JPH08201954A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain the silver halide photographic sensitive material high in spectral sensitivity in the red wavelength region and small in residual dye stains by spectrally sensitizing at least one of silver halide emulsion layers with a specified dye. CONSTITUTION: At least one of the silver halide emulsion layer of the photosensitive material formed on a support is spectrally sensitized with at least one kind of 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 a -N(R) group or an 0, S, Se, or Te atom: each of R<1> and R<3> is a <=10 C aliphatic group; each of R and R<2> is an aliphatic or aryl or heterocyclic group; L<1> is a substituted methine carbon group; each of L<2> and L<3> is an optionally substituted methine carbon group; each of l<1> and l<2> and m<1> is 0 or 1; M<1> is an ion needed for canceling the total charge of the molecule; and n<1> is a number needed 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) Spectral sensitization region is appropriate and spectral sensitization efficiency is excellent (2) No adverse effect due to other additives (3) No fog or gamma deterioration during aging of the photosensitive material Stable (4) Not diffusible to other layers (5) It is required that the processed light-sensitive material has 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 spectral sensitizing dye, improvement of residual color is an important technical section in the present situation.

Conventionally, as a spectral sensitizing dye for sensitizing a red light region, there are, for example, Belgian Patent No. 541,245 and US Patent No. 2,47.
5,163, 2,493,747, 2,493,748, 2,743,272
No.3, No.3,335,010, No.3,672,905, No.3,674,499,
French Patent 2,113,248, German Patent 1,024,800, 2,153,
570, 2,300,321, JP-A-54-18726, 61-11736
JP-A-5-134346, JP-A-5-289222 and JP-A-3-171135 disclose that complex cyanines and complex merocyanines are effective. Further, JP-A-49-11121, 51-33622, 51-115821
No. 51-115822, No. 58-72937, No. 61-203446, JP-A-2-256045, No. 3-15042 cyanine described in,
U.S. Patents 2,493,747, 2,493,748, 2,519,001
And the merocyanine dyes described in JP-A-51-106422 and JP-A-59-214030 are known to be 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 363,104 was disclosed.
The dyes described in JP-A Nos. 363,107 and 363,107 are recognized to have a remarkable effect of improving the residual color stain. However, the photographic performance of the light-sensitive materials containing these dyes was found to change when stored over time. Also, JP-A-62-227142, JP-A-4-328542,
JP-A-5-224337 discloses a technique of increasing the 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 objects of the present invention have been achieved by the following.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the following general formula [SI]. A silver halide photographic light-sensitive material, which is spectrally sensitized with at least one of the dyes described below.

[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 a -N (R)-group, an oxygen atom, a sulfur atom, a selenium atom or Represents 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 substituted methine carbon, and L ² and L ³ each represent an optionally substituted methine carbon. l ¹ , l ² and m ¹ are 0
Alternatively, it is an integer of 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 at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the following general formula [S-II]. A silver halide photographic light-sensitive material, which is spectrally sensitized with at least one of the dyes described below.

[0016]

[Chemical 4]

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 substituted methine carbon. L ¹² and L
Each ¹³ represents 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 above general formula [SI] or [SI]
The silver halide grains spectrally sensitized with at least one of the dyes represented by the formula I) are contained in an amount of from 10 ^-8 mol to 1 mol of silver.
A silver halide photographic light-sensitive material containing at least one of 10 ^-4 mol of an iridium compound.

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-NHCO-] group, [an alkyl group -SO ₂ -NHCO-] group, [an alkyl group -SO ₂ -
Examples thereof include a group that ionically dissociates in an aqueous alkaline solution such as NHSO ₂ −] group and sulfamoyl group.

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 such as methyl, ethyl, n-propyl, n-pentyl, isobutyl), an alkenyl group having 3 to 10 atoms (for example, each group such as 3-butenyl, 2-propenyl), or the number of carbon atoms. And 3 to 10 aralkyl groups (for example, groups such as benzyl and phenethyl).

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
-), Thienyl group (2-), sulforanyl group, tetrahydrofuryl group, piperidinyl group and the like. R, R ¹ ,
Each group of 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, etc.) , An 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,
It may be substituted with a substituent such as a phenyl group, a carboxyphenyl group and the like) and an acyl group (for example, an acetyl group, a 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 each group has carboxybenzyl, acetylaminosulfonylmethyl, acetylaminocarbonylmethyl, methanesulfonylaminocarbonylmethyl, methanesulfonylaminosulfonylmethyl, sulfamoylethyl, etc., and is substituted with a water-solubilizing group As a p-sulfophenyl group, p-carboxyphenyl group There are various groups such as
Specific examples of the heterocyclic group substituted with the water-solubilizing group include 4-sulfothienyl group and 5-carboxypyridyl group.

In these, R ¹ and R ¹¹ are alkyl groups substituted with sulfo groups, 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 other ring groups. .

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, t-pentyl). , Each group such as hexyl). V ¹ , V ² , V ³
And an alkoxy group represented by V ⁴ , for example,
Each group such as methoxy, ethoxy, propoxy and the like can be mentioned.

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. Examples of the condensed ring in which V 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 and 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 [2,3-d]
Examples of the condensed ring include thiazole, 4,5,6,7-tetrahydrobenzoselenazole, naphtho [1,2-d] selenazole, and a 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ¹ and Z ^2. To be The above-mentioned substituents represented by V ¹ , V ² , V ³ and V ⁴ and the condensed ring to be formed may have a substituent at any position, for example, a halogen atom (fluorine atom, Chlorine atom, bromine atom, iodine atom), trifluoromethyl group, alkoxy group (eg, unsubstituted alkyl groups such as methoxy, ethoxy and butoxy, substituted alkoxy groups such as 2-methoxyethoxy and benzyloxy), hydroxy group , A cyano group, an aryloxy group (eg, substituted or unsubstituted groups such as phenoxy or tolyloxy), or an aryl group (eg, substituted or unsubstituted groups such as phenyl or p-chlorophenyl), a styryl group, a hetero group A cyclic group (eg,
Each group such as furyl and thienyl), a carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl),
Sulfamoyl group (eg, groups such as sulfamoyl, N, N-dimethylsulfamoyl, etc.), acylamino group (eg, groups such as acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.) Groups), alkoxycarbonyl groups (eg, groups such as ethoxycarbonyl), sulfonamide groups (eg, groups such as methanesulfonylamide, benzenesulfonamide), sulfonyl groups (eg, methanesulfonyl, p-toluenesulfonyl, etc.) Group) Arbitrary groups, such as a carboxy group, are mentioned.

Examples of the group substituted on the methine carbon represented by L ¹ , L ² , L ³ and L ¹¹ , L ¹² and L ¹³ include:
Lower alkyl groups (eg, groups such as methyl and ethyl),
There are groups such as a phenyl group (for example, groups such as phenyl and carboxyphenyl), an alkoxy group (for example, groups such as methoxy and ethoxy), and aralkyl (for example, group 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, and has a higher spectral sensitivity than conventionally known dyes in which L ¹ and L ¹¹ are CH groups. Is obtained, and the dye has the effect of being easily drifted in the treatment bath, and has a preferable effect of significantly reducing the residual color contamination.

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 the invention is not limited to these compounds.

[0033]

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[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

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[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

The above compounds are described, for example, in "Cyanine Soybean and Relayed Compounds" (1964, published by Inter Science Publishers) by FM Hama, US Pat. It can be easily synthesized with reference to the conventionally known method described.

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

Synthesis Example 1 (Exemplified Compound S-4) 4-oxo-5- [2- [7- (3-sulfopropyl) -6 (7H) -dioxolo [4,5-f] benzoxazolilidene] 2.6 g of propylidene] -2-thioxothiazolidin-3-ylacetic acid was mixed with 4 g of p-toluenesulfonic acid methyl ester and heated and stirred at 130 ° C. for 120 minutes.

After returning 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 gentle heating under reflux for 20 minutes, then
It was 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 1.3 g of a dye. The absorption maximum wavelength in the methanol solution was 599 mm. (Ε = 100,000) Synthesis Example 2 (Exemplified Compound S-30) 4-oxo-5- [2- [7- (3-sulfopropyl) -6 (7H) -dioxolo [4,5-f] benzothiazoli Ridene] propylidene] -2-thioxothiazolidin-3-ylacetic acid 2.7 g was added to dimethyl sulfate 2.5.
It was mixed with g and heated and stirred 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, gently heating to reflux for 20 minutes, then cooling. It was allowed to crystallize. The precipitate was collected by filtration and washed with an ethanol solvent. The obtained crude crystals were recrystallized from a methanol solvent to obtain 1.5 g of a dye. The absorption maximum wavelength in the methanol solution was 630 mm. (Ε = 104,000) The addition amount of the compound according to the present invention varies largely depending on the conditions used and the type of emulsion, but is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ per mol of silver halide. Mol, more preferably 2 × 10 ⁻⁶ to 2 × 10 ⁻³ mol.

The above-mentioned general formula [S
The compounds represented by -I] and [S-II] can be added to the silver halide emulsion by a conventionally known method. For example, the protonated dissolution addition method described in JP-A-50-80826 and JP-A-50-80827, US Pat. No. 3,822,135, JP-A-50-11
Method of dispersing and adding together with a surfactant described in No. 419, U.S. Pat.Nos. 3,676,147, 3,469,987, 4,247,627, JP-A-51-59942, 53-16624, 53-102732, 53-102732, 53-
No. 102733, No. 53-137131, a method of dispersing and adding to a hydrophilic substrate, a method of adding as a solid solution of East German Patent 143,324, or Research Disclosure No. 2
1,802, JP-B-50-40659, JP-A-59-148053, a water-soluble solvent that dissolves a dye (for example, a low boiling point solvent such as water, methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohol). , High-boiling point solvents such as dimethylformamide, methylcellosolve, phenylcellosolve, etc.) or a method in which they are dissolved in a mixed solvent thereof and added, and the like are arbitrarily selected and added into the emulsion.

The photosensitive dyes represented by the above general formulas [SI] and [S-II] may be added at any stage in the emulsion production process from physical ripening to coating after chemical ripening. Preferably, it is added between the physical ripening and the end of chemical ripening. The addition of the compound according to the present invention during the physical ripening or 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 a higher spectral sensitivity. , Preferably used.

The photosensitive dyes represented by the general formulas [SI] and [S-II] can also 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 photosensitizing dye used in the present invention can further enhance the spectral sensitivity by using a compound which brings about a supersensitizing effect. Examples of such a compound having a supersensitizing effect include U.S. Pat. Nos. 2,933,390 and 3,416,927.
No. 3,51,664, 3,615,613, 3,615,632,
3,635,721, JP-A-3-15042, 3-110545, 4-
Compounds having a pyrimidinylamino group or a triazinylamino group described in 255841 etc., British Patent No. 1,137,580
Aromatic organic formaldehyde condensates described in JP-A No. 61-169833, calixarene derivatives described in JP-A No. 4-184332, halogenated benzotriazole derivatives described in US Pat. No. 4,030,927, JP-A-59-142541. Issue 59-
Bispyridinium compounds described in 188641, JP-A-59-191
Aromatic heterocyclic quaternary salt compounds described in 032, JP-A-60-7934
No. 8, electron donating compound, a polymer containing an aminoallylidene malononitrile unit described in US Pat. No. 4,307,183,
A hydroxytetrazaindene derivative described in JP-A-4-149937, a 1,3-oxadiazole derivative described in U.S. Pat.No. 3,615,633, and an amino-1,2,3,4-described in U.S. Pat.
Examples thereof include thiatriazole derivatives. The timing of addition of these supersensitizers is not particularly limited, and can be arbitrarily added according to the timing of addition of the photosensitive dye according to the present invention. The addition amount is selected in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and the addition amount is 1/10 to 10/1 with the photosensitive dye.

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

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

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 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, and specifically, iridium trichloride, iridium tribromide, iridium tetrachloride,
Examples include iridium tetrabromide, potassium hexachloroiridium (III), potassium hexabromoiridium (III), sodium hexachloroiridium (IV), potassium hexabromoiridium (IV), etc. Combinations of two or more species may be used.

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

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention, if necessary. For example, 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 in addition to the light-sensitive silver halide emulsion layer. Sensitizers, couplers, high boiling solvents, antifoggants, stabilizers, development inhibitors,
Bleaching accelerator, fixing accelerator, anti-color mixing agent, formalin scavenger, toning agent, hardener, surfactant, thickener, plasticizer, sliding agent, UV absorber, anti-irradiation dye, filter light absorbing dye, A polymer latex, a heavy metal, an antistatic agent, a matting agent and the like can be incorporated by various methods. The support that can be used in the silver halide photographic light-sensitive material of the present invention includes cellulose triacetate, cellulose nitrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polystyrene, baryta paper, polyethylene and the like. Examples thereof include paper, glass and metal laminated with. These supports are subjected to a surface treatment if necessary.

The above-mentioned additives are described in more detail in Research Disclosure, Vol. 176, Item / 17643 (197).
December 1988), Volume 184 Item / 18431 (August 1979) and Volume 187
It is described in Item / 18716 (November 1979).

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James The Theory of the Photographic Process 4
Edition (The Theory of the Photographic Process, fourth
Edition) pages 291-334 and the Journal of the Ame.
The developer described in rican Chemical Society, Vol. 73, page 3,100 (1951) can be effectively used.

[0056]

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 per mol of silver, 0.5 mol of silver iodide) was prepared by the simultaneous mixing method.
A mol% and others silver bromide) emulsion was prepared.

K ₂ IrCl ₆ was added in an amount of 8 × 10 ^-7 mol per mol of silver during the mixing step from the formation of 5% of the final reached average particle size to the arrival of the final reached average particle size. 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. , Cubic monodisperse particles with an average particle size of 0.3 μm (variation coefficient 10
%) Was obtained.

To this emulsion was added p-citric acid and sodium chloride.
After adjusting H to 5.8 and pAg to 7.0, 1-phenyl-5-mercaptotetrazole and 4-hydroxy- were prepared by optimal chemical aging at 60 ° C using sodium thiosulfate pentahydrate and chloroauric acid. Ripening was stopped by adding 6-methyl-1,3,3a, 7-tetrazaindene, 60 mg and 600 mg, respectively, per mol of silver.

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

[0061]

[Chemical 12]

(Preparation of silver halide photographic emulsion B) An emulsion of silver chloroiodobromide (40 mol% of silver chloride per 0.5 mol of silver, 0.5 mol% of silver iodide and others of silver bromide) emulsion is prepared by the simultaneous mixing method. did.

Denatured gelatin treated with phenyl isocyanate was desalted by the flocculation method and dispersed in gelatin to obtain the compound [A] as an antifungal agent.
The mixture of [B] and [C] was added to obtain an emulsion composed of cubic monodisperse grains (variation coefficient: 10%) having an average grain size of 0.3 μm.
This emulsion was adjusted to pH 5.8 with citric acid and sodium chloride, pAg
Was adjusted to 7.0, and then subjected to optimum chemical aging at 60 ° C with sodium thiosulfate pentahydrate and chloroauric acid, and then 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1 1,3,3a, 7-Tetrazaindene per 1 mol of silver
Aging was stopped by adding 60 mg and 600 mg.

The emulsion thus obtained was chemically sensitized in the same manner as 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 having the following formulation (1) was used, in which the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ^2.
And an emulsion protective layer of the following formulation (2) so that the amount of gelatin will be 1.0 g / m ^2, and on the other undercoat layer on the opposite side. According to the following prescription (3), a backing layer is coated so that the amount of gelatin becomes 2.4 g / m ^2, and a backing protective layer of the following prescription (4) has a gelatin amount of 1.0 g / m ² A sample was obtained by coating in this manner.

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

[0067]

[Chemical 13]

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 silica 3 mg with an average particle size of 3.5 μm / M ² Hardener: 1,3-vinylsulfonyl-2-propanol 40mg / m ² Formulation (3) [Backing layer composition] Gelatin 2.4g / m ² Surfactant: Saponin 0.1g / m ² SA-1 6mg / 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

[0069]

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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: Monodisperse polymethylmethacrylate with an average particle size of 5.0 μm 50 mg / m ² Hardener: Glyoxal 35 mg / m ² Obtained samples are 2 each Of the sample, one of them as it is, and the other of the sample at 20% RH in order to evaluate the stability under high temperature.
It was left for 3 days in an environment of 50 ° C. for forced deterioration.

(Evaluation of photographic performance) A wedge was adhered to the obtained sample, exposed for 10 ^-5 seconds through a Ratten filter No. 21, and a developing solution and a fixing solution having the compositions shown below were charged. Processing was carried out under the following conditions using an automatic processor for processing GR-26S (manufactured by Konica Corporation).

The density of the obtained sample was measured with an optical densitometer PDA-65 (manufactured by Konica Corporation).
The reciprocal of the exposure dose at 0.3 was taken and indicated as a relative value with the sensitivity of the sample immediately after coating and drying of sample No. 1 taken as 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 highest rank is "5" when there is no residual color, and "4", "3", and so on according to the degree of occurrence of residual color.
“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 0.25g 5-Methylbenzotriazole 0.4g Add water to make 1 liter and adjust pH to 1 with potassium hydroxide.
Adjusted to 0.5.

[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 sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 8.5 g When using the fixer in 500 ml water The above composition A and composition B were melted in this order and finished to 1 l for use. The pH of this fixer 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 results obtained are shown in Tables 1 and 2. .

[0079]

[Table 1]

[0080]

[Table 2]

As is clear from Tables 1 and 2, the silver halide photographic light-sensitive material of 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. Further, it can be seen that the compound according to the present invention is superior in terms of residual color contamination as compared with the comparative compounds [I] to [V].

Example 2 Each layer having the constitution shown in Tables 3 and 4 below was coated with titanium oxide on a support having polyethylene laminated 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 liquid 26.7 g of yellow coupler (EY-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2)
To 6.67 g, stain inhibitor (HQ-1) 0.67 g and high boiling point organic solvent (DNP) 6.67 g, 60 ml of ethyl acetate was added and dissolved, and this solution was mixed with 20 ml of surfactant (SA-4) 7 ml 10 % Gelatin aqueous solution 220 ml was emulsified and dispersed using an ultrasonic homogenizer 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. Also, as a hardener, the second layer and the fourth layer
(HD-2) was added to the layer and (HD-1) was added to the 7th layer. As the coating aid, surfactants (SA-2), (S
A-3) was added to adjust the surface tension.

[0086]

[Table 3]

[0087]

[Table 4]

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

[0089]

[Chemical 15]

[0090]

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[0091]

[Chemical 17]

[0092]

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[0093]

[Chemical 19]

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

Blue-Sensitive Silver Halide Emulsion (Em-B) Monodisperse cubic emulsion with average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 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 / mol AgX green-sensitive silver halide Emulsion (Em-G) Monodisperse cubic emulsion with average grain size 0.43 μm, coefficient of variation = 0.08, silver chloride content 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, variation coefficient = 0.08, silver chloride content 99.5 mol % Monodisperse cubic emulsion Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX inhibitor 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (Table 5) 2 × 10 ⁻⁴ mol / mol AgX Supersensitizer SS-13 3 × 10 ⁻⁴ mol / mol AgX The structural formulas of the compounds used in each monodisperse cubic emulsion are shown below.

[0096]

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Based on the above-mentioned layer structure, the irradiation prevention dyes and 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 these were evaluated as follows.

<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 the treatment was completed, sensitometric measurement was carried out with a PDA-65 type densitometer (manufactured by Konica). Sensitivity in the table is sample N
The sensitivity of the fresh sample of o.1 was set as 100 and shown as a relative value.

Residual color The unexposed sample was processed using the following processing steps, and the yellow density of the obtained sample was measured by Gredarkark D-122.
This was performed using a model densitometer.

The concentration of the sample is expressed as 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 process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleaching / fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds Composition of each processing solution is as follows. Show.

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

Color developer A Tank solution Replenisher Pure water 800ml 800ml Triethanolamine 10g 18g N, N-diethylhydroxylamine 5g 9g Potassium chloride 2.4g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g 1.8g N- Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water Is added to bring the total volume to 1000 ml.
Is adjusted to 10.10 and the pH of the replenisher is adjusted to 10.60.

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 was added. Adjust the total volume to 1000 ml and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (same as tank solution and replenisher solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1000 ml, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

Color developer B tank solution Replenisher 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 dyes (colorants of the present invention and comparative dyes shown in Table 5) 50 mg 50 mg Water Is added to bring the total volume to 1000 ml.
Was adjusted to 10.10 and for the replenisher was adjusted to 10.60. The results obtained are shown in Table 5 below.

[0108]

[Table 5]

As is clear from Table 5, the dyes of the present invention exhibit 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.

[0111]

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 at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that at least one of said silver halide emulsion layers is spectrally sensitized with at least one dye represented by the following formula [SI]. Embedded image In the formula, Z ¹ and Z ² each independently represent a 5- or 6-membered nitrogen-containing heterocyclic group, and Z ³ represents a —N (R)-group, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. Represent 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, R,
At least one of R ¹ , R ² and R ³ represents a group substituting the water-solubilizing group. L ¹ represents a substituted methine carbon,
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 at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that at least one of said silver halide emulsion layers is spectrally sensitized with at least one dye represented by the following formula [S-II]. Embedded image In the formula, Y ¹¹ , Y ¹² and Y ¹³ are each independently —N (R ¹⁰ ).
Represents a 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
May combine with each other to form a condensed ring together with the azole ring. L ¹¹ represents a substituted methine carbon. L ¹² and L ¹³ each represent an optionally substituted methine carbon. m ² is 0
Further, it represents an integer of 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 above general formula [SI] or [S-II].
In silver halide grains which are spectrally sensitized by at least one dye represented is, per mole of silver 10 ^-8 moles to 10 ^-4
A silver halide photographic light-sensitive material containing at least one mol of an iridium compound.