JPH10246930A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material high in spectral sensitivity and small in residual dye stains after processing, by incorporating a specified methine compound. SOLUTION: This photographic sensitive material contains at least one of the methine compounds represented by the formula in which Z<1> is an atomic necessary to form a thiazoline ring; each of V<1> and V<2> is an aliphatic or aromatic group each optionally substituted; each of L<1> Z-L<4> is methine group; M<1> is a counter ion necessary to neutralize the charge in the molecule; and n<1> is an integer of >=0 necessary to neutralize this charge. It is preferred that this photosensitive material is exposed to laser beams in the oscillation wavelength region of 620-690nm or the beams from a light emitting diode in the same wavelength region, and it is processed by using a developing solution in a pH of <=11.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having high sensitivity and little residual coloring after processing, and a method for exposing and processing the same.

[0002]

2. Description of the Related Art In recent years, there has been a demand for faster image forming processing of silver halide photographic materials. However, if the image forming processing time constituted by the steps of development, fixing, and washing with water is shortened, it becomes difficult to secure the time required for the elution or decomposition reaction of the dye or sensitizing dye contained in the photosensitive material. For this reason, even in a photographic light-sensitive material in which no color residue occurs after processing in the conventional processing, the color residue derived from these dyes and pigments may be significant.

[0003] Hitherto, the decolorization efficiency has been increased by making the dye water-soluble, and the processing solution has also been improved to improve the decolorization efficiency. That is, as a technique for reducing the color residue, for example, Research Disclosure, 207th
Volume, No. 20733 (July 1981),
(1) a method of adding a water-soluble stilbene compound, a nonionic surfactant, or a mixture of both to a developer;
There are known (2) a method in which a photographic element after bleaching and fixing is treated with an oxidizing agent to destroy a dye, and (3) a method using a persulfuric acid bleaching bath as a bleaching bath. However, even when these techniques are used, they are insufficient when the degree of color remaining is large.

Further, a method of decolorizing a dye is disclosed in
4-4739, 64-15734, 64-35
No. 440, JP-A Nos. 1-9451 and 1-221444.
And JP-A-1-35441 and JP-A-1-159645. Each of these methods is a method of adding an additive to a developing solution or the like, and has an effect of decoloring, but is not sufficiently satisfactory. Also, in a similar manner,
112169 and 63-136717 propose a decolorizing method by destroying the association of sensitizing dyes. This method is also a method in which an additive is added to the processing solution, but shows an excellent decolorization efficiency.
No. 0 (Japanese Patent Application No. 1-136579) is effective. Disadvantages include the fact that the decolorizing effect of the processing solution decreases over time or as it is used, so that management of the processing solution is required. As described above, sensitizing dyes having less color residue by making them water-soluble are also known (for example, US Pat. No. 4,252,502).
No. 24), many of which are technically required to be further improved, such as low spectral sensitivity or insufficient color retention.

On the other hand, in the field of printing photosensitive materials, the scanner method is used.
It has been widely used in recent years. Image form by scanner method
Various light sources have been put to practical use in commercial recording apparatuses. Special
Laser light source having an oscillation wavelength of 620-690 nm
(For example, He-N having an oscillation wavelength around 633 nm
e-laser, a semiconductor laser having an oscillation wavelength around 670 nm
With an emission wavelength between 620 and 690 nm
Light emitting diode light sources are popular in terms of stability and image quality
doing. Each point on the photosensitive material by scanning exposure is 10 ^-3−
10^-7Exposure in a short time of seconds, the feeling of use
Is optical material highly sensitive even in such a short exposure time?
High contrast is required.

A thiazole sensitizing dye is disclosed in Japanese Patent Application Laid-Open No. 3-105399 as a sensitizing dye having a sufficiently low level of residual color and a high spectral sensitivity. U.S. Pat. No. 5,116,722 discloses certain trinuclear merocyanine dyes that are exposed with a light source in the wavelength range of 600-690 nm. However, although these dyes have relatively high spectral sensitivity, the degree of color retention after processing has not been sufficiently satisfactory.

Thus, there has been a strong demand for a silver halide photographic light-sensitive material having high sensitivity in the wavelength range of 620 to 690 nm and having little residual color after processing.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high spectral sensitivity and little residual color after processing, and a method for exposing and processing the same. Another object of the present invention is to provide a silver halide photographic light-sensitive material characterized by performing processing with a low processing solution pH and a small processing solution replenishing amount.

[0009]

The object of the present invention has been achieved by the following means as a result of intensive studies. That is,

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

[0011]

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Where Z¹Forms a thiazoline ring
Represents the required atomic group. V¹And V ^TwoIs unsubstituted or
Aliphatic group having a substituent, or unsubstituted or substituted
Represents an aromatic group having L¹, L^Two, L^ThreeAnd L^Four
Represents a methine group. M¹Is the pair needed to neutralize the charge
Represents an ion, n¹Is necessary to neutralize intramolecular charge.
It represents a number of 0 or more. (2) The methine compound according to (1) is represented by the following general formula (II)
The halogenation according to (1), which is represented by the following formula:
Silver photographic photosensitive material. General formula (II)

[0013]

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Where Z¹¹Forms a thiazoline ring
Represents the required atomic group. V¹¹And V ¹²Is unsubstituted or
Aliphatic group having a substituent, or unsubstituted or substituted
V represents an aromatic group having¹¹And V¹²Group represented by
At least one has a carboxyl group or a sulfo group
Shows at least one substituted aliphatic or aromatic group
You. L¹¹, L¹², L¹³And L¹⁴Represents a methine group. M
¹¹Represents a counter ion required to neutralize the charge, and n¹¹Is
Indicates the number of zero or more necessary to neutralize the charge in the molecule.
You. (3) The methine compound according to (1) is represented by the following general formula (III)
The halogenation according to (1), which is represented by the following formula:
Silver photographic photosensitive material. General formula (III)

[0015]

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Where Z^{twenty one}Forms a thiazoline ring
Represents the required atomic group. V^{twenty one}And V ^{twenty two}Is a carboxyl group
Or an aliphatic group having at least one sulfo group substituted or
Represents an aromatic group. L^{twenty one}, L^{twenty two}, L^{twenty three}And L^{twenty four}Is meth
Represents a group. M^{twenty one}Is the counter ion required to neutralize the charge
And n^{twenty one}Is 0 required to neutralize the charge in the molecule.
Represents the above numbers. (4) Laser light having an oscillation wavelength of 620-690 nm
(1) to (3), characterized by exposing by a source
The method for exposing a silver halide photographic light-sensitive material as described above. (5) A light emitting die having an emission wavelength of 620-690 nm
(1) characterized by exposing with an auto light source.
Exposure method for silver halide photographic light-sensitive material described in (3)
Law. (6) The silver halide photographic light-sensitive material according to (1) to (3).
Is processed using a developer having a pH of 11.5 or less.
Processing silver halide photographic light-sensitive materials, characterized by the following:
Law. (7) The silver halide photographic light-sensitive material according to (1) to (3).
The replenishing amounts of the developer and the fixing solution are each 20-20.
0ml / m^Two Processing using an automatic processor
A method for processing a silver halide photographic material.

The methine compounds represented by the general formulas (I), (II) and (III) of the present invention will be described in detail below.

The thiazoline ring completed by Z ¹ , Z ¹¹ and Z ²¹ may have a substituent. Specific examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atom), having 1 to 12 carbon atoms, preferably 1 carbon atom
To 6 unsubstituted alkyl groups (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl), and an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (for example, methoxy, Ethoxy, propoxy, isopropoxy), hydroxy group, carbon number 2
To 12, preferably an alkoxycarbonyl group having 2 to 5 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), an alkylcarbonyloxy group having 2 to 10, preferably 2 to 5 carbon atoms (eg, acetyloxy, propionyloxy) ), A phenyl group, a hydroxyphenyl group, a group having 3 to 15, preferably 5 to 10 carbon atoms and having an amide group and an aromatic ring simultaneously (for example, p-acetylaminophenyl, m-acetylaminophenyl, Pyrrolecarboxamide,
m-hydroxybenzamide, 2,6-dihydroxybenzamide, 2-furancarboxamide, 2-thiophencarboxamide), a furyl group, a pyrrolyl group, etc., and more preferably an unsubstituted alkyl having 1 to 3 carbon atoms. Groups (eg, methyl, ethyl, n
-Propyl, isopropyl), preferably an alkoxy group having 1 to 3 carbon atoms (for example, methoxy, ethoxy, propoxy, isopropoxy), and a phenyl group, particularly preferably a methyl group, a methoxy group, and a phenyl group.

V ¹ , V ² , V ¹¹ and V ¹² are each independently unsubstituted or substituted carbon atoms having 1 to 1 carbon atoms.
2, preferably an aliphatic group having 1 to 8 carbon atoms, or an unsubstituted or substituted aromatic group having 1 to 12 carbon atoms, preferably 3 to 9 carbon atoms. Where V
At least one of the group represented by ¹¹ and V ¹² has as at least one substituent a carboxyl group or a sulfo group. The group represented by V ²¹ and V ²² is an aliphatic group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, or 1 to 12 carbon atoms, preferably 1 to 12 carbon atoms, substituted by at least one carboxyl group or sulfo group. Represents an aromatic group represented by Formulas 3 to 9. When V ¹ , V ² , V ¹¹ , V ¹² , V ²¹ and V ²² are substituted aliphatic groups, preferred examples of the substituent include a sulfo group, a carboxy group, a hydroxy group, a sulfate group, a halogen atom (for example, , A fluorine atom, a chlorine atom, a bromine atom), an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (the alkoxy group may be further substituted with a sulfo group or a hydroxy group), C2 to C5, preferably C2 to C3 alkoxycarbonyl, C1 to C4 alkylsulfonyl, sulfamoyl, unsubstituted or substituted carbamoyl (substituted by C1 to C4 alkyl) Carbamoyl group), substituted or unsubstituted phenyl group (preferable substituents are sulfo group, carboxy group and hydroxy group) Vinyl group. When V ¹ , V ² , V ¹¹ , V ¹² , V ²¹ and V ²² are a substituted aliphatic group, a preferred example is —CH
₂ CONHSO ₂ CH ₃ , 2- as a sulfoalkyl group
Sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 3-sulfobutyl group, 2
A carboxyalkyl group such as -hydroxy-3-sulfopropyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-carboxypropyl group, 3-carboxybutyl group; Examples of the alkyl group include a hydroxyethyl group, a 3-hydroxypropyl group, a 2-sulfatoethyl group, a 3-sulfatopropyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group,
2- (3-sulfopropoxy) ethyl group, 2- (2-hydroxyethoxy) ethyl group, ethoxycarbonylethyl group, methylsulfonylethyl group, sulfamoylalkyl group as 2-sulfamoylethyl group, carbamoylalkyl group 2-carbamoylethyl group, 2-
Preferred examples include a phenethyl group, a p-carboxyphenethyl group, an o-sulfophenethyl group, a p-hydroxyphenethyl group, an allyl group, a phenoxyethyl group, such as an N, N-dimethylcarbamoylethyl group,
More preferably, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-carboxypropyl Group. When V ¹ , V ² , V ¹¹ and V ¹² are unsubstituted aliphatic groups, preferred examples include methyl, ethyl, propyl, butyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. And more preferably a methyl group and an ethyl group.

When V ¹ , V ² , V ¹¹ and V ¹² are an unsubstituted aromatic group, preferred examples include a phenyl group, 2
-Pyridyl group, 3-pyridyl group, 4-pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, furanyl group, thiophenyl group, pyrrolinyl group, oxazolinyl group, thiazolinyl group, isoxazolinyl group, isothiazolinyl group, imidazolinyl group, Examples thereof include a pyrazolinyl group and a naphthyl group, and more preferred are a phenyl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a furanyl group, a thiophenyl group, and a pyrrolinyl group. When V ¹ , V ² , V ¹¹ , V ¹² , V ²¹ and V ²² are substituted aromatic groups, examples of the aromatic group include a phenyl group,
2-pyridyl group, 3-pyridyl group, 4-pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, furanyl group, thiophenyl group, pyrrolinyl group, oxazolinyl group, thiazolinyl group, isoxazolinyl group, isothiazolinyl group, imidazolinyl group , A pyrazolinyl group, a naphthyl group and the like. Examples of these substituents include an aliphatic group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and 1 to 12 carbon atoms, preferably 3 to 9 aromatic groups, sulfo groups, carboxy groups, hydroxy groups, sulfate groups, amino groups, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms), C1 to C6, preferably C1 to C6 4 unsubstituted or substituted alkoxy groups (alkoxy groups are further substituted with sulfo groups or hydroxy groups) Alkoxycarbonyl group having 2 to 5 carbon atoms, preferably 2 to 3 carbon atoms, alkylsulfonyl group having 1 to 4 carbon atoms, sulfamoyl group, unsubstituted or substituted carbamoyl group (1 to 4 carbon atoms). And a carbamoyl group substituted with an alkyl group). V ¹ , V ² , V ¹¹ ,
When V ¹² , V ²¹ and V ²² are substituted aromatic groups, a preferred example is a sulfo-substituted aromatic group having 2
-Sulfophenyl group, 3-sulfophenyl group, 4-sulfophenyl group, 3,5-disulfophenyl group, 2,4,
2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 4-carboxy-2 group as a carboxy-substituted aromatic group such as 6-trisulfophenyl group and 4-methyl-2-sulfophenyl group. -Methylphenyl group, 2-carboxy-4-methylphenyl group, 3-hydroxy-4-carboxyphenyl group and the like,
Examples of the aromatic group substituted with a hydroxy group include a 4-hydroxyphenyl group and a 3,5-dihydroxyphenyl group. More preferably, a 2-sulfophenyl group, 3-
Sulfophenyl group, 4-sulfophenyl group, 3,5-disulfophenyl group, 2,4,6-trisulfophenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 4- Carboki-2-
Examples include a methylphenyl group, a 2-carboxy-4-methylphenyl group, and a 3-hydroxy-4-carboxyphenyl group.

Particularly preferred as V ¹ , V ² , V ¹¹ and V ¹² are 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl and 2-carboxyethyl. , A 3-carboxypropyl group, an ethyl group, and a methyl group. Particularly preferred as V ²¹ and V ²² are a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group,
A sulfobutyl group, a carboxymethyl group, a 2-carboxyethyl group, and a 3-carboxypropyl group.

L ¹ , L ² , L ³ , L ⁴ , L ¹¹ , L ¹² , L
¹³ , L ¹⁴ , L ²¹ , L ²² , L ²³ and L ²⁴ each independently represent a methine group which may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 7 carbon atoms, such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, -Carboxyethyl, benzyl and the like), a substituted or unsubstituted aryl group (preferably having 6 to 10 carbon atoms, more preferably having 6 to 8 carbon atoms, for example, phenyl, toluyl, chlorophenyl, o-carboxyphenyl), A heterocyclic group (eg, pyridyl, thienyl, furanyl, pyridyl, barbituric acid), a halogen atom (eg, chlorine,
Bromine), an alkoxy group (eg, methoxy, ethoxy), an amino group (preferably having 1 to 12 carbon atoms,
More preferred are those having 6 to 12, for example, diphenylamino, methylphenylamino, 4-acetylpiperazin-1-yl) and the like.
A methyl group or an ethyl group is particularly preferred. The groups on these methine groups may be linked to each other to form a ring such as a cyclopentene ring or a cyclohexene ring, or may form a ring with an auxochrome.

M ¹ , M ¹¹ and M ²¹ can be represented by the formulas to indicate the presence or absence of a cation or anion when a counter ion is required to neutralize the ionic charge in the molecule of the compound. include. A compound is a cation,
Whether the compound is an anion or a compound having no net ionic charge depends on its molecular structure and substituents. Typical cations as counterions are hydrogen ions,
Examples include inorganic or organic ammonium ions (eg, triethylammonium ion, pyridinium ion), alkali metal ions (eg, sodium ion, potassium ion), and alkaline earth metal ions (eg, calcium ion, magnesium ion).
Typical anions as counterions include halide ions (eg, fluoride ion, chloride ion, bromide ion, iodide ion), arylsulfonate ions (eg, p-toluenesulfonate ion, p-toluene ion). Chlorobenzenesulfonic acid ion), alkylsulfonic acid ion (for example, methanesulfonic acid ion), aryldisulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid) Acid ions), alkyl sulfate ions (eg, methyl sulfate ion, ethyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate, pyrophosphate ion, acetate ion, trifluoromethanesulfonic acid ion, hexa Fluorophosphoric acid Such as emissions, and the like. As the counter ion, an ionic polymer, another organic compound having a reverse charge, or a metal complex ion (for example, bis (1,2-benzenedithiolato) nickelate (III) ion) can be used. Preferred as M ¹ are hydrogen ion, sodium ion, potassium ion, triethylammonium ion, pyridinium ion, iodide ion, bromide ion, chloride ion, methanesulfonate ion and p-toluenesulfonate ion,
More preferred are hydrogen ions, sodium ions,
Potassium ion and triethylammonium ion.

The general formulas (I) and (II) of the present invention are described below.
And specific examples of the methine compound represented by the general formula (III), but the scope of the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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In the present invention, general formulas (I) and (II)
And the synthesis of a methine compound represented by the general formula (III)
FM Harmer, Heterocyclic Compounds-Heterocyclic Compounds-Cyanine Soybeans and Related Compounds-
Cyanine dyes and related compounds-) '' (John
John Wiley & Sons, New York London, 1964), DM Starmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry. (Heterocyclic Compounds-S
pecial topics in heterocyclic chemistry), 482-51
Page 5 (John Wiley and Sons
& Sons), New York / London, 1977), and the synthesis examples of merocyanine compounds described in the references cited therein can be easily performed by those skilled in the art.

Next, a general method for synthesizing the compound according to the present invention will be described with reference to examples, but the method for synthesizing the compound according to the present invention is not limited thereto. (Scheme 1)

[0034]

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Synthesis of Exemplified Compound I-6 2.1 g of 2-methylthiazolinio-3- (3-propanesulfonate), 4.0 g of 2-methyl-1,1,3,3-tetramethoxypropane, anhydrous Acetic acid 10 ml, acetic acid 5
ml was placed in a 100 ml flask and stirred on a steam bath for 3 hours. Cool to room temperature, add 90 ml of ethyl acetate and add
After stirring for 0 minutes, the ethyl acetate layer was removed by decantation to obtain an oil. Acetonitrile 3
0 ml and 1.5 g of 3-ethylrhodanine were added and the mixture was stirred at room temperature, and 3 g of triethylamine was added dropwise. The reaction solution turned purple. After stirring for 1 hour, 40 ml of methanol was added to the reaction solution and stirred, and 1.2 g of sodium acetate dissolved in 50 ml of methanol was added dropwise. The resulting precipitate was collected by filtration, washed with methanol, and then purified by recrystallization from methanol to obtain Compound I-6. Other compounds of the present invention can be synthesized in the same manner as in the above synthesis examples.

The general formulas (I), (II) and (II) of the present invention
The methine compound represented by I) is preferably used as a spectral sensitizing dye, and other spectral sensitizing dyes used in combination therewith include, for example, `` Heterocyclic Compounds '' by FM Harmer Cyanine Soy and Related Compounds (Heterocycl
ic compounds-Cyanine dyes and related compounds
-) "(John Wile and Sands
y & Sons). Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure Vol. 176, 17643 (1978).
December 2013) Page 23, IV, J, or JP-B-49-255
No. 00, No. 43-4933, JP-A-59-19032
And No. 59-192242.

The general formulas (I), (II) and (II) of the present invention
The methine compound represented by I) can be present in any layer in a silver halide photographic light-sensitive material, and in a hydrophilic colloid layer containing photosensitive silver halide grains, the photosensitive silver halide It preferably exists in a state of being adsorbed on the particles.

The general formulas (I), (II) and (II) of the present invention
In order to incorporate the methine compound represented by I) into the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion, or may be dispersed in water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3
3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol,
A solvent such as 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or the like may be dissolved alone or in a mixed solvent and added to the emulsion. Further, as described in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24,185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving the same and adding this dispersion to an emulsion, No. 23,389, JP-B-44-27,
No. 555, JP-B-57-22091, etc., the dye is dissolved in an acid and the solution is added to the emulsion, or an acid or base is added to make an aqueous solution and added to the emulsion. As described in U.S. Pat. Nos. 3,822,135 and 4,006,026, an aqueous solution or a colloidal dispersion in the presence of a surfactant is added to an emulsion. Method, JP-A-53-102,
No. 733, JP-A-58-105,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As described in (1), a method in which a dye is dissolved using a compound that causes a red shift, and the solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The methine compound to be used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat.
No. 56; U.S. Pat. No. 4,225,666;
As disclosed in the specifications such as JP-A-184,142 and JP-A-60-196,749, the stage before silver halide grain formation and / or before desalting, during and / or during desalting. The period from after salting to before the start of chemical ripening,
As disclosed in the specification of JP-A-113,920, etc., at any time during or immediately before chemical ripening or during the process, or at any time before the emulsion is coated before the emulsion is coated after chemical ripening. May be. Also, U.S. Pat.
No. 5,666, JP-A-58-7,629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle formation step and during chemical ripening. It may be divided and added during the process or after the completion of chemical ripening, or may be divided and added before or during the chemical ripening or after the completion of the chemical ripening. May also be changed and added.

The amount of the compound represented by formulas (I), (II) and (III) of the present invention varies depending on the shape and size of silver halide grains. 0.1 to 4 mmol, preferably 0.1 to 4 mmol per
It is 2 to 2.5 mmol, and may be used in combination with another sensitizing dye.

The silver halide emulsion prepared according to the present invention can be used for both color photographic materials and black-and-white photographic materials. Examples of the color photographic light-sensitive material include color paper, color photographic film and color reversal film, and examples of the black-and-white photographic light-sensitive material include X-ray film, general photographic film, and printing photographic material.

The method of exposing the silver halide photographic light-sensitive material of the present invention will be described. Exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, laser light, light emitting diode, and CRT can be used. The exposure time is usually 1/1000 second to 1 second, which is usually used for cameras.
An exposure shorter than 1/1000 second, for example, an exposure of 1/10 ⁴ to 1/10 ⁶ seconds using a xenon flashlight can be used, and an exposure longer than 1 second can be used. If necessary, the spectral composition of light used for exposure can be adjusted by a color filter. Electron beam, X-ray, γ-ray, α
It may be exposed by light emitted from a phosphor excited by a line or the like.

In particular, in the present invention, a laser light source and a light emitting diode light source are preferably used. Laser light using helium-neon gas, argon gas, krypton gas, carbon dioxide gas, etc. as the laser oscillation medium, laser using solid such as ruby, cadmium as oscillation medium, other liquid lasers, semiconductor lasers, etc. There is. These laser beams are different from the light used for ordinary illumination, etc., and they are coherent light with a single frequency and the same phase and sharp direction. The photosensitive material needs to have spectral characteristics matching the oscillation wavelength of the laser used.

Light emitting diodes (LEDs) having various emission center wavelengths and luminous efficiencies depending on the composition and structure of the LED material constituting the element and the material used for the substrate are used. Examples of light-emitting diodes having an emission center wavelength in the visible region include GaP / GaP (555 nm), GaP: N / GaP (565 nm),
GaAs _0.15 P _0.85 : N / GaP (585 nm), GaAs _0.25 P _0.75 : N /
GaP (610 nm), GaAs _0.35 P _0.65 : N / GaP (630 nm), GaAs _0.6 P
_0.4 : N / GaAs (650 nm), GaAlAs: DH / GaAlAs (660 nm), GaP:
Zn, O / GaP (700 nm) and the like can be mentioned. Since the emission spectrum of these light-emitting diodes has a half width of about 40 nm, a silver halide photographic light-sensitive material for exposure as a light source needs to have spectral characteristics matching the emission wavelength of the light-emitting diode used. .

The silver halide photographic light-sensitive material of the present invention is preferably a laser light source having an oscillation wavelength of 620 to 690 nm, more preferably a He-Ne laser, 670.
a semiconductor laser having an oscillation wavelength in the vicinity of nm, and 62
This is a case where light is exposed by a light emitting diode having an emission wavelength in the range of 0 to 690 nm.

The processing method of the silver halide photographic light-sensitive material of the present invention will be described. In the photographic processing of the light-sensitive material using the present invention, any of known methods can be used, and a known processing solution can be used. The processing temperature is usually selected between 18 ° C and 50 ° C.
The temperature may be lower than 8 ° C or higher than 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied. Black-and-white developers include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone), aminophenols Known developing agents such as (for example, N-methyl-p-aminophenol) and isoascorbates (for example, sodium erythorbate) can be used alone or in combination. Color developers are generally
It consists of an alkaline aqueous solution containing a color developing agent. Color developing agents include known primary aromatic amine developers such as phenylenediamines (eg, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N -Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. In addition, L. F. A. Messon, "Photographic Processing Chemistry", Focal Press (1966), pages 226-229, U.S. Pat. Nos. 2,193,015, 2,592,364, JP-A-48-64933, etc. May be used.

The developing solution may further include a pH buffer such as a sulfite, a carbonate, a borate and a phosphate of an alkali metal, a development inhibitor such as a bromide, an iodide and an organic antifoggant, or an antifoggant. Agents and the like.
If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity improvers, U.S. Pat. No. 4,083,723
No. 2, the polycarboxylic acid chelating agent disclosed in West Germany (O
LS) No. 2,622,950.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. As the bleaching agent, for example, iron (III), cobalt (III)
And compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like. For example, organic complex salts of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediamine tetracomplex, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetracomplex iron (III) and ammonium ethylenediaminetetracomplex iron (III) are particularly useful. The ethylenediamine tetracomplex iron (III) complex is useful both in an independent bleaching solution and in a single bath bleach-fixing solution.

The bleaching or bleach-fixing solution is disclosed in US Pat.
Nos. 042,520 and 3,241,966, Shoko 4
In addition to the bleaching accelerators described in JP-A-5-8506 and JP-B-45-8836 and the thiol compounds described in JP-A-53-65732, various additives can also be added.
After the bleaching or the bleaching / fixing treatment, a washing treatment or a stabilizing bath treatment may be used.

More preferably, the compound represented by the general formula (I) of the present invention:
The methine compounds represented by (II) and (III) are used in a black-and-white silver halide photographic light-sensitive material, and the pH of the developing solution during the processing is 11.5 or less. This is the case when processing is carried out using an automatic developing machine whose amount is 10-500 ml / m ² , particularly preferably 20-200 ml / m ² . The automatic developing machine is described in JP-A-4-369643.

Next, the specific constitution of the silver halide photographic light-sensitive material of the present invention will be described. The silver halide emulsion according to the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide and silver iodobromide as silver halide, but the silver chloride content is 30 mol% or more. Is preferable, and 50 mol% or more is more preferable. The content of silver iodide is preferably at most 5 mol%, more preferably at most 2 mol%.

The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but is preferably cubic or tabular.

The photographic emulsion used in the present invention is P. Glafki
by des Chimie et Physique Photographique (Paul Mo
ntel, 1967), GFDufin Photographi
c Emulsion Chemistry (The Focal Press, 1966
Year), Making and Coating Photo by VLZelikman et al
graphic Emulsion (The Focal Press, 1964)
It can be prepared using the method described in, for example.

That is, any of an acidic method and a neutral method may be used, but it is preferable to carry out the reaction under acidic conditions. As a method for reacting the soluble silver salt and the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds, described in JP-A-53-82408 and JP-A-55-7.
No. 7737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The addition amount of the silver halide solvent varies depending on the type of the compound used, the target grain size, and the halogen composition.
A mole of 10 ^-5 to 10 ^-2 mole is preferred.

According to the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above paragraph to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
08 μm to 0.4 μm.

The silver halide emulsion used in the present invention is:
It may contain a metal belonging to Group VIII. In order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound and the like. Preferred as these heavy metals are metal coordination complexes, and hexacoordinate complexes represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (wherein, M is a heavy metal selected from Ir, Ru, Rh, Re, and Cr. L is a bridging ligand. Y is oxygen or sulfur. M = 0, 1, 2 and n = 0, 1, 2
-, 3-. Preferable examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyanate Nate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. In order to increase the sensitivity, an iron compound is preferably contained, and a metal coordination complex having a cyan ligand as a ligand is particularly preferable. These compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the compounds, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, bromic acid,
Hydrofluoric acid, etc.) or alkali halides (for example, K
Cl, NaCl, KBr, NaBr, etc.) can be used. It is also possible to add and dissolve another silver halide grain doped with these compounds in advance. Specific examples of the metal coordination complex are shown below. 1. [Rh (H ₂ O) Cl ₅ ] ^2-2 . [RuCl _6] ^3- 3. [Ru (NO) Cl ₅ ] ^2-4 . [RhCl _6] ^3- 5. [Ru (H ₂ 0) Cl ₅ ] ^{2 -6} . _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 7. [Ru ₂ Cl ₁₀ O] ^2-8 . [Re (NO) Cl ₅ ] ^2-9 . [Ir (NO) Cl _5] ^2- 10. [Ir (H ₂ 0) Cl _5] ^2- 11. [Re (H ₂ 0) Cl _5] ^2- 12. [RhBr _6] ^3- 13. [ReCl _6] ^3- 14. [IrCl _6] ^3- 15. _{[Re (NS) Cl 4 (SeCN} ) ] ^{2 _-.} 16 [Cr (CN) _6] ^3- 17. [Fe (CN) _6] ^3-

The addition amount of these compounds is from 1 × 10 ^-8 to 1 × 10 ^-2 mol, preferably from 5 × 10 ^-8 to 2 × 10 ^-4 mol, per mol of silver in the silver halide emulsion. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. .

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Other US Patents 1,5
No. 74,944, No. 2,410,689, No. 2,
278,947, 2,728,668, 3,501,313, and 3,656,955, German Patent 1,422,869, JP-B-56
No. 24937, JP-A-55-45016 and the like can also be used. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ^{-5 to} 5 × 10 ^-4 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compound represented by (IX).
Further, a low-decomposition active selenium compound can also be preferably used. The low decomposition active selenium compound is AgNO3 10
Of a selenium compound, 0.5 mmol of a selenium compound, and 40 mmol of a 2- (N-morpholino) ethanesulfonic acid buffer at a water / 1,4-dioxane volume ratio of 1/1 (pH
= 6.3) is a selenium compound having a half-life of 6 hours or more when reacted at 40 ° C. This low-decomposition active selenium compound is disclosed in Japanese Patent Application No. Hei 7-28881.
It is preferable to use the compound examples of SE-04 to SE-10.

The tellurium sensitizer used in the present invention is a compound that forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and the compounds described in Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferred.

[0062] The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, Preferably 10 ^{−7 to} 5 × 10
^Use about ^-4 moles. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, and the pAg
Is 6-11, preferably 7-10, and the temperature is 40-95 ° C, preferably 45-85 ° C.
As the noble metal sensitizer used in the present invention, gold, platinum,
Palladium, iridium and the like can be mentioned, but gold sensitization is particularly preferable. The gold sensitizer used in the present invention may have an oxidation number of gold of +1 or +3. Specifically, chloroauric acid,
Potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide and the like, and 10 ^-7 to 10 ⁻ per mol of silver halide. ^{About 2} moles can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. The silver halide emulsion of the present invention is disclosed in European Patent (EP) -2.
A thiosulfonic acid compound may be added by the method described in U.S. Pat. The addition amount of the thiosulfonic acid compound varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but it is 1 × 10 ⁻⁷ mol or more per mol of silver halide. , 5
× 10 ^-2 mol or less is preferred. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (e.g., those having different average grain sizes, different halogen compositions, different crystal habits, different chemical habits, Those with different conditions) may be used in combination.

There are no particular restrictions on other additives of the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 1
Volume 76 Item 17643 (RD17643) and 1
87, Item 18716 (RD18716) can be referred to. RD17643 and RD18
The locations of various additives described in Table 716 are listed below (Table 1).

[0064]

[Table 1]

The dye will be described in more detail. Colloidal silver and dyes are used in the light-sensitive material of the present invention to prevent irradiation and halation, in particular, to separate the spectral sensitivity distribution of each light-sensitive layer and to ensure safety against safelight. Such dyes include, for example, U.S. Pat. Nos. 506,385, 1,177,429 and 1,1.
No. 31,884, No. 1,338,799, No. 1,38
5,371, 1,467,214, 1,43
Nos. 8,102 and 1,553,516, JP-A-48-48
Nos. 85, 130, 49-114, 420, 52-
Nos. 117, 123, 55-161, 233, 59
-111,640, JP-B-39-22,069, JP-B-43-13,168, JP-B-62-273527, U.S. Pat. Nos. 3,247,127 and 3,469,985,
Oxonol dyes having a pyrazolone nucleus, a barbitur nucleus or a barbituric acid nucleus described in U.S. Pat. No. 4,078,933, and the like, U.S. Pat. Nos. 2,533,472 and 3,37.
Other oxonol dyes described in JP-A No. 9,533, British Patent No. 1,278,621, JP-A Nos. 1-134447 and 1-183652, British Patent 575,691
Nos. 680,631, 599,623, 78
6,907, 907,125, 1,045,6
09, U.S. Pat. No. 4,255,326, and JP-A-59-326.
Azo dyes described in JP-A No. 211,043;
Azomethine dyes described in US Pat. Nos. 2,865,752 and -100,116 and 54-118,247; British Patent Nos. 2,014,598 and 750,031;
Anthraquinone dyes described in U.S. Pat.
No. 8,009, No. 2,688,541, No. 2,53
No. 8,008, British Patent Nos. 584,609 and 1,21
0,252, JP-A-50-40,625, 51-
No. 3,623, No. 51-10,927, No. 54-11
8,247, JP-B-48-3,286, and 59-3
7,303 and the like, JP-B-28-3,082, JP-B-44-16,594 and JP-A-59-303.
-28,898 and the like; triarylmethane dyes described in British Patent Nos. 446,538 and 1,335,422; JP-A-59-228,250; , 075,653, 1,15
No. 3,341, No. 1,284,730, No. 1,47
No. 5,228, 1,542,807, etc .; and merocyanine dyes described in U.S. Pat. Nos. 2,843,486, 3,294,539, and JP-A-1-291247. And the like.

In order to prevent the diffusion of these dyes, the following methods are mentioned. For example, a dye may be ballasted to make it diffusion resistant. Further, for example, a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye is coexisted in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules is disclosed in U.S. Pat. 564
Nos. 4,124,386 and 3,625,694. Further, a method of dyeing a specific layer using a dye solid which is insoluble in water is disclosed in JP-A-56-1263.
No. 9, No. 55-155350, No. 55-155351
No. 63-27838, No. 63-197943,
It is disclosed in European Patent No. 15,601 and the like. Further, a method of dyeing a specific layer using metal salt fine particles to which a dye is adsorbed is disclosed in U.S. Pat. Nos. 2,719,088 and 2,496,8.
No. 41, 2,496,843, JP-A-60-452
No. 37, etc.

As the antifoggants and stabilizers of the above additives, azoles (for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, Benzotriazoles, aminotriazoles, etc., mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, preferably 1-phenyl -5-mercaptotetrazole), thioketo compounds (eg, oxazolinethione), azaindenes (eg, triazaindenes, tetraazaindenes, pentaazaindene) S, preferably 4-hydroxy-substituted-1,3,3a, 7- tetraazaindenes), benzenethiosulfonate benzenesulfinate, it can be preferably used benzenesulfonic acid amide.

The color coupler is preferably a non-diffusible one having a hydrophobic group called a ballast group in the molecule or a polymerized one. The coupler may be either 4-equivalent or 2-equivalent to silver ion.
Further, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor during development (a so-called DIR coupler) may be included. Further, the product of the coupling reaction may be colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. Preferred examples are described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144.
Page 14 upper right column line 14 to page 18 upper left column last line and page 30 upper right column line 6 to page 35 lower right column line 11; EP 4, page 15 to line 27, page 5 line 30 to Page 28, last line, page 45, 29
Lines 31 to 31, page 47, lines 23 to 63, line 50.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers and the like, and yellow couplers are acylacetamide couplers. (For example, benzoylacetoanilides, pivaloylacetoanilides), and the like, and examples of cyan couplers include naphthol couplers and phenol couplers. U.S. Pat. Nos. 3772002 and 27721 as cyan couplers
No. 62, No. 3758308, No. 4126396, No. 4334011, No. 4327173, No. 34466
Phenol couplers having an ethyl group at the meta position of the phenol nucleus, 2,5-diacylamino-substituted phenol couplers, and phenylureido groups at the 2 position described in JP-A Nos. 22,43333999, 4445159, and 4427767. Phenol couplers having an acylamino group at the 5-position and naphthols substituted with a sulfonamide or amide at the 5-position are preferred because of their excellent image fastness. The couplers and the like can be used in combination of two or more in the same layer in order to satisfy the characteristics required for the light-sensitive material, and the same compound can be added to two or more different layers.

Hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarins,
Spirochroman, p-alkoxyphenols, hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenolic hydroxyl groups of these compounds were silylated and alkylated. Ether or ester derivatives are typical examples.
Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer on a support, and at least one of the emulsion layers contains the methine compound of the above formula (I). Is preferred. As the support used in the present invention, a transparent film such as a cellulose triacetate film or polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. In order to increase the reflectance in the visible light wavelength region, coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, and hydrophobic resins containing dispersed light-reflecting substances Used as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support having a reflective layer, or a reflective material used in combination, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, There are a polyamide film, a polycarbonate film, a polystyrene film, a vinyl chloride resin and the like, and these supports can be appropriately selected depending on the purpose of use.

[0072]

Next, the present invention will be described in more detail with reference to Examples, but it should be understood that the present invention is by no means restricted to such specific Examples. Example 1 Preparation of Emulsion A 1 liquid 1 liter water 20 g gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml sodium chloride 27 0.1 g Potassium bromide 21.0 g Ammonium hexachloroiridate (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridate (III) (0.001% aqueous solution) 6 ml

Solution 2 and solution 3 were added simultaneously to solution 1 kept at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally a silver chloroiodobromide cubic emulsion A containing 70 mol% of silver chloride and having an average grain size of 0.25 μm.
I got Preparation of Coated Samples Emulsion A was added with 3.8 × 10 ⁻⁴ mol / mol Ag of the compound shown in Table 5 and subjected to spectral sensitization. Furthermore, KBr 3.4 ×
10 ⁻⁴ mol / mol Ag, compound 1 3.2 × 10 ⁻⁴ mol / mol Ag, compound 2 8.0 × 10 ⁻⁴ mol / mol A
g, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound 3
0 × 10 ⁻⁴ mol / mol Ag, compound 4 was 6.0 × 10 ^−4.
Mol / mol Ag, 35 wt% polyethyl acrylate latex based on gelatin, 20 wt% colloidal silica having a particle size of 10 μm based on gelatin, and 4 wt% compound 5 based on gelatin were added to a polyester support. the Ag3.7g / m ^2, gelatin 1.6 g / m ²
It was applied so that On this, a protective layer upper layer and a protective layer lower layer of the following composition, and a UL layer of the following composition under this were applied. Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound 6 (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound 7 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound 8 20 mg / m ² Lower layer of protective layer Gelatin 0.5 g / m ² Compound 9 15 mg / m ² 1,5-Dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate Latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound 5 40 mg / m ² Compound 10 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound 11 40 mg / m ² Compound 12 20 mg / m ² Compound 13 90 mg / m ² 1,3-divinylsulfonyl-2-propanol 60 mg / m ² Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound 5 120 mg / m ² Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio) , Average particle size 0.25μ) 200mg / m ²

[0076]

Embedded image

[0077]

Embedded image

Evaluation of photographic performance The obtained sample was exposed to xenon flash light having an emission time of 10 ^-5 seconds through an interference filter having peaks at 633 nm and 670 nm and a continuous wedge. Sensitometry was performed using -710S under the conditions shown in Table 2. The reciprocal of the exposure amount giving a density of 1.5 is defined as the sensitivity, and the relative sensitivity when the sensitivity of Sample No. a-6 is set to 100. The residual coloring after the treatment was visually evaluated on a 10-point scale. The one with the most residual coloring was set to 10, and the one with the least remaining coloring was set to 1.

[0079]

[Table 2]

The developer and fixer used have the compositions shown in Tables 3 and 4. Developer composition

[0081]

[Table 3]

Fixer composition

[0083]

[Table 4]

(Evaluation Results)

[0085]

[Table 5]

(Comparative dye)

[0087]

Embedded image

The comparative dye C-1 which is a thiacarbocyanine dye (JP-A-3-59637, page 3, lower left column, compound I-1) has a poor sensitivity balance between 633 nm and 670 nm, and lacks sensitivity. I have. Also, the residual coloring is very large. This is presumably because this dye shows J-association. Comparative dye C-2 which is a rhodacyanine dye (JP-A-3-59637, page 9, upper left column, compound II-3)
In 6), the balance between the 633 nm and 670 nm sensitivities is poor, and the sensitivity at 670 nm is very low. Also, there are many residual colorings. Comparative dye C-3 which is a trinuclear merocyanine dye
(US Pat. No. 5,116,722, pages 7-8, compound I-12) has a good balance between 633 nm and 670 nm sensitivity, but lacks sensitivity. Also, there are many residual colorings. Comparative dye C-4 having a benzoxazole ring structure
(JP-A-60-131533, page 8, Example 11)
Although the sensitivity of 633 nm and 670 nm is well-balanced, the sensitivity is insufficient. Also, there are many residual colorings. The dye C-5 having a thiazole ring structure for comparison has poor sensitivity at 633 nm and 670 nm, and particularly lacks sensitivity at 633 nm. Also, there are many residual colorings. Compared with these dyes, the dyes I-1, I-11, I-13, I-19, I-19 of the present invention
-20, I-22 and I-27 are 620-690 nm
Has a gentle sensitivity distribution in the range, the sensitivity difference in exposure by the light source within this wavelength range is small. In addition, it can be seen that sample numbers a-6 to a-12 have very little residual coloring after the treatment.

The exposure of each sample was performed at 633 nm and 670 n.
He-Ne laser instead of m interference filter, 67
The same result was obtained by using a semiconductor laser having an oscillation wavelength of 0 nm and a light emitting diode having an emission wavelength of 670 nm.

Example 2 Table 6 shows the results when the linear speed of the automatic developing machine was increased in Example 1 and the developing time was set to 20 seconds.

[0091]

[Table 6]

Incidentally, 633 of sample number a-6 of Example 1 was used.
The nm sensitivity and the 670 nm sensitivity are set to 100 as a reference.
Samples b-6 to b- using the methine compound of the present invention
Sample No. 12 maintains the same sensitivity and the same level of residual color as the corresponding sample of Example 1 even after rapid processing, whereas Samples b-1 to b-5 using the comparative dyes It can be seen that the sensitivity tends to decrease and the residual coloring tends to increase as compared with the corresponding dyes of Example 1. Thus, the sample using the methine compound of the present invention exhibits particularly excellent performance in rapid processing.

Example 3 A silver chlorobromide emulsion having a coating silver amount of 3.6 g / m ² and a silver chloride content of 70 mol% per mol of silver was coated on the automatic developing machine FG-710S used for the evaluation of sensitivity. The film has a blackening ratio of 5
0%, 180 ml / m ² with developer and fixer
150m ² running processing was carried out while replenishing with. The sample of Example 1 was processed using this liquid, and the sensitivity and the residual color were evaluated. Table 7 shows the results.

[0094]

[Table 7]

From Table 7, it can be seen that Samples c-6 to c-12 using the methine compound of the present invention have the same sensitivity and color retention as the corresponding samples of Example 1 even with the low replenisher. While the samples c-1 to c-5 using the comparative dyes tend to have reduced sensitivity and increased color retention after processing as compared with the corresponding dyes of Example 1 respectively. You can see that there is. As described above, the sample using the dye of the present invention shows particularly excellent performance with respect to the low replenishment processing solution.

Example 4 A coated sample containing only the compound represented by the compound was prepared in the same manner as in Example 1, and the photographic performance was evaluated in the same manner as in Example 1. As a result, the sample of the present invention had higher sensitivity at 633 nm and 670 nm and less color retention after processing than the sample using the comparative dye, even in the emulsion containing no nucleating agent.

[0097]

The silver halide photographic material having a methine compound according to the present invention has high sensitivity to a laser light source having an oscillation wavelength of 620-690 nm and a light-emitting diode light source having an emission wavelength of 620-690 nm. It has little residual coloring and shows good performance even in rapid processing and low replenishment processing.

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[Procedure amendment]

[Submission date] August 22, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0083

[Correction method] Change

[Correction contents]

[0083]

[Table 4] In use, it is diluted at a ratio of 2 parts of water to 1 part of the above concentrated liquid. The pH of the working solution is 4.8.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction contents]

Example 2 Table 6 shows the results when the linear speed of the automatic developing machine was increased and the developing time was set to 12 seconds in Example 1.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0093

[Correction method] Change

[Correction contents]

Example 3 A silver chlorobromide emulsion having a coating amount of 3.6 g / m ² and a silver chloride content of 70 mol% per mol of silver was coated on the automatic developing machine FG-710S used in the evaluation of sensitivity. The film has a blackening ratio of 5
0%, 180 ml / m ^{2 with} replenishment of mother liquor for both developer and fixer
150m ² running processing was performed while replenishing with. The sample of Example 1 was processed using this liquid, and the sensitivity and the residual color were evaluated. Table 7 shows the results.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/31 G03C 5/31 5/395 5/395

Claims (7)

[Claims] 1. A methine compound represented by the following general formula (I):
Characterized by containing at least one of the following:
Silver halide photographic material. General formula (I)Where Z¹Is the group of atoms necessary to form a thiazoline ring
Represents V¹And V ^TwoIs unsubstituted or has a substituent
Aliphatic group or unsubstituted or substituted aromatic
Represents a group. L¹, L^Two, L^ThreeAnd L^FourRepresents a methine group
Represent. M¹Indicates the counter ion required to neutralize the charge.
Then n¹Is 0 or more necessary to neutralize the charge in the molecule
Represents the number of 2. The methine compound according to claim 1, wherein
2. The method according to claim 1, wherein the compound is represented by the general formula (II).
Silver halide photographic material. General formula (II)Where Z¹¹Is the group of atoms necessary to form a thiazoline ring
Represents V¹¹And V ¹²Is unsubstituted or has a substituent
Aliphatic group or unsubstituted or substituted aromatic
V represents a group¹¹And V¹²At least one of the groups represented by
One is that the carboxyl or sulfo group has at least one
Represents a substituted aliphatic group or an aromatic group. L¹¹,
L¹², L¹³And L¹⁴Represents a methine group. M¹¹Is the charge
Represents a counter ion required for neutralization, and n¹¹Is the electron in the molecule
Represents the number of zero or more necessary to neutralize the load. 3. The silver halide photographic material according to claim 1, wherein the methine compound according to claim 1 is represented by the following general formula (III). General formula (III) In the formula, Z ²¹ represents an atom group necessary for forming a thiazoline ring. . V ²¹ and V ²² represent an aliphatic group or an aromatic group substituted with at least one carboxyl group or sulfo group. L ²¹ , L ²² , L ²³ and L ²⁴ represent a methine group. M ²¹ represents a counter ion necessary for neutralizing the charge,
n ²¹ represents a number of 0 or more necessary to neutralize the charge in the molecule. 4. The method according to claim 1, wherein the exposure is performed by a laser light source having an oscillation wavelength of 620-690 nm.
4. The method for exposing a silver halide photographic light-sensitive material according to any one of items 1 to 3. 5. The method for exposing a silver halide photographic light-sensitive material according to claim 1, wherein the exposure is performed by a light-emitting diode light source having an emission wavelength of 620 to 690 nm. 6. A method for processing a silver halide photographic light-sensitive material, comprising processing the silver halide photographic light-sensitive material according to claim 1 using a developer having a pH of 11.5 or less. . 7. The silver halide photographic material according to claim 1, wherein the replenishing amounts of the developing solution and the fixing solution are each 20.
Method for processing a silver halide photographic material, which comprises processing using an automatic developing machine is -200ml / m ^2.