JPH10186560A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material enhanced in spectral sensitivity in the wavelength region covering from red to near infrared regions and freed of residual dye stains by spectrally sensitizing at least one of emulsion layers with a specified dye. SOLUTION: At least one of the silver halide emulsion layers contains silver halide grains spectrally sensitized with at least one of the dyes represented by the formula in which each of Y<1> -Y<4> is, independently, a -N(R)- group or an O, S, Se, or Te atom; either of Y<3> and Y<4> is a -N(R<4> )- group; R<1> is an <=8C aliphatic group substituted by a water-solubilizing group; each of R, R<2> , R<3> , and R<4> is an aliphatic, aryl, or heterocyclic group; Z<1> is a nonmetallic atomic group necessary to form a 5- or 6-membered N-containing heterocyclic group; W is a an O or S atom or the like; each of L<1> and L<2> is, independently, optionally substituted methine grope; each of E<1> and E<2> is, independently, an electron withdrawing group; l<1> is 0 or 1; M<1> is an ion for cancelling the total charge of the molecule; and n<1> is a number of the ions necessary to the molecule charge.

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 improved spectral sensitivity in a red to near-infrared light wavelength region and free from residual color contamination. Things.

[0002]

2. Description of the Related Art The photosensitive wavelength range of silver halide emulsions (hereinafter, referred to as "halogenated emulsions" or simply "emulsions") is expanded.
Means for increasing the sensitivity are well known as a spectral sensitization technique, and as the spectral sensitizing dye used for this purpose, many compounds such as a cyanine dye and a merocyanine dye are known.

[0003] These spectral sensitizing dyes must not only extend the photosensitive wavelength range of the silver halide emulsion but also satisfy the following conditions.

[0004] 1) Spectral sensitization range is appropriate 2) Spectral sensitization efficiency is high 3) No adverse effect is exerted on the characteristic curve such as fogging or gamma change 4) Halogenation containing sensitizing dye The photographic performance such as fog should not be changed when the silver photographic material is aged (especially when stored under high temperature and high humidity). 5) The added photosensitive dye diffuses into the layer of different photosensitive wavelength range. Does not cause color turbidity. 6) After development and fixing, the photosensitive dye does not come off after washing with water and does not cause color contamination. However, the spectral sensitizing dyes disclosed hitherto are still at levels that sufficiently satisfy all of these conditions. Has not been reached.

[0005] In particular, as the development processing time is shortened and the recycling of the anhydrous washing and the processing solution is introduced, the dye tends to remain. As a result, color contamination (hereinafter referred to as "residual color contamination") appears on the processed photosensitive material, and there is a problem that the commercial value is significantly reduced. That is, in the case of photosensitive dyes, improvement of residual color contamination has become an important technical problem.

As photosensitive dyes for spectrally sensitizing a red light wavelength region, for example, Soviet Patent No. 871,648, Belgian Patent No. 541,245, US Pat.
No. 47, 2,493,748, 2,743,27
2, 3,335,010, French patent 2,113,
No. 248, German Patent 1,024,800 and 2,15
No. 3,570, No. 2,300,321, European Patent 36
3,104,363,107, JP-A-3-171
No. 135, No. 5-134346, No. 5-273684
No. 6-75323, No. 6-75324, No. 6-
No. 75325, No. 6-130538, No. 6-2587
57, 7-13287, 7-219110, 8-82887, 8-201953, 8-22
Complex cyanine dyes and complex merocyanine dyes described in JP-A Nos. 0678 and 8-220679, JP-A-49-11121 and JP-A-51-33622.
No. 51-115821, No. 51-115822
Nos. 58-72937, 61-203446, JP-A-2-25645, 3-15042, and 6-
Cyanine dyes described in US Pat.
493,747, 2,493,748, 2,5
19,001, JP-A-51-106422, 59
It is known that merocyanine dyes described in JP-A-214030 and JP-A-6-317868 are effective.
Some of these dyes reduce residual color contamination by introducing a water-soluble group into the molecule, but they are not sufficient, or decrease sensitivity due to a decrease in spectral sensitivity or aging of the coating solution. However, there was a problem such as the tendency to occur, and it was not yet satisfactory. JP-A-54-18726, 59
-135461, 62-446045, 5-2
JP-A Nos. 24337, 5-281644 and the like disclose techniques for increasing the spectral sensitivity and reducing the load of residual color contamination by using them together with a supersensitizer, but they are still insufficient.

Recently disclosed British Patent 2,282,23
No. 2, JP-A-6-313943 and JP-A-7-159920
The dyes described in U.S. Pat. Nos. 8,819,954 and EP 735,416 have a remarkable effect of improving residual color contamination, but the light-sensitive materials spectrally sensitized using these dyes are red to near red. Insufficient sensitization of outside light area,
JP-A-5-289222, JP-A-7-62256, JP-A-7-62256
The dyes disclosed in U.S. Pat. Nos. 2,613,11 and 8,137,042 effectively sensitize the long wavelength region of red light, but the level of residual color contamination is insufficient, and further improvement has been demanded.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material having improved spectral sensitivity in the red to near-infrared light wavelength region and free from residual color contamination. .

[0009]

The above object of the present invention is achieved by the following constitution.

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

[0011]

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Wherein Y ¹ , Y ² , Y ³ and Y ⁴ are each
And independently represents an —N (R) — group, an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, and one of Y ³ and Y ⁴ represents —
This is an N (R ⁴ )-group, and Y ¹ , Y ² and Y ³ are not simultaneously a sulfur atom. R ¹ has 8 carbon atoms substituted with a water-solubilizing group.
Represents the following aliphatic group, wherein R, R ² , R ³ and R ⁴ are each
Represents an aliphatic group, an aryl group or a heterocyclic group;
At least two groups of R ² , R ³ and R ⁴ replace the water solubilizing groups. Z ¹ represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group which may be condensed, and W represents an oxygen atom, a sulfur atom, a ＮN (R) group, ＝ C <
(E ¹ ) represents an (E ² ) group. L ¹ and L ² each independently represent a substituted or unsubstituted methine carbon, E ¹ and E ² each independently represent an electron-withdrawing group, and bond to each other to form a keto ring or an acidic heterocyclic ring. It may be formed. l ¹ is 0 or 1
Where M ¹ represents an ion necessary to offset the total charge of the molecule, and n ¹ represents a number required to neutralize the charge of the molecule. (2). In a silver halide photographic material comprising at least one photosensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is formed of a dye represented by the following general formula [S-II]. A silver halide photographic light-sensitive material comprising silver halide grains spectrally sensitized by at least one kind.

[0013]

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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 or a selenium atom. R ¹¹ represents an aliphatic group having a carbon number of 8 or less substituted with a water solubilizing group, R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ each represent an aliphatic group, an aryl group or a heterocyclic group; ¹⁰ , R
^12, at least three groups of R ¹³ and R ¹⁴ are substituting water-solubilizing group. Z ¹¹ represents a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic 5-membered ring optionally fused, L ¹¹ and L
Each of ¹² independently represents a substituted or unsubstituted methine carbon, M ¹¹ represents an ion required to offset the total charge of the molecule, and n ¹¹ represents a number required to neutralize the charge of the molecule. (3). The silver halide grains spectrally sensitized with at least one of the dyes represented by the above general formula [SI] or [S-II] contain 10 ^-8 to 10 ^-4 mol of iridium per mol of silver. A silver halide photographic light-sensitive material containing a compound and having a silver halide composition of at least 50 mol% of silver chloride.

Hereinafter, the present invention will be described in detail.

In the present invention, the above general formulas [SI] and [SI]
R], R ¹ , R ² , R ³ ,
Examples of the water-solubilizing group substituted for R ⁴ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include acid groups such as a sulfo group, a carboxy group, a phosphono group, a sulfate group, and a sulfino group.

R, R ¹ , R ² , R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R
^12, The aliphatic group represented by R ¹³ and R ¹⁴ for example, branched or straight chain alkyl group having 1 to 8 carbon atoms (e.g., methyl, ethyl, n- propyl, n- pentyl,
Each group such as isobutyl), an alkenyl group having 3 to 8 atoms (for example, each group such as 3-butenyl and 2-propenyl) or an aralkyl group having 3 to 8 carbon atoms (for example, each group such as benzyl and phenethyl) Group).

The aryl group represented by R, R ² , R ³ , R ⁴ , R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ is, for example, a phenyl group, and the heterocyclic group is, for example, a pyridyl group ( 2-, 4-), a pyrazyl group, a furyl group (2-), a thienyl group (2-), a sulfolanyl group, a tetrahydrofuryl group, a piperidinyl group, a pyrrole group, an imidazolyl group, and the like.

R, R ¹ , R ² , R ³ , R ⁴ , R ¹⁰ , R ¹¹ , R
¹² , R ¹³ and R ¹⁴ are each a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), an aryloxy group (eg, a phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (for example, 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, ethoxy group) It may be substituted with a substituent such as a carbonyl group, a butoxycarbonyl group, an aryl group (for example, a phenyl group, a carboxyphenyl group, etc.), an acyl group (for example, an acetyl group, a benzoyl group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl,
4-sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl,
Specific examples of the aryl group in which each group such as p-carboxybenzyl is substituted with a water-solubilizing group include p-sulfophenyl groups and p-carboxyphenyl groups, and the water-solubilizing group is substituted. Specific examples of such heterocyclic groups include groups such as a 4-sulfothienyl group and a 3-carboxypyridyl group.

In these, R ¹ and R ¹¹ are alkyl groups substituted with a sulfo group, and R, R ² , R ³ , R ⁴ ,
It is preferred that at least two of R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ are each a carboxymethyl group.

Examples of the 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ¹ include a basic heterocyclic ring which forms a cyanine dye, such as an oxazole ring (eg, oxazole, benzoxazole, naphthoxazole) etc),
Thiazole ring (eg, thiazolidine, thiazole, benzothiazole, naphthothiazole, etc.), imidazole ring (eg, imidazole, benzimidazole, naphthimidazole, etc.), selenazole ring (eg, selenazole, benzoselenazole, naphthoselenazole, etc.), tetrazole And a ring such as a ring (eg, tetrazole, benzotetrazole, naphthotetrazole), a pyridine ring (eg, pyridine, quinoline), and a pyrrole ring (eg, pyrrole, indole, indolenine).

Examples of the nitrogen-containing 5-membered heterocyclic ring represented by Z ¹¹ include the 5-membered heterocyclic rings described above for Z ¹ .

The above-mentioned heterocyclic ring represented by Z ¹ and Z ¹¹ may have a substituent at any position, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), Trifluoromethyl group, alkoxy group (for example,
Methoxy, ethoxy, butoxy, etc., unsubstituted alkoxy groups, 2-methoxyethoxy, benzyloxy, etc., substituted alkoxy groups, hydroxy group, cyano group, aryloxy group (eg, phenoxy, tolyloxy, etc.
Unsubstituted groups), aryl group (substituted or unsubstituted groups such as phenyl, p-chlorophenyl, p-tolyl, and p-methoxyphenyl), styryl group, and heterocyclic group (e.g., furyl, thienyl) Carbamoyl group (for example, carbamoyl, N-ethylcarbamoyl, etc.), sulfamoyl group (for example, sulfamoyl, N, N-dimethylsulfamoyl, etc.), acylamino group (for example, acetyl) Amino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl, etc.), sulfonamide group (eg, methanesulfonylamide, benzene) Each group such as sulfonamide), a sulfonyl group (for example, methanesulfonyl, p Each group) carboxy groups such as toluenesulfonyl, alkyl groups (e.g., methyl, ethyl, include any group in each group), isopropyl and the like.

Examples of the group substituted on the methine carbon represented by L ¹ , L ² , L ¹¹ and L ¹² include, for example, a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, phenyl group). , Carboxyphenyl, etc.),
There are groups such as an alkoxy group (for example, each group such as methoxy and ethoxy), an aryloxy group (for example, each group such as phenoxy and carboxyphenoxy), an aralkyl (for example, a group such as benzyl), and a fluorine atom.

The dye of the present invention generally has a high spectral sensitivity when one of the methine carbons represented by L ¹ and L ² is substituted, but has a property that the dye is liable to drift in a processing bath. It has a favorable effect of reducing residual color contamination.

The electron-withdrawing groups represented by E ¹ and E ² are selected from groups having a Hammett σ _p value of more than 0.3, and specifically include a cyano group and a carbamoyl group (for example, carbamoyl group, morpholino group). Carbonyl group, N-methylcarbamoyl group, etc.), alkoxycarbonyl group (for example,
Methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, morpholinosulfonyl group, N, N-dimethylsulfamoyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), sulfonyl group (For example, methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.).

The Hammett σ _p value is a substituent constant determined by Hammett et al. From the electronic effect of the substituent on the hydrolysis of the benzoate, and is described in Journal of Organic Chemistry, Vol. 23, 420-4.
27 (1958), Experimental Chemistry Course 14 (Maruzen Publishing Co.), Physical Organic Chemistry (Mc
(Graw Hill Book, 1940), Drag Design, Volume VII (Academic Press)
New York, 1976) and the structure-activity relationship of drugs (Nankodo, 1979).

Examples of the keto ring formed by E ¹ and E ² and the acidic hetero ring include the following compounds.

[0030]

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In the formula, R ^a and R ^b each represent a lower alkyl group, an aryl group or a heterocyclic group, and specific examples of the lower alkyl group include methyl, ethyl, propyl, 2-hydroxyethyl and 2-methoxyethyl. , Trifluoroethyl,
Examples include substituted and unsubstituted groups such as allyl, carboxymethyl, carboxyethyl, 2-sulfoethyl, and benzyl. Examples of the aryl group and heterocyclic group represented by R ^a and R ^b include those described above for R, R ² , R ³ , R ⁴ , R ¹⁰ , R ¹² , R ¹³ and R ^14. .

M ¹ and M ¹¹ each represent a cation or an acid anion. Specific examples of the cation include a proton,
Examples thereof include an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium) and an inorganic cation (for example, each cation such as lithium, sodium, and calcium). Specific examples of the acid anion include, for example, a halogen ion (for example, chlorine ion, Bromide ion, iodine ion, etc.), p-toluenesulfonic acid ion,
Examples include perchlorate ion and 4-boron fluoride ion. n ¹ and n ¹¹ are 0 when an inner salt is formed to neutralize the charge.

The 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.

[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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[0039]

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[0040]

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The above-mentioned compounds are described, for example, in "Cyanine Soybeans and Related Compounds" by FM Harama (1964, published by Inter Science Publishers), US Pat. Nos. 2,454,629 and 2, 493,748, British Patent 489,335, EP 730,008 and the like, and can be easily synthesized with reference to conventionally known methods.

The following are specific synthesis examples. Other exemplified compounds can be synthesized by the same method.

Synthesis Example 1 (Exemplified Compound S-9) 4-oxo-5- [3-carboxymethyl-4-oxo-5- [1-[[3- (3-sulfopropyl) -2 (3
H) -Benzoxazolylidene] methyl] propylidene] 1,3-thiazolidine-2-ylidene] -2-thiooxothiazolidine-3-ylacetic acid 3.29 g with dimethylsulfate 6.3 g and 120 at 130 ° C. The mixture was heated and stirred for minutes. After returning to room temperature, isopropyl ether was added to the viscous reaction product, and the mixture was stirred and allowed to stand. Then, the supernatant was decanted and removed. To this is added 4-oxo-2-thioxooxazolidin-
0.9 g of 3-ylacetic acid was added, followed by 10 ml of pyridine.
Was added thereto, and the mixture was gently heated to reflux for 20 minutes, and 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 0.5 g of a dye. The maximum absorption wavelength in the methanol solution was 589 nm.

The addition amount of the compound 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, the respective photosensitive dyes may be added to the emulsion simultaneously or separately at different times, and the order and time interval at that time may be arbitrarily determined according to 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).

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.I. H. The Theory of the Photographic Process by James 4
Edition (The Theory of the Photo)
graphic Process, fourth Ed
ition) pages 291-334 and the Journal of the American Chemical Society (Journ)
al of the American Chemica
l Society) 73, 3,100 (195
The developer described in 1) can be used effectively.

[0057]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) NaC was prepared so that the silver halide composition was 70 mol% of silver chloride and 30 mol% of silver bromide.
1, an aqueous solution containing gelatin and an antifoaming agent, an aqueous solution of silver nitrate and an antifoaming agent, 2 × 10 ⁻⁷ mol of K ₂ per mol of silver
RhCl ₆ and 1 × 10 ^-6 mole of Na ₂ I per mole of silver
NaCl containing rCl ₆ and an aqueous solution of KBr were mixed by a control double jet method to grow silver halide grains. At this time, silver potential EAg 130 mV, pH
It mixed under the conditions of 3.0.

Thereafter, the pH was lowered using denatured gelatin treated with phenyl isocyanate, desalted by the usual flocculation method, raised to pH, dispersed by adding water, and re-poured.
After adjusting the H and performing a desalting operation three times, the resultant is dispersed in gelatin, and has a silver halide grain having an average particle size of 0.18 μm, cubic, and monodispersed (coefficient of variation in particle size distribution of 13%). A silver halide emulsion was obtained.

The emulsion thus obtained was adjusted to pH 5.4 and a silver potential EAg of 50 mV.
and 0.5 g of sulfur flower, and then chemically sensitized at 54 ° C. for 50 minutes. At the end of ripening, 900 mg of 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene per mole of silver was added. Then, 50 mg of 1-phenyl-5-mercaptotetrazole and 200 mg of KI were added to obtain a silver halide emulsion A.

(Preparation of silver halide photographic light-sensitive material) A 100-μm-thick polyethylene terephthalate support having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941). On one side, the following formula (4)
, An antihalation layer of the following formula (1), a lower layer and an upper layer of the emulsion protective layer of the following formulas (3) and (2), and the following formula (5) on the other surface. And a backing protective layer of the following formula (6) were simultaneously coated to obtain silver halide photographic material samples 1 to 12.

Formulation (1) (Composition of photosensitive silver halide emulsion layer) Gelatin 1.5 mg / m ² Silver halide emulsion A Silver amount 3.5 mg / m ² Sensitizing dye: described in Table 1 10 mg / m ² fog Inhibitor: 5-nitroindazole 10 mg / m ² Antifoggant: 2-mercaptohypoxanthine 10 mg / m ² Surfactant: saponin 0.10 mg / m ² Surfactant: sodium sulfosuccinate isopentyl normal decyl ester 8.0 mg / M ² Hydroquinone 100 mg / m ² 8-Mercaptoadenine 3 mg / m ² Polymer latex P 0.5 mg / m ² Hardener H-1 60 mg / m ²

[0063]

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Formulation (2) (Emulsion protective layer upper layer composition) Gelatin 0.8 mg / m ² surfactant: S-2 (sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² surfactant: S-3

[0065]

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Matting agent: Monodispersed silica having an average particle diameter of 3.5 μm 20 mg / m ² Hardener: Formalin 30 mg / m ² Formulation (3) (Emulsion protective layer lower layer composition) Gelatin 0.6 g / m ² Surfactant : ^S-2 5mg / m 2 surfactant: S-3 2mg / m ² polymer latex P 0.3 g / m ² formulation (4) (anti-halation layer composition) gelatin 0.7 mg / m ² surfactant: saponin 0.1 mg / m ² 1-phenyl-5-mercaptotetrazole 2 mg / m ² Dye A

[0067]

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Formula (5) (Backing Layer Composition) Gelatin 2.4 mg / m ² Dyes (a), (b), (c)

[0069]

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Surfactant: sodium dodecylbenzenesulfonate 50 mg / m ² Prescription (6) (backing protective layer composition) Gelatin 1 mg / m ² Matting agent: monodisperse polymethyl methacrylate 50 mg / m ^{2 having an} average particle size of 5.0 μm Surfactant: S-2 10 mg / m ² Hardener: glyoxal 25 mg / m ² Hardener: 2-hydroxy-4,6-dichlorotriazine 35 mg / m ² Exposure to Nos. 1 to 12 was performed by using an image setter DT-R3075 manufactured by Dainippon Screen Co., Ltd., changing the laser intensity in a step pattern in which the screen percentage was changed stepwise. The evaluation was performed on a sample that had been subjected to 100 m ² development processing at a replenishment rate of 150 ml / m ² using a developing machine GR-27 and then processed.

[Developer Solution Formulation] (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-methylbenzotriazole 200 ml 1-phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount for adjusting the pH of the working solution to 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Disodium ethylenediaminetetraacetate 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg The above composition A and composition B in 500 ml of water when using a developer.
And finished to 1 liter. pH is 1
0.4.

[Fixing Solution Formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g acetic acid (90% W / W aqueous solution) 8.1 ml (composition B) pure water (ion-exchanged water) 17 ml sulfuric acid (50% W / W aqueous solution) 5.8 g aluminum sulfate (content in terms of Al ₂ O ₃ is 8.1) 26.5 g of the above composition A and composition B in 500 ml of water when using a fixing solution.
And finished to 1 liter. (PH =
Approximately 4.3) << Evaluation Method >> Sample No. was evaluated for sensitivity. The relative sensitivity of 1 was set to 100 and expressed as the reciprocal of the laser intensity.

The evaluation of the residual color was carried out by visually evaluating the unexposed sample which was processed, and expressed by five ranks. 5 is a level without residual color,
2 and 1 are levels at which residual colors cannot be used strongly.

Table 1 shows the results.

[0075]

[Table 1]

[0076]

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As is apparent from Table 1, the sample of the present invention had higher red light sensitivity and less residual color contamination than the comparative sample. That is, it is understood that the compound of the present invention satisfies both characteristics of high color sensitization efficiency and high dissolution.

[0078]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material in which the spectral sensitivity in the red to near-infrared light wavelength region is enhanced and the residual color contamination is eliminated.

Claims (3)

[Claims] 1. A silver halide photographic material comprising at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula [SI] A silver halide photographic material comprising silver halide grains spectrally sensitized by at least one of the dyes represented by Embedded image Wherein Y ¹ , Y ² , Y ³ and Y ⁴ are each independently —N
Represents an (R)-group, an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom, and one of Y ³ and Y ⁴ is —N (R ⁴ )
And Y ¹ , Y ² and Y ³ are not simultaneously a sulfur atom. R ¹ represents an aliphatic group having a carbon number of 8 or less substituted by a water solubilizing group, R, R ² , R ³ and R ⁴ each represent an aliphatic group, an aryl group or a heterocyclic group; R ² ,
At least two groups of R ³ and R ⁴ replace the water solubilizing groups. Z ¹ represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group which may be condensed, and W represents an oxygen atom, a sulfur atom, a ＮN (R) group, ＝ C <(E ¹ )
(E ² ) represents a group. L ¹ and L ² each independently represent a substituted or unsubstituted methine carbon, E ¹ and E ² each independently represent an electron-withdrawing group, and bond to each other to form a keto ring or an acidic heterocyclic ring. It may be formed. l ¹ represents an integer of 0 or 1, M ¹ represents an ion required to offset the total charge of the molecule, and n ¹ represents a number required to neutralize the charge of the molecule. ] 2. A silver halide photographic material comprising at least one photosensitive silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula [S-II] A silver halide photographic material comprising silver halide grains spectrally sensitized by at least one of the dyes represented by Embedded image [Wherein, Y ¹¹ , Y ¹² and Y ¹³ each independently represent -N
(R ¹⁰⁾ - represents group, an oxygen atom, a sulfur atom, a selenium atom. R ¹¹ represents an aliphatic group having a carbon number of 8 or less substituted with a water solubilizing group, R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ each represent an aliphatic group, an aryl group or a heterocyclic group; ¹⁰ ,
At least three groups of R ¹² , R ¹³ and R ¹⁴ replace a water solubilizing group. Z ¹¹ is an optionally condensed nitrogen-containing complex 5
L ¹¹ and L ¹² each independently represent a substituted or unsubstituted methine carbon, and M ¹¹ represents an ion required to offset the total charge of the molecule. And n ¹¹ represents the number necessary to neutralize the charge of the molecule. ] 3. The compound represented by the general formula [SI] or the general formula [S-
Silver halide grains which are spectrally sensitized by at least one dye represented by II] is, per mole of silver ^10-8
A silver halide photographic material comprising ^-4 mol of an iridium compound and having a silver halide composition of at least 50 mol% of silver chloride.