromethyl group, alkoxy group (for example, each unsubstituted alkyl group such as methoxy, ethoxy, butoxy, 2-methoxyethoxy, benzyloxy and the like). Substituted alkoxy groups), hydroxy group, cyano group, aryloxy group (eg, substituted or unsubstituted groups such as phenoxy, tolyloxy, etc.), or aryl group (eg,
Substituted or unsubstituted groups such as phenyl and p-chlorophenyl), styryl groups, heterocyclic groups (such as furyl and thienyl groups), carbamoyl groups (such as carbamoyl and N-ethylcarbamoyl groups) A sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, etc.), an acylamino group (eg, acetylamino, propionylamino, benzoylamino, etc.), an acyl group (eg, acetyl, benzoyl, etc.) Each group), an alkoxycarbonyl group (for example, a group such as ethoxycarbonyl), a sulfonamide group (for example, a group such as methanesulfonylamide, benzenesulfonamide), a sulfonyl group (for example, methanesulfonyl, p-).
Each group such as toluenesulfonyl) and any group such as carboxy group.

Examples of the halogen atom substituted for L ¹ and L ¹¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. Examples of the group substituted on the methine carbon represented by L ² , L ³ and L ¹² , L ¹³ include a lower alkyl group (for example, each group such as methyl and ethyl), a phenyl group (for example, phenyl, carboxyphenyl). Etc.), alkoxy groups (eg, groups such as methoxy, ethoxy, etc.) and aralkyl (eg, groups such as benzyl).

The dye of the present invention is characterized in that the methine carbons represented by L ¹ and L ¹¹ are substituted with a halogen atom, and compared with the conventionally known dyes in which L ¹ and L ¹¹ are CH groups. High spectral sensitivity can be obtained, and the dye can be easily drifted in the processing bath, which has a preferable effect of significantly reducing the residual color stain.

M ¹ and M ¹¹ each represent a cation or an acid anion, and a specific example of the cation is a proton,
Examples thereof include organic ammonium ions (eg, respective ions of triethylammonium, triethanolammonium, etc.) and inorganic cations (eg, respective cations of lithium, sodium, potassium, calcium, etc.), and specific examples of the acid anion include halogen ions (eg, chlorine ion). Ion, bromine ion, iodine ion, etc.), p-toluenesulfonate ion, perchlorate ion, 4-boron fluoride ion and the like. n ¹ and n ² are 0 when the charge is neutralized by forming an intramolecular salt.

General formulas [SI] and [S-II] of the present invention
Specific examples of the photosensitive dye represented by are shown below, but are not limited to these compounds.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The above-mentioned compounds are, for example, "Cyanine Soybean and Relayed Compounds" (1964, published by Inter Science Publishers) by FM Hama, US Pat. No. 2,475,163, and the same. It can be easily synthesized by referring to a conventionally known method described in 3,672,405.

Specific synthetic examples are given below, but other exemplified compounds can also be synthesized by the same method.

Synthesis Example 1 (Exemplified Compound S-3) 4-oxo-5- {2-fluoro-2- [7- (3-sulfopropyl) -6 (7H) -dioxolo [4,5-
f] Benzoxazolilidene] ethylidene} -2-thioxothiazolidin-3-ylacetic acid (2.5 g) was mixed with p-toluenesulfonic acid methyl ester (4 g) and the mixture was heated with stirring at 130 ° C for 120 minutes.

After returning to room temperature, isopropyl ether was added to the viscous reaction product and the mixture was left to stir with stirring, and then the supernatant liquid was removed by tilting. 2-methylthio-3-thieno [2,3
-D] thiazolioacetic acid p-toluenesulfonate 1.5
g and then 10 ml of pyridine were added and the mixture was gently heated to reflux for 20 minutes, then cooled and crystallized. The precipitate was collected by filtration and washed with an ethanol solvent. The obtained crude crystals were recrystallized from a methanol solvent to obtain 1.1 g of a dye.

Synthesis Example 2 (Exemplified Compound S-29) 4-oxo-5- {2-fluoro-2- [7- (3-sulfopropyl) -6 (7H) -dioxolo [4,5-
f] Benzothiazolilidene] ethylidene} -2-thioxothiazolidin-3-ylacetic acid (2.6 g) was mixed with dimethyl sulfate (2.5 g) and the mixture was heated with stirring at 130 ° C. for 60 minutes.
The mixture was returned to room temperature, isopropyl ether was added to the viscous reaction product, and the mixture was allowed to stand with stirring, and then the supernatant liquid was decanted and removed. To this was added 1.5 g of 2-methylthio-3-thieno [2,3-d] thiazolioacetic acid p-toluenesulfonate, followed by addition of 10 ml of pyridine and 1 ml of triethylamine.
The mixture was gently heated to reflux for 0 minutes, then cooled and crystallized. The precipitate was collected by filtration and washed with an ethanol solvent. The crude crystals obtained were recrystallized from a methanol solvent to obtain 1.3 g of a dye.

The addition amount of the dye according to the present invention varies greatly depending on the conditions used and the type of emulsion, but is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ mol per mol of silver halide, More preferably, it is in the range of 2 × 10 ⁻⁶ to 2 × 10 ⁻³ mol.

The above general formula [S] used in the present invention
The compounds represented by -I] and [S-II] can be added to a silver halide emulsion by a conventionally known method. For example, the protonated dissolution addition method described in JP-A Nos. 50-80826 and 50-80827, U.S. Pat.
No. 2,135, JP-A-50-11419, a method of dispersing and adding together with a surfactant, U.S. Pat.
No. 47, 3,469,987, 4,247,62
7, JP-A-51-59942, and JP-A-53-16624.
No. 53-102732, No. 53-102733
No. 53-137131, a method of dispersing in a hydrophilic substrate, a method of adding as a solid solution described in East German Patent 143,324, or Research Disclosure No. 21,802, Japanese Patent Publication No. 50-40659. And a water-soluble solvent for dissolving a dye represented by JP-A-59-148053 (for example, low-boiling solvents such as water, methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohol; dimethylformamide, methyl cellosolve; A high boiling point solvent such as phenyl cellosolve) alone or in a mixed solvent thereof may be added to the emulsion by using any method.

The photosensitive dyes represented by the general formulas [SI] and [S-II] may be added at any stage in the emulsion production process from physical ripening to completion of chemical ripening. It is preferably added during the period from physical ripening to completion of chemical ripening. Addition of the compound according to the present invention during physical ripening, prior to the addition of the chemical sensitizer in the chemical ripening step, or immediately after the addition of the chemical sensitizer, has the effect of obtaining higher spectral sensitivity. Are preferably used.

The photosensitive dyes represented by the general formulas [SI] and [S-II] can be used in combination with other photosensitive dyes. In this case, each of the light-sensitive dyes may be added to the emulsion at the same time or separately at different times, and the order and time interval at that time may be arbitrarily determined depending on the purpose.

The spectral sensitivity of the photosensitive dye used in the present invention can be further improved by using a compound having a supersensitizing effect. Compounds having such a supersensitizing effect include, for example, U.S. Pat. Nos. 2,933,390, 3,416,927, 3,511,664, 3,615,613 and 3,615. 615,632, 3,635,721, JP-A-3-15042, 3
Compounds having a pyrimidinylamino group or a triazinylamino group described in, for example, JP-A-110545 and JP-A-4-2555841; British Patent No. 1,137,580;
Aromatic formaldehyde condensates described in JP-A-169833, calixarene derivatives described in JP-A-4-184332, halogenated benzotriazole derivatives described in U.S. Pat. No. 4,030,927, JP-A-59-1
Nos. 42541 and 59-188641, bispyridinium compounds described in JP-A-59-190332, quaternary salts of aromatic heterocycles described in JP-A-59-190332, electron-donating compounds described in JP-A-60-79348, U.S. Pat. No. 307,183, polymers containing aminoallylidenemalononitrile units, hydroxytetrazaindene derivatives described in JP-A-4-149937, 1,3-oxadiazole derivatives described in U.S. Pat. No. 3,615,633. U.S. Pat.
And amino-1,2,3,4-thiatriazole derivatives described in No. 0,404. The timing of adding these supersensitizers is not particularly limited, and they can be arbitrarily added according to the timing of adding the photosensitive dye according to the present invention. Silver halide 1
The amount is selected from the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol, and the photosensitive dye is used in an addition molar ratio of 1/10 to 10/1.

The silver halide emulsion according to the present invention is preferably an emulsion having a halogen composition wherein silver chloride containing 10 ^-8 to 10 ^-4 mol of iridium compound per mol of silver is at least 50 mol%, more preferably, Iridium compound is silver 1
It is contained in an amount of 10 ^-7 to 10 ^-5 mol per mol.

Any silver halide grains such as cubic crystals, octahedral crystals, and tabular crystals having an aspect ratio of 5 or more can be used, and (standard deviation of grain size) / (average of grain size) × 100.
Monodisperse particles having a coefficient of variation of 15% or less are preferred.

The average grain size of the silver halide grains is not particularly limited, but is 0.05 to 2.0 μm, preferably 0.1 to 2.0 μm.
1.0 μm.

The iridium compound according to the present invention is, for example,
Conventionally known compounds described in JP-B-43-4935 and JP-B-45-32738 can be used,
Specifically, iridium trichloride, iridium tribromide, iridium tetrachloride, iridium tetrabromide, potassium hexachloroiridate (III), hexabromoiridium (II
I) Potassium acid, sodium hexachloroiridate (IV), potassium hexabromoiridium (IV), and the like may be used, and these may be used alone or in combination of two or more.

The hydrophilic protective colloid used for preparing the silver halide photographic light-sensitive material of the present invention includes gelatin used in usual silver halide emulsions and gelatin derivatives such as acetylated gelatin and phthalated gelatin. , Water-soluble cellulose derivatives and other synthetic or natural hydrophilic polymers.

In the silver halide photographic light-sensitive material of the present invention, various techniques and additives known in the art can be used as needed. For example, in addition to the photosensitive silver halide emulsion layer, auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer can be provided. Sensitizer, coupler, high boiling point solvent, antifoggant, stabilizer, development inhibitor,
Bleaching accelerators, fixing accelerators, color mixture inhibitors, formalin scavengers, toning agents, hardeners, surfactants, thickeners, plasticizers, slippers, ultraviolet absorbers, antiirradiation dyes, filter light absorbing dyes, Polymer latex, heavy metals, antistatic agents, matting agents, etc. can be incorporated by various methods. The support which can be used in the silver halide photographic light-sensitive material of the present invention includes cellulose triacetate, cellulose nitrate, polyester such as polyethylene terephthalate and polyethylene naphthalate, polyolefin such as polyethylene, polystyrene, baryta paper, polyethylene and the like. Paper, glass, metal, and the like. These supports are subjected to a base treatment as required.

These additives mentioned above are described in more detail in Research Disclosure, Vol. 176, Item / 1.
7643 (December 1978), Volume 184, Item /
18431 (August 1979) and 187 Item
/ 18716 (November 1979).

The development processing of the silver halide photographic light-sensitive material of the present invention is carried out, for example, by T.W. H. The Theory of the Photographic Process 4th Edition by James (The Theory of the Photog
radical Process, fourth Edi
291-334 and the Journal of
The American Chemical Society (Journa
l of the American Chemica
l Society) 73, 3,100 (195
The developer described in 1) can be used effectively.

[0057]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide photographic emulsion A) Silver chloroiodobromide (40 mol% of silver chloride, 0.5 mol% of silver iodide per mol of silver, etc.) was brominated by the simultaneous mixing method. A silver) emulsion was prepared.

During the mixing process from the formation of 5% of the final reached average particle size to the final reached average particle size, K ₂ IrC
₁₆ × 8 ^-7 mol per mol of silver was added. After desalting by a flocculation method using modified gelatin treated with phenyl isocyanate, it is dispersed in gelatin, and a mixture of the following compounds [A], [B] and [C] is added as an antifungal agent. An emulsion consisting of cubic monodisperse grains (variation coefficient 10%) having an average grain size of 0.3 μm was obtained.

To this emulsion was added p-citric acid and sodium chloride.
After adjusting H to 5.8 and pAg to 7.0, it was optimally chemically aged at 60 ° C. using sodium thiosulfate pentahydrate and chloroauric acid, and then 1-phenyl-5-mercaptotetrazole was added. 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene was added in an amount of 60 m
The ripening was stopped by adding g and 600 mg.

Next, the additives SA-1 and NU shown below were added.
An appropriate amount of -1, NA-1, LX-1 and HD-1 was added to prepare an emulsion coating solution.

[0062]

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(Preparation of silver halide photographic emulsion B) Emulsion of silver chloroiodobromide (silver bromide 40 mol%, silver iodide 0.5 mol% and other silver bromide per mol of silver) using a simultaneous mixing method. Was prepared.

Denatured gelatin treated with phenyl isocyanate was desalted by the flocculation method and then dispersed in gelatin to obtain the compound [A] as an antifungal agent.
A mixture of [B] and [C] is added, and the average particle size is 0.3 μm.
Of cubic monodisperse grains (coefficient of variation: 10%). The pH of this emulsion was adjusted to 5.8 with citric acid and sodium chloride and the pAg was adjusted to 7.0, after which it was optimally chemically ripened at 60 ° C. with sodium thiosulfate pentahydrate and chloroauric acid. 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene, 60 mg and 6 per mol silver, respectively
The ripening was stopped by adding 00 mg.

The emulsion thus obtained was chemically sensitized in the same manner as in the above emulsion A, and the same additives were added to prepare an emulsion coating solution.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) On the undercoat layer, a silver halide emulsion layer of the following formula (1) with a gelatin amount of 2.0 g
/ M ² and a silver amount of 3.2 g / m ^2, and an emulsion protective layer of the following formula (2) is further coated thereon with a gelatin amount of 1.0 g / m ^2.
by coating so as to be g / m ^2, also on the opposite side of the other subbing layer, a backing layer was coated as the amount of gelatin is 2.4 g / m ² according to the following formulation (3) Further, a backing protective layer having the following formulation (4) was further applied thereon so that the amount of gelatin would be 1.0 g / m ² to obtain a sample.

Formulation (1) [Silver halide emulsion layer composition] Gelatin 2.0 g / m ² Silver halide emulsion: Emulsions A and B 3.2 g / m ² Photosensitive dye: Compound of the present invention and comparative compound 2 × 10 ^-4 mol / mol silver Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: Adenine 10 mg / m ² : 1-phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: Saponin 0.1 g / m ² SA-1 8 mg / m ² Hydrazine derivative: NU-1 35 mg / m ² Nucleation accelerator: NA-1 70 mg / m ² Latex polymer: Lx-1 1.0 g / m ² polyethylene glycol (molecular weight 4000) 0.1 g / m ² Hardener: HD-1 60 mg / m ²

[0068]

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Formulation (2) [Emulsion protective layer composition] Gelatin 0.9 g / m ² Surfactant: SA-2 10 mg / m ² SA-3 10 mg / m ² Matting agent: Monodisperse with an average particle size of 3.5 μm Silica 3 mg / m ² Hardener: 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Formulation (3) [Backing layer composition] Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² SA-1 6 mg / m ² colloidal silica 100 mg / m ² Coloring dye: F-1 30 mg / m ² F-2 75 mg / m ² F-3 30 mg / m ²

[0070]

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Formulation (4) [Backing protective layer composition] Gelatin 1.0 g / m ² Surfactant: SA-2 10 mg / m ² Matting agent: Monodispersed polymethylmethacrylate 50 mg / m with an average particle size of 5.0 μm ² Hardener: Glyoxal 35 mg / m ² Each of the obtained samples was divided into 2 minutes, one of them was left as it was, and the other was subjected to 20% R to evaluate stability under high temperature.
H, left in an environment of 50 ° C. for 3 days for forced deterioration.

(Evaluation of Photographic Performance) A wedge was attached to the obtained sample, and the Ratten filter No. 1 through 21
0 gives ^-5 sec exposure were treated under the following conditions with a developer and fixer rapid processing automatic processor GR-26S was charged having the following composition (manufactured by Konica Corporation]).

The obtained sample was used as an optical densitometer PDA-65.
(Konica Corp.), the density was measured, and the sensitivity was measured by the reciprocal of the exposure amount at the fog density + 0.3 in the usual way.
o. It was shown as a relative value with the sensitivity of the sample immediately after coating and drying of No. 1 being 100.

The residual color contamination rank was evaluated by visually observing the residual color when five sheets of unexposed film were developed and fixed, and the residual color was visually observed. The one with no residual color is given the highest rank of "5",
In the following, “4”, “3”, and
“2” and “1” and their ranks are sequentially lowered and evaluated. Ranks "2" and "1" are levels that are not practically preferable.

[Developer composition] Potassium sulfite 60.0 g Hydroquinone 15.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 0.5 g Potassium carbonate 50.0 g Potassium bromide 5.0 g 2-mercaptobenzimidazole 0.25 g 5-methylbenzotriazole 0.4 g Water was added to make 1 liter, and the pH was adjusted to 10.5 with potassium hydroxide.

[Fixer Formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17.0 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 8. When using 5 g of fixer, the above composition A and composition B are added to 500 ml of water.
And finished to 1 l before use. P of this fixer
H was adjusted to 4.8 with acetic acid.

[Development Processing Conditions] (Process) (Temperature) (Time) Development 38 ° C. 20 seconds Fixing 35 ° C. 20 seconds Washing 30 ° C. 15 seconds Drying 50 ° C. 15 seconds The obtained results are shown in Tables 1 and 2. .

[0078]

[Table 1]

[0079]

[Table 2]

As is clear from Tables 1 and 2, the silver halide photographic light-sensitive material according to the present invention has good photographic performance in which fogging and sensitivity fluctuation are suppressed as compared with the comparative sample both on the same day and over time (substitute thermo). Was given. This effect was remarkably observed in the silver halide photographic emulsion containing the iridium compound. In addition, the compound according to the present invention is a comparative compound [I]
It can be seen that the residual color contamination is also superior to that of [V].

Example 2 Each layer having the constitution shown in Tables 3 and 4 below was coated with titanium oxide on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the other side. It was coated on the side of the contained polyethylene layer to prepare a multilayer silver halide color photographic light-sensitive material sample. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (EY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (S
T-2) 6.67 g, stain inhibitor (HQ-1) 0.
To 67 g and 6.67 g of a high boiling organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was added to 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SA-4) using an ultrasonic homogenizer. It was emulsified and dispersed to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation dye (F-6) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardener, (HD-2) was added to the second and fourth layers, and (HD-1) was added to the seventh layer.
As the coating aid, surfactants (SA-2) and (SA-
3) was added to adjust the surface tension.

[0085]

[Table 3]

[0086]

[Table 4]

The structural formulas of the compounds used in the above-mentioned layers are shown below.

[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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The compositions of the silver halide emulsions (EM-B), (EM-G) and (EM-R) in Tables 1 and 2 are shown below.

Blue-Sensitive Silver Halide Emulsion (Em-B) Monodispersed cubic emulsion having an average grain size of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX inhibitor 6 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / Molar AgX Green-sensitive silver halide emulsion (Em-G) Monodisperse cubic emulsion having an average grain size of 0.43 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX inhibitor 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Red-sensitive silver halide emulsion (Em-R) average grain size 0.50 μm, coefficient of variation = .08, monodispersed cubic emulsion of sodium thiosulfate 99.5 mol% silver chloride content of 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX suppression agent 6 × 10 ^-4 mol / mol AgX Sensitizing dye (Table 5) 2 × 10 ⁻⁴ mol / mol AgX Supersensitizer SS-1 3 × 10 ⁻⁴ mol / mol AgX The structural formulas of the compounds used in each monodisperse cubic emulsion are shown below.

[0095]

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Based on the above-mentioned layer structure, the irradiation preventing dyes and the light-sensitive dyes in each of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsions in the sixth layer of Table 3 were changed as shown in Table 5. , Samples 42 to 57 were prepared, and the following evaluations were performed on these.

<Evaluation> Relative Sensitivity Each sample was measured using a sensitometer KS-7 type (manufactured by Konica)
After unexposed to red color by the primary color separation filter, the following color developer A was opened and processed according to the following processing steps. After processing, PDA-65 type densitometer (made by Konica)
Sensitometric measurement was carried out. The sensitivities in the table are sample No. The sensitivity of the fresh sample of No. 1 was set as 100 and shown as a relative value.

The residual color unexposed sample was processed using the following processing steps, and the yellow density of the obtained sample was measured by Gredarkark D-12.
It was performed using a type 2 densitometer.

The concentration of the sample is represented by a relative value where the absorption of the support is 0. The results are shown in Table 5.

The processing steps are shown below.

Processing Step Temperature Time Color Development 35.0 ± 0.3 ° C. 45 seconds Bleach-fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds The composition of each treatment liquid is shown below.

The replenishing amount of each processing solution is 80 ml per 1 m ^{2 of} silver halide color photographic light-sensitive material.

Color developing solution A Tank solution Replenishing solution Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1. 8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g 8.2 g Optical brightener (4,4′-diaminostilbene sulfonic acid derivative) 1.0 g 1 2.8 g Potassium carbonate 27 g 27 g Water is added to bring the total volume to 1000 ml, and the pH is adjusted to 10.10 in the tank solution and 10.60 in the replenisher.

Bleach-fix solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water In addition, the total amount is adjusted to 1000 ml, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 0.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water was added to bring the total volume to 1000 ml, and sulfuric acid or water was added. Adjust the pH to 7.0 with potassium oxide.

Color developing solution B Tank solution Replenishing solution Pure water 800 ml 800 ml Triethanolamine 10 g 18 g Potassium chloride 5 g 9 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.4 g N-ethyl-β-methanesulfonamidoethyl -3 -Methyl-4-aminoaniline sulfate 1.0 g 1.8 g 4,4'-diaminostilbene sulfonic acid derivative 5.4 g 8.2 g Potassium carbonate 1.0 g 1.8 g Photosensitive dye (dye of the present invention shown in Table 5 And comparative dye) 50 mg 50 mg Water was added to make the total amount 1000 ml, and the pH was adjusted to 10.10 in the tank liquid and 10.60 in the replenisher. The results obtained are shown in Table 5 below.

[0107]

[Table 5]

As can be seen from Table 5, the dyes of the present invention have better spectral sensitization properties than the comparative dyes and have very little residual color stain.

That is, even in the residual color test with the model processing solution (color developer B) prepared by assuming that the dye flowing out in the continuous processing of the light-sensitive material was accumulated, the light-sensitive material containing the dye of the present invention was also tested. Shows that the dye is not redeposited, and that the light-sensitive material containing the dye represented by the general formula [S-II] is excellent in that it has less residual color contamination.

[0110]

According to the present invention, a silver halide photographic light-sensitive material having high spectral sensitivity in the red light region and less residual color contamination can be obtained.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has a spectral enhancement represented by the following general formula [SI]. A silver halide photographic light-sensitive material containing a sensitizing dye. Embedded image In the formula, Z ¹ and Z ² each independently represent a 5- or 6-membered nitrogen-containing heterocyclic group, Z ³ is a —N (R)-group, an oxygen atom,
Represents a sulfur atom, a selenium atom or a tellurium atom. R ¹ and R ³ each represent an aliphatic group having 10 or less carbon atoms, and R and R ² each represent an aliphatic group, an aryl group or a heterocyclic group.
However, at least one of R, R ¹ , R ² and R ³ represents a group substituting the water-solubilizing group. L ¹ represents a methine carbon substituted with a halogen atom, and L ² and L ³ each represent an optionally substituted methine carbon. l ¹ , l ² and m ¹ are integers of 0 or 1. M ¹ represents an ion necessary for canceling the total charge of the molecule, and n ¹ represents the number necessary for neutralizing the total charge of the molecule. 2. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has a spectral enhancement represented by the following general formula [S-II]. A silver halide photographic light-sensitive material containing a sensitizing dye. Embedded image In the formula, Y ¹¹ , Y ¹² and Y ¹³ are each independently -N (R
¹⁰ ) -group, oxygen atom, sulfur atom, selenium atom or tellurium atom. R ¹¹ and R ¹³ each represent an aliphatic group having 10 or less carbon atoms, and R ¹⁰ and R ¹² each represent an aliphatic group, an aryl group or a heterocyclic group. However, at least one of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represents a group substituting the water-solubilizing group.
V ¹ , V ² , V ³ and V ⁴ are each a hydrogen atom, an alkyl group,
Represents an alkoxy group and an aryl group, and is V ¹ and V ² , or V ³
And V ⁴ may combine with each other to form a condensed ring together with the azole ring. L ¹¹ represents a methine carbon substituted with a halogen atom. L ¹² and L ¹³ each represent an optionally substituted methine carbon. m ² represents an integer of 0 or 1, M ¹¹ represents an ion necessary to cancel the total charge of the molecule, and n ² represents a number necessary to neutralize the total charge of the molecule. 3. The silver halide grain in the silver halide emulsion layer contains at least one iridium compound in an amount of 10 ⁻⁸ mol to 10 ⁻⁴ mol per mol of silver. The silver halide photographic light-sensitive material according to claim 2.