JPH09244175A - Methine compound and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material having high spectral sensitivity and forming a fine photographic image almost free from a residual color after development by incorporating a specified methine compd. and a silver halide photographic sensitive material contg. the urethine compd. as sensitizing dyes. SOLUTION: This sensitive material contains at least one kind of methine compd. represented by formula I or II. In the formula I, each of R11 -R14 is H or an alkyl, R15 is an alkyl substd. by at least one sulfo group, R16 is an aryl or a heterocyclic group, each of L11 and L12 is methine, M11 is a counter ion required to neutralize an electric charge and n11 is an integer of 0-4. In the formula II, each of R21 and R22 is H, each of R23 and R24 is an alkyl and R25 , R26 , L21 , L22 , M21 and n21 have the same meanings as R15 , R16 , L11 , L12 , M11 and n11 in the formula I, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a methine compound useful as a sensitizing dye for a silver halide photographic light-sensitive material, and a silver halide photographic light-sensitive material containing the methine compound.

[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, when the image forming processing time of the silver halide photographic light-sensitive material according to the conventional technique is shortened, the time necessary for the elution or decomposition reaction of the dye or the sensitizing or desensitizing dye contained in the light-sensitive material cannot be secured, Even in the case where no color residue is generated in the conventional processing time, there is a problem that the color residue due to these dyes or pigments becomes remarkable.

[0003] Hitherto, decolorization efficiency has been increased by making such dyes water-soluble, and improvements have also been made in processing solutions for improving the decolorization efficiency. That is, as a method for reducing the color residue, for example, Research Disclosur (Research Disclosur)
e), Vol. 207, 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. (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, these methods are not sufficient when the degree of color residue is large, and do not actively promote the desorption and elution processes of the sensitizing dye, and are therefore not particularly suitable for rapid decolorization treatment.

Further, a method of decolorizing a dye is disclosed in
4-4739, 64-15734, 64-35.
No. 440, JP-A Nos. 1-9451 and 1-21444.
No. 1-35441, No. 1-159645 and the like. All of these are methods of adding an additive to a development processing solution and the like, and although they have a decolorizing effect, they are not sufficiently satisfactory. In a similar manner, Japanese Patent Application Laid-Open No.
No. 0151 and No. 1-35441 propose a decolorizing treatment method by breaking the association of sensitizing dyes. This method is also a method of adding an additive to the processing solution,
It shows excellent decolorization efficiency, and the method described in JP-A-2-71260 is particularly effective. As a drawback, the decolorizing effect of the treatment liquid decreases with time or as it is used, and therefore management of the treatment liquid is required.

On the other hand, as described above, sensitizing dyes having a small amount of residual color by making them water-soluble are known, but most of them have low spectral sensitivity or the degree of residual color is not sufficient. Problems (eg, US Pat. No. 425
0224). JP-A-3-105399 discloses a thiazole-based sensitizing dye as a sensitizing dye having a sufficiently small color residue and a high spectral sensitivity. However, although this thiazole dye is excellent in spectral sensitivity, it cannot be said that the color residue is sufficiently reduced in the developing step.

As described above, in order to desorb a dye in an image forming process such as a photograph, the dye is generally desorbed by eluting the dye. However, a dye excellent in both the spectral sensitivity and the degree of residual color is obtained. Not been. On the other hand, with the spread of small-sized development processing equipment (minilabs), it is desirable that the decolorization process be performed in the shortest possible time by the simplest method. Further, the waste liquid of the processing agent is as small as possible in order to prevent environmental pollution. The advent of systems and dyes is desired.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
It is to provide a novel methine compound having a high spectral sensitivity and having little color residue after image formation such as development processing.
Secondly, it is to provide a silver halide photographic light-sensitive material having high spectral sensitivity and capable of obtaining a good photographic image with less color residue after image formation such as development processing.

[0008]

As a result of intensive studies, the object of the present invention has been achieved by the following silver halide photographic material and methine compound.

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

[0010]

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In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or an alkyl group. R ₁₅ represents an alkyl group substituted with at least one sulfo group.
R ₁₆ represents an aryl group or a heterocyclic group. L ₁₁ and L ₁₂ each independently represent a methine group. M ₁₁ represents a counter ion necessary for neutralizing the charge, and n ₁₁ represents an integer of 0 or more and 4 or less. (2) The silver halide photographic light-sensitive material according to (1), wherein the methine compound represented by the general formula (I) is a methine compound represented by the following general formula (II). General formula (II)

[0012]

[Chemical 6]

In the formula, R ₂₁ and R ₂₂ represent a hydrogen atom,
R ₂₃ and R ₂₄ each independently represent an alkyl group. R
₂₅ is synonymous with R ₁₅ , R ₂₆ is synonymous with R ₁₆ , L ₂₁ and L ₂₂ are synonymous with L ₁₁ and L ₁₂ , M ₂₁ is synonymous with M ₁₁ , n ₂₁ is n _11.
Is synonymous with (3) The silver halide photographic light-sensitive material according to (1), wherein the methine compound represented by the general formula (I) is a methine compound represented by the following general formula (III). General formula (III)

[0014]

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Where R₃₁And R₃₂Represents a hydrogen atom,
R₃₃And R₃₄Each independently represents an alkyl group. R
₃₅Represents an alkyl group substituted with one sulfo group. R₃₆Is
R₁₆Synonymous with L₃₁And L₃₂Is L₁₁And L₁₂Synonymous with,
M₃₁Is M₁₁Synonymous with n₃₁Is n ₁₁Is synonymous with (4) The methine compound represented by the general formula (I) is
Characterized by being a methine compound represented by the general formula (IV)
The silver halide photographic light-sensitive material as described in (3) above. General formula (IV)

[0016]

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In the formula, R ₄₁ and R ₄₂ represent a hydrogen atom,
R ₄₃ and R ₄₄ each independently represent an alkyl group. R
₄₅ represents an alkyl group in which one sulfo group is substituted. R ₄₆ represents a phenyl group or a pyridyl group. L ₄₁ and L ₄₂ are synonymous with L ₁₁ and L ₁₂ , M ₄₁ is synonymous with M ₁₁ , n ₄₁ is n _11.
Is synonymous with (5) A methine compound represented by the general formula (IV) according to (4).

[0018]

DETAILED DESCRIPTION OF THE INVENTION General formulas II), (I
The methine compounds represented by I), (III) and (IV) will be described in detail below.

R₁₁, R₁₂, R₁₃, R₁₄Is a hydrogen atom or
Represents an alkyl group. R_{twenty three}, R_{twenty four}, R ₃₃, R₃₄, R₄₃And
And R₄₄Represents an alkyl group. R₁₁, R₁₂, R₁₃, R₁₄,
R_{twenty three}, R_{twenty four}, R₃₃, R₃₄, R₄₃And R₄₄Is represented by
The group preferably has 1 to 12 carbon atoms, more preferably
Is an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms
You. Examples of the substituent include a hydroxy group, a sulfo group, and a sulfur group.
Rufato group, carboxy group, halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, iodine atom), carbon number
Alkoxy having 1 to 6, preferably 1 to 4 carbon atoms
Group (alkoxy group may further have a substituent)
I), an alkylsulfonyl group having 1 to 4 carbon atoms, a sulfone
Famoyl group (Alkyl group having 1 to 4 carbon atoms
May be substituted), carbamoyl group (having 1 carbon atom)
It may be further substituted with an alkyl group of Ishi 4),
Substituted or unsubstituted phenyl group, substituted or unsubstituted hetero
Examples thereof include a ring group, a vinyl group and an allyl group.

Preferred examples of R ₁₁ and R ₁₂ include a hydrogen atom, a methyl group, an ethyl group, a propyl group and a butyl group, more preferably a hydrogen atom, a methyl group and an ethyl group, and most preferably It is a hydrogen atom. R ₁₃ , R ₁₄
Preferred examples of are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, and the like, and an alkyl group is more preferable, and a methyl group, ethyl, and a propyl group are particularly preferable. R ₂₃ , R ₂₄ , R ₃₃ , R
Preferred examples of ₃₄ , R ₄₃ and R ₄₄ include a methyl group,
Examples thereof include an ethyl group, a propyl group, a butyl group and a benzyl group, with a methyl group, an ethyl group and a propyl group being particularly preferable.

R ₁₅ and R ₂₅ are substituted with at least one sulfo group and have 1 to 10 carbon atoms, preferably 2 carbon atoms.
And represents an alkyl group of 6 to 6. R ₃₅ and R ₄₅ each represent an alkyl group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms, which is substituted with one sulfo group. These substituents may further have a substituent. Examples of the substituent include a hydroxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group, a vinyl group, an allyl group, etc. Is mentioned. Preferred examples of R ₁₅ , R ₂₅ , R ₃₅ and R ₄₅ are 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 3-bromo-4-sulfobutyl group and 5-sulfo. Although a pentyl group and the like can be mentioned, particularly preferable ones are 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group and 4-sulfobutyl group.

R ₁₆ , R ₂₆ and R ₃₆ have 6 to 1 carbon atoms.
2, preferably 6 to 9 substituted or unsubstituted aryl group, 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms
Represents a substituted or unsubstituted heterocyclic group. Examples of the substituent include 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.
A substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, cyclopropyl), having 6 to 1 carbon atoms
5, preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (eg, phenyl, tolyl, o-carboxyphenyl, o-methoxyphenyl), a heterocyclic group (eg, pyridyl, thienyl, furyl, pyrazyl, thiazolyl). , Morpholyl), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), carbon number 1
To 12, preferably an alkoxy group having 1 to 8 carbon atoms (eg methoxy group, ethoxy group), an amino group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atom (eg, amino group, dimethylamino group, methylphenylamino) Base,
4-acetylpiperazin-1-yl group) and the like. Examples of the aryl group of R ₁₆ , R ₂₆ and R ₃₆ include:
Phenyl group, tolyl group, p-chlorophenyl group, o-hydroxyphenyl group, m-methoxyphenyl group, m-
Examples thereof include (phenylsulfamoyl) phenyl group and p- (phenylcarbamoyl) phenyl group.
Preferred are phenyl group and tolyl group. Examples of the heterocyclic group for R ₁₆ , R ₂₆ and R ₃₆ include 2-pyridyl group,
Examples include 3-pyridyl group, 4-pyridyl group, pyrazyl group, thienyl group, furyl group, thiazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group and morpholyl group, and preferably 2-pyridyl group and 3-pyridyl group. Group, 4-pyridyl group, pyrazyl group, and thienyl group.

R ₄₆ has 6 to 12 carbon atoms, preferably 6 carbon atoms
A substituted or unsubstituted phenyl group having 9 to 9 carbon atoms, or a substituted or unsubstituted pyridyl group having 5 to 12 carbon atoms, preferably 5 to 8 carbon atoms. Particularly preferred as R ₁₆ , R ₂₆ , R ₃₆ and R ₄₆ are a phenyl group and a 3-pyridyl group.

L ₁₁ , L ₁₂ , L ₂₁ , L ₂₂ , L ₃₁ , L ₃₂ , L
₄₁ and L ₄₂ each independently represent a substituted or unsubstituted methine group. Examples of the substituent include a carbon number of 1 to 8,
Preferably, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, cyclopropyl), a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms ( For example, phenyl, tolyl, o-carboxyphenyl, o-methoxyphenyl), heterocyclic group (for example, pyridyl, thienyl, furyl, pyrazyl, thiazolyl, morpholyl), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, Iodine atom), an alkoxy group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (eg, a methoxy group,
Ethoxy group), an amino group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (eg, amino group, dimethylamino group, methylphenylamino group, 4-acetylpiperazin-1-yl group) and the like. L ₁₁ , L ₁₂ , L ₂₁ ,
L ₂₂ , L ₃₁ , L ₃₂ , L ₄₁ and L ₄₂ are particularly preferably an unsubstituted methine group or a methine group substituted with a methyl group or an ethyl group.

M ₁₁ , M ₂₁ , M ₃₁ and M ₄₁ are for indicating the presence or absence of a cation or anion when a counterion is required to neutralize the ionic charge in the molecule of the compound. Included in the formula. Whether it is a cation, an anion, or a compound having no net ionic charge depends on its molecular structure and substituents.

Typical cations as counterions are 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). In addition, typical anions as counterions include halide ions (for example, fluoride ion, chloride ion, bromide ion, iodide ion), aryl sulfonate ions (for example, p-toluene sulfonate ion, p ion). -Chlorobenzene sulfonate ion), alkyl sulfonate ion (for example, methane sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene disulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalene) Disulfonate ion), alkylsulfate ion (for example, methylsulfate ion, ethylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate, pyrophosphate ion, acetate ion, trifluoromethanesulfonate ion, Hexafluorophosphoric acid On and the like. The counterion may be an ionic polymer, another organic compound having an opposite charge, or a metal complex ion (for example, bis (1,2-benzenedithiolato) nickel (III) acid ion).

Preferred as M ₁₁ , M ₂₁ , M ₃₁ and M ₄₁ are sodium ion, potassium ion, triethylammonium ion and pyridinium ion,
More preferred are sodium ion, potassium ion and triethylammonium ion. n ₁₁ ,
n ₂₁ , n ₃₁ , and n ₄₁ are 0 or more and 4 required for neutralizing the charge.
The following integers are represented, and 1 is preferable.

In the general formula (IV), preferably R ₄₃
And R ₄₄ each represent a methyl group, an ethyl group, a propyl group or a butyl group, and R ₄₅ represents a 2-sulfoethyl group,
3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 3-bromo-4-sulfobutyl group or 5-
Represents a sulfopentyl group, and R ₄₆ represents a phenyl group or 3-
A compound which represents a pyridyl group, among which R ₄₃ and R ₄₄ each represent a methyl group, an ethyl or a propyl group, and among them, R ₄₅ represents a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group. Group or 4
A sulfobutyl group.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0030]

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[0031]

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[0032]

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[0033]

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The methine compound represented by the general formula (I) can be easily synthesized by those skilled in the art by referring to the following literatures and the synthesis examples described in the literatures cited therein. a) Dokradi Academia Nauk SSSR (Do
kl. Akad. Nauk SSSR), 177, 869 (19)
67 years). b) "Heterocyclic Compounds-Cyanine Die and." by FM Harmer.
Related Compounds (Heterocyclic compound
s-Cyanine dyes and related compounds-) '' (John Wiley & Sons),
New York London, 1964).

C) DM Starmer (DM St
Armer), "Heterocyclic Compounds-Special topics
in heterocyclic chemistry, pp. 482-515 (John ・
Willie & Sons (New York, London, 1977).

D) Japanese Patent Publication Nos. 47-4085 and 46
-549, U.S. Patent 3,625,698, U.S. Patent 3,567,458. Specific synthesis examples are shown below, but the synthesis method of the methine compound of the present invention is not limited thereby. Other dyes represented by the general formula (I) can also be synthesized according to the following synthesis method.

[0037]

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Synthesis of Intermediate II-1 3- (2,4,4-trimethyloxazolinio) propanesulfonate 4.6 g, N, N'-diphenylformamidine 7.9 g, acetonitrile 30 ml, acetic anhydride 2 ml. The mixture was placed in a 100 ml three-necked flask and stirred on a steam bath for 1 hour. After cooling, the precipitated crystals were collected by filtration and washed with acetonitrile. Yield 3.5g.

Synthesis of Intermediate II-2 3- (2-Ethyl-4,4-dimethyloxazolinio)
Propane sulfonate 4.6 g, N, N'-diphenylformamidine 9.9 g, acetonitrile 50 ml,
0.5 ml of acetic anhydride was placed in a 100 ml three-necked flask and stirred on an oil bath at 120 ° C. for 1 hour. After cooling, the solvent was distilled off under reduced pressure and the residue was formed on a Sephadex LH-20 column to obtain the target compound. Yield 2.8g.

Synthesis of Intermediate II-3 5.0 g of 3- (2,4,4-trimethyloxazolinio) propane sulfonate, 7.5 g of triethyl orthopropionate, 10 ml of m-cresol in 100 m
The mixture was placed in a 3-necked flask and stirred on a steam bath for 6 hours. After cooling, the precipitated crystals were collected by filtration and washed with ethyl acetate.
Yield 5.5g.

Synthesis of Exemplified Compound I-1 1.7 g of Intermediate II-1, 1.0 g of 4-oxo-3-phenyl-2-thioxoxazoline, ethanol
20 ml and acetic anhydride 0.5 ml were put into a 100 ml flask and heated to 80 ° C. 1 g of triethylamine was added and reacted for 50 minutes. After cooling, the solvent was distilled off under reduced pressure,
The residue was dissolved in 50 ml of ethanol. 50 ml of a 2% ethanol solution of sodium acetate was added dropwise, and the precipitated yellow crystals were collected by filtration. When recrystallized from methanol and purified,
800 mg of the target compound was obtained. λ max 436 nm.

Synthesis of Exemplified Compound I-2 2.1 g of Intermediate II-2, 1.5 g of 4-oxo-3-phenyl-2-thioxoxazoline, 50 ml of acetonitrile, 0.5 ml of acetic anhydride, 1 ml of triethylamine in 100 ml flask. Take 1 on steam bath
Allowed to react for hours. After cooling, the solvent was distilled off under reduced pressure, and the residue was dissolved in 50 ml of ethanol. 50 ml of a 2% ethanol solution of sodium acetate was added dropwise, and the precipitated yellow crystals were collected by filtration. Recrystallization from methanol and purification gave 450 mg of the desired compound. λmax 448 nm.

Synthesis of Exemplified Compound I-3 1.6 g of Intermediate II-1, 1.0 g of 4-oxo-3-phenyl-2-thioxoxazoline, pyridine 2
0 ml and 0.5 ml of acetic anhydride were placed in a 100 ml flask and reacted on a steam bath for 2 hours. After cooling, the solvent was distilled off under reduced pressure, and the residue was purified with a Sephadex LH-20 column. 50 ml of the obtained pyridinium salt was added to ethanol.
Dissolved in 50 ml of 2% ethanol solution of sodium acetate
Is added dropwise, and 100 ml of isopropyl alcohol is further added.
Was added and the precipitated yellow crystals were collected by filtration. Recrystallization from methanol and purification gave 450 mg of the desired compound. λ max 432 nm.

Synthesis of Exemplified Compound I-8 Intermediate II-1 1.7 g, 4-oxo-3-phenyl-2-thioxoxazoline 1.0 g, acetonitrile 20 ml, acetic anhydride 1 ml, triethylamine
1 ml was placed in a 100 ml flask and reacted at room temperature for 1 hour. After cooling, the solvent was distilled off under reduced pressure, and the residue was purified with a Sephadex LH-20 column. The obtained triethylammonium salt was dissolved in 50 ml of ethanol, 50 ml of a 2% sodium acetate ethanol solution was added dropwise, and the precipitated yellow crystals were collected by filtration. Recrystallization from methanol and purification yielded 970 mg of the target compound. λmax 44
2 nm.

The compounds represented by the general formulas (I), (II), (III) and (IV) of the present invention can be present in any layer in a silver halide photographic light-sensitive material. In the hydrophilic colloid layer containing silver halide grains, it is preferably present in a state of being adsorbed on the photosensitive silver halide grains.

The sensitizing dyes represented by formulas (I), (II), (III) and (IV) of the present invention can be incorporated in the silver halide emulsion of the present invention by directly adding them to the emulsion. May be dispersed, or water, methanol, ethanol,
Propanol, acetone, methyl cellosolve, 2,2
3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2
It may be added to the emulsion by dissolving it in a solvent such as propanol or N, N-dimethylformamide alone or in a mixed solvent. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is placed in an emulsion. As described in JP-B-46-24,185 and the like, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding the dispersion to an emulsion, JP-B-44 No. 23,389, Japanese Patent Publication No. 44-2
No. 7,555, Japanese Patent Publication No. 57-22,091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an aqueous solution is prepared by coexisting an acid or a base into the emulsion. As described in US Pat. No. 3,822,135, US Pat. No. 4,006,026, etc.,
A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion;
No. 2,733 and JP-A-58-105,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, JP-A-51-74,6.
As described in No. 24, it is also possible to use a method of dissolving a dye by using a red-shifting compound and adding the solution to an emulsion. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step of emulsion preparation which has been recognized to be useful so far. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat. No. 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196,749, etc., 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 such as JP-A-13,920, etc., at any time during the process immediately before or during the process of chemical ripening, and at any time before the application of the emulsion before the coating after the chemical ripening. May be. Also, U.S. Pat.
No. 66, 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 forming step and during the chemical ripening step. Alternatively, it may be added separately after the completion of the chemical ripening, or before the chemical ripening or during the process and after the completion, and may be added separately. May be added.

The amount of the compounds represented by the general formulas (I), (II), (III) and (IV) used in the present invention varies depending on the shape and size of the silver halide grains. It is 0.1 to 4 mmol, preferably 0.2 to 2.5 mmol, and may be used in combination with other sensitizing dyes. 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. There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure
sure) Volume 176 Item 17643 (RD17643)
187 items and item 18716 (RD18716)
Can be referred to. The places where the various additives are described in RD17643 and RD18716 are listed below (Table 1).

[0049]

[Table 1]

Colloidal silver and dyes are used in the light-sensitive material of the present invention to prevent irradiation and halation, particularly to separate the spectral sensitivity distribution of each light-sensitive layer and to secure safety against safelight. Examples of such dyes include the dyes described in Japanese Patent Application No. 6-175430, page 20, and means for preventing the diffusion of these dyes are described in pages 20 to 21. You can list the method.

Among the above additives, antifoggants and stabilizers include 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 oxazoline thione), 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 type having a hydrophobic group called a ballast group in the molecule or a polymerized type. 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.

Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers. (For example, benzoylacetanilides, pivaloylacetanilides), and the like, and 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.

As the anti-fading agent, 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.

Photographic processing of a light-sensitive material using the present invention includes
Any of the 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, but may be lower than 18 ° 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) and 3-pyrazolidones (eg, 1-phenyl-3-
Known developing agents such as pyrazolidone) and aminophenols (for example, N-methyl-p-aminophenol) can be used alone or in combination. The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers,
For example, 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",
226-229 of the Focal Press (1966)
, U.S. Pat. Nos. 2,193,015 and 2,592,3
No. 64, JP-A-48-64933, etc. may be used.

The developer may be a pH buffering agent such as alkali metal sulfite, carbonate, borate, and phosphate, a development inhibitor such as bromide, iodide, or an organic antifoggant, or an antifoggant. Agents and the like can be included.
If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler, Fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, US 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. Examples of bleaching agents include iron (III) and cobalt (III)
Compounds of polyvalent metals such as chromium, chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used. For example, organic complex salts of ferricyanide, dichromate, iron (III) or cobalt (III), for example, ethylenediamine tetracomplex, nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosophenol and the like can be used. Of these, potassium ferricyanide, ethylenediaminetetracomplex iron (III) sodium salt and ethylenediaminetetracomplex iron (III) ammonium salt are particularly useful. The ethylenediaminetetracomplex iron (III) complex salt is useful both in the independent bleaching solution and in the one-bath bleach-fixing solution.

Bleaching or bleach-fixing solutions are described 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.

As the support used in the present invention, a transparent film such as a cellulose triacetate film or polyethylene terephthalate, which is usually used in 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 synthetic paper,
A transparent support provided with a reflective layer or combined with a reflective substance, for example, a glass plate, a polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film, a polystyrene film, a vinyl chloride resin, etc. Yes, these supports can be appropriately selected depending on the purpose of use.

Exposure for obtaining a photographic image may be carried out by using a usual method. That is, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, laser, LED,
Any of various known light sources such as a CRT can be used. The exposure time is usually 1/1000 second to 1 second, which is usually used in a camera, or is shorter than 1/1000 second, for example, 1/10 ⁴ to 1/1 / using a xenon flash lamp.
Exposures of 10 ⁶ seconds can be used, and exposures longer than 1 second can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light can also be used for exposure. Further, exposure may be performed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like.

[0061]

EXAMPLES Examples will be described below in order to more specifically explain the contents of the present invention, but the present invention is not limited to these examples. Example 1 1N silver nitrate aqueous solution, 0.98 mol of potassium bromide and
An aqueous solution containing 0.02 mol of potassium iodide was mixed with 2% by weight of deionized bone gelatin, 1.5% by weight of ammonia,
In an aqueous solution containing 0.04% of potassium bromide, the temperature was 5
The mixture was mixed by the double jet method while maintaining the temperature at 0 ° C. to obtain a silver bromide emulsion. This emulsion was washed with water and desalted, and then gold-sensitized and sulfur-sensitized so as to obtain optimum sensitivity. The emulsion thus obtained had an average diameter of 1 μm and an average thickness of 0.1 μm.
The particles were tabular grains having a size of 15 μm. To 45 g of this emulsion, a methanol solution of a sensitizing dye according to the present invention shown in (Table 2) was added and mixed and stirred at 40 ° C. Further, 10 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 15 g of a 10% gel of deionized gelatin and 55 ml of water were added, and coated on a polyethylene terephthalate film base as follows. did.

[0062] coating solution amount is silver amount 2.5 g / m ^2, set so that the amount of gelatin 3.8 g / m ^2, dodecylbenzenesulfonic acid such as the amount of gelatin 1.0 g / m ² in the upper layer Sodium 0.22 g / l, p-sulfostyrene sodium homopolymer 0.50 g / l, 2,4
An aqueous solution containing 3.1 g / liter of sodium dichloro-6-hydroxy-1,3,5-triazine and 50 g / liter of gelatin was simultaneously applied.

These samples were exposed to light of 3200 lux at a color temperature of 2854K for 10 ^-2 seconds using a xenon lamp and 10 ^-6
Optical wedge exposure for 2 seconds was performed. After the exposure, it was processed for 45 seconds using a CEPROS-M automatic developing machine manufactured by Fuji Photo Film Co., Ltd. The density of the developed film was measured using a densitometer manufactured by Fuji Photo Film Co., Ltd. to determine white light sensitivity and fog. The reference point of the optical density for which the sensitivity was determined is [fog +
0.3]. The sensitivity is shown as relative sensitivity to 100 (reference). Further, as a sample for measuring a color residue, a sample which was similarly processed by the automatic developing machine without exposing each sample was used. Using a 607 color analyzer manufactured by Hitachi, Ltd., the absorbance of the remaining sensitizing dye at the absorption maximum wavelength was measured by a reflection measurement method.

The following compounds were used as comparative compounds other than the present invention. (Comparative compound)

[0065]

Embedded image

The obtained results are shown as relative values (Table-
See 2).

[0067]

[Table 2]

As is clear from the results shown in Table 2, the sensitizing dye represented by the general formula (I) is excellent in both sensitivity and residual color. (The color residue in the table is preferably 0.09 or less, and if it exceeds this value, it will be discerned as a color residue by careful observation, and it will be difficult to put it on the market.
Anything over 1 is discriminated as a significant residual color. ) For example, the sample obtained by the dye I-8 has greatly improved residual color as compared with the compound (C-2) used for comparison, and shows high sensitivity. It can also be seen that the compounds of the invention have low fog. From these results, it can be understood that the sample containing the sensitizing dye according to the present invention has less color residue, higher sensitivity, and lower fog than those containing the comparative compound.

Example 2 An aqueous solution of silver nitrate, 1.5 × 10 ⁻⁷ mol of potassium pentachloroacharodium (III) / mol of silver, and 1 mol of silver
2 × 10 ^-7 mol hexachloroiridium (II
I) A potassium bromide / potassium chloride mixed aqueous solution containing potassium acid was mixed with a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione by the double jet method to give an average particle size of 0.22 μm and a silver chloride content of 70%. Mol%
To obtain a silver chlorobromide emulsion. Conversion is performed by adding 1 × 10 ^-3 mol of potassium iodide aqueous solution per mol of silver.
After washing with water according to the flow curation method, a methanol solution of a sensitizing dye according to the present invention shown in (Table 3) was added.

Then, an aqueous gelatin solution was added to adjust the pH to 5.
After adjusting to 9, pAg 7.3, sodium benzenesulfonate, benzenesulfinic acid, sodium thiosulfate pentahydrate and chloroauric acid were added and heated at 60 ° C. for 45 minutes for chemical sensitization. As a stabilizer, 4-hydroxy-
150 mg of 6-methyltetrazaindene was added, and further 100 mg of proxel was added as a preservative. The silver halide emulsion thus prepared was coated on a polyethylene terephthalate film base which had been subjected to an antistatic treatment in the same manner as in Example 1. The sample was exposed in exactly the same manner as in Example 1, and FG-680A manufactured by Fuji Photo Film Co., Ltd. was automatically developed using GD-D1 as a developing solution and GR-F1 as a fixing solution (each manufactured by Fuji Photo Film Co., Ltd.). The treatment was performed at 35 ° C. for 30 seconds using a machine. The measurement of sensitivity and residual color was performed in the same manner as in Example 1. The results (Table-3)
It was shown to.

[0071]

[Table 3]

From the results shown in (Table 3), it can be understood that the present invention provides a high sensitivity even in the silver chlorobromide emulsion, and the color residue and the fog are suppressed low.

Example 3 The multilayer color photographic light-sensitive material (Test No. 4-1) shown in Sample 13 of Example 4 of Japanese Patent Publication No. 5-18412 and
A sample (Test No. 4-2) was prepared by adding Exemplified Compound I-11 according to the present invention in place of the sensitizing dye represented by Compound I-1 in this photographic light-sensitive material, and after storing at room temperature for 2 days, Exposure and development were performed by the method described in the above patent, and the red light sensitivity was measured. In addition, development processing was performed without exposure, and the color residue after the processing was measured. The results are shown in (Table-4).

[0074]

[Table 4]

As is clear from the results shown in (Table 4), it can be seen that the present invention is excellent in sensitivity and residual color even in a multilayer color photographic light-sensitive material.

[0076]

The silver halide photographic light-sensitive material of the present invention comprises:
It has high sensitivity and good color retention and fog.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one methine compound represented by the following general formula (I). General formula (I) In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or an alkyl group. R ₁₅ represents an alkyl group substituted with at least one sulfo group. R ₁₆ represents an aryl group or a heterocyclic group. L ₁₁ and L ₁₂ each independently represent a methine group. M ₁₁ represents a counter ion necessary for neutralizing the charge, and n ₁₁ represents an integer of 0 or more and 4 or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the methine compound represented by the general formula (I) is a methine compound represented by the following general formula (II). General formula (II) In the formula, R ₂₁ and R ₂₂ represent a hydrogen atom, and R ₂₃ and R _22
24 independently represents an alkyl group. R ₂₅ is synonymous with R ₁₅ , R ₂₆ is synonymous with R ₁₆ , L ₂₁ and L ₂₂ are L ₁₁ and L
Synonymous with ₁₂ , M ₂₁ is synonymous with M _11, and n ₂₁ is synonymous with n ₁₁ . 3. A methine compound represented by the general formula (I).
Is a methine compound represented by the following general formula (III):
The silver halide photographic light-sensitive material according to claim 1,
material. General formula (III):Where R₃₁And R₃₂Represents a hydrogen atom, R₃₃And R
₃₄Each independently represents an alkyl group. R₃₅Is a sulfo group
Represents an alkyl group substituted by 1. R₃₆Is R₁₆Synonymous with,
L₃₁And L₃₂Is L₁₁And L₁₂Synonymous with, M₃₁Is M₁₁When
Synonymous, n₃₁Is n ₁₁Is synonymous with 4. The silver halide photographic light-sensitive material according to claim 1, wherein the methine compound represented by the general formula (I) is a methine compound represented by the following general formula (IV). General formula (IV) In the formula, R ₄₁ and R ₄₂ represent a hydrogen atom, and R ₄₃ and R _42
44 each independently represents an alkyl group. R ₄₅ represents an alkyl group in which one sulfo group is substituted. R ₄₆ represents a phenyl group or a pyridyl group. L ₄₁ and L ₄₂ are L ₁₁ and L
Synonymous with ₁₂ , M ₄₁ is synonymous with M _11, and n ₄₁ is synonymous with n ₁₁ . 5. A methine compound represented by the general formula (IV) according to claim 4.