JP2000231174A - Silver halide photosensitive material containing methine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photosensitive material having high sensitivity containing a new methine compd. by incorporating at least one kind of silver halide emulsion containing a specified methine compd. SOLUTION: The photosensitive material contains at least one kind of silver halide emulsion containing a compd. expressed by the formula of (Dye1)-(L1-[Dye2]n1)m1. In the formula, each of Dye1 and Dye2 is a methine chromophore, and at least one or more of Dye1 and Dye2 is a cyanine chromophore containing a benzoxazole nuclear, Dye1 has higher adsorption power to silver halide particles than Dye2, L1 is a connecting group, and each of n1 and m1 is an integer 1 to 5. In the compd. of the formula, each of Dye1 and Dye2 is an oxacarbonocyanine chromophore. Further, in the compd. of the formula, the reduction potential of Dye1 is higher than the reduction potential of Dye2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel methine compound, particularly to a silver halide light-sensitive material containing a linked methine compound in which two chromophores are linked.

[0002]

2. Description of the Related Art Methine compounds have been conventionally used as spectral sensitizing dyes for silver halide photographic materials. Techniques which have heretofore been known as techniques for improving the light absorption of silver halide grains are described below. In order to improve the light absorptivity per grain, it is necessary to increase the adsorption density of the sensitizing dye to the silver halide grains. Adsorb, no more. Several proposals have been made to solve this problem. PBGilman, Jr. et al.
ographic Sciece and Engineering, Volume 20, Volume 3
No. 97, p. 97 (1976), a cationic dye was adsorbed on the first layer, and an anionic dye was adsorbed on the second layer using electrostatic force. GBBird et al. In U.S. Pat.
In 316, multiple dyes were adsorbed on silver halide grains in multiple layers and sensitized by the contribution of Forster-type excitation energy transfer. Sugimoto et al., JP-A-63-138,341, JP-A-64-84,
In No. 244, spectral sensitization was performed by energy transfer from the luminescent dye. However, all of these attempts have attempted to adsorb the dye in an amount equal to or greater than the saturated adsorption amount to the silver halide grains, but none of them has a high sensitivity-improving effect and has problems such as an increase in intrinsic desensitization. Was. On the other hand, two or more unconjugated dye chromophores are linked by a covalent bond.
Regarding the component-linked dye, U.S. Pat.
2,425,772, 2,518,732, 2,521,944, 2,59
No. 2,196 or EP 565,083. However, these were not aimed at improving the light absorption. GBBird et al. In U.S. Pat.Nos. 3,622,317 and 3,976,493, adsorbed linked sensitizing dye molecules having multiple cyanine chromophores to increase light absorption and increase energy transfer, as aggressively aimed at improving light absorption. Sensitization, but no remarkable increase in sensitivity was obtained. Ukai et al., In JP-A-64-91134, combine at least one substantially non-adsorbable dye containing at least two sulfo or carboxy groups with a spectral sensitizing dye that can be adsorbed on silver halide. Has been proposed. In addition, Bishwa Karma et al. Disclosed in Japanese Patent Application Laid-Open No. 6-27,578 a spectral sensitization using a two-component linked dye in which an adsorbable cyanine dye and a non-adsorbable oxonol were linked to silver halide. Sensitivity has not been fully achieved. As described above, sufficient sensitivity has not been achieved by any of the methods of the patents and literatures, and further technical development needs to be performed.

[0003]

Accordingly, an object of the present invention is to provide a high-sensitivity silver halide light-sensitive material containing a novel methine compound.

[0004]

The above objects of the present invention have been attained by the following means. (A) A silver halide photosensitive material comprising at least one silver halide emulsion containing a compound represented by the following general formula (1). Formula (1) (Dye1)-(L1- [Dye2] n1) m1 In the formula, Dye1 and Dye2 are methine chromophores, and at least one of Dye1 and Dye2 is a cyanine chromophore containing a benzoxazole nucleus. In addition, Dye 1 has stronger adsorption power to silver halide grains than Dye 2. L1 represents a linking group. n1 and m1 are each an integer from 1 to 5. (B) The silver halide photosensitive material described in (a), wherein in the compound represented by the general formula (1), Dye1 and Dye2 are each an oxacarbocyanine chromophore. (C) Among the silver halide photosensitive materials described in (b), in the compound represented by the general formula (1), the reduction potential of Dye1 is more noble than the reduction potential of Dye2. material. (D) Among the silver halide photosensitive materials described in (c), in the compound represented by the general formula (1), the maximum absorption wavelength of Dye1 in the silver halide emulsion is longer than the maximum absorption wavelength of Dye2. A silver halide light-sensitive material, characterized in that: (E) A silver halide photosensitive material, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2) among the silver halide photosensitive materials described in (a). General formula (2)

[0005]

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In the formula, R ₁ and R ₂ each represent an optionally substituted alkyl group. V1, V2, V3, V4, V5, V6, V7, V8, V9, V10, V1
1, V12, V13, V14, V15 and V16 each represent a hydrogen atom or a substituent. M1, M2, M3, M4, M5 and M6 each represent a methine group. L1 represents an optionally substituted divalent linking group. Z represents a charge neutralizing ion. y represents the number required to neutralize the charge. In (a), a silver halide emulsion spectrally sensitized with the compound represented by the general formula (1) is preferable.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the methine compound of the present invention will be described in detail. Dye1 and Dye2 are methine chromophores, but at least one of Dye1 and Dye2 is a cyanine chromophore containing a benzoxazole nucleus, and Dye1 is a Dye1
Stronger adsorption power to silver halide grains than ye2. The methine chromophore may be any, but is preferably a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, a styryl dye, an oxonol dye, a coumarin dye, a xanthene dye, an acridine dye, and oxazine. Dyes and thiazine dyes. For more information on these dyes, see FM Harmer, Heterocyclic Compoun
ds-Cyanine Dyes and Related Compounds, John & Wiley
& Sons, New York, London, 1964, DMSturmer
Author, Heterocyclic Compounds-Special Topics in Hete
rocyclic Chemistry, Chapter 18, Section 14, 482 to 5
Page 15, John & Wiley & Sons, New York, London, 197
7th year, Mitsuo Maeda, Laser Research, Vol. 8, No. 694
Pp. 803, 958 (1980), FPSchaefer
Author, Dye Laser, Springer, 1973. The cyanine chromophore represents a chromophore represented by the following general formula (3). General formula (3)

[0008]

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In the formula, Z ₁ and Z ₂ each represent a 5- or 6-membered nitrogen-containing heterocyclic ring, which may be further condensed with an aromatic ring (such as a benzene ring). R ₃ and R ₄ each represent an alkyl group. M7, M8, M9, M10, M11, M12, and M13 each represent a methine group. k ₁ and k ₃ are 0 or 1. k ₂
Represents an integer from 0 to 3. C ₁ represents an ion for neutralizing charge. d ₁ represents a number necessary for neutralization of electric charge.

Examples of the benzoxazole nucleus contained in Dye1 and Dye2 include, for example, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-ethyl-5-methylbenzoxazolyl , 2-3-methyl-5-methoxybenzoxazolyl, 2-3-ethyl-
5-phenylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropylbenzoxazolyl, 2-3-ethyl-5-p-bromophenylbenzoxazolyl, 2-4 -Methoxy-3-ethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl,
2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-γ-naphthoxazolyl, 2-3- (1-
Naphthoxyethyl) benzoxazolyl, 2-3,5-
Dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2-3-ethyl-5-methoxybenzoxazolyl, 2- 5-phenyl-3-sulfoethylbenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-
Examples thereof include 3-dimethyl-5,6-dimethylthiobenzooxazolyl, and 2-benzoxazolyl having another substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, propyl), a halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom), a nitro group, an alkoxy group (eg, methoxy, ethoxy), an aryl group ( For example, phenyl), an aryloxy group (for example, phenoxy), an amide group, a carbamoyl group, a sulfo group, a hydroxy group, a carboxy group,
Examples include an alkylthio group and a cyano group. Hereinafter, these substituents are referred to as a substituent group X.

Next, a preferred combination of Dye1 and Dye2 will be described. In the general formula (1), each of Dye1 and Dye2 is preferably an oxacarbocyanine chromophore. Further, it is preferable that the reduction potential of Dye1 is more noble than the reduction potential of Dye2. Further, it is preferable that the maximum absorption wavelength of Dye1 in the silver halide emulsion is longer than the maximum absorption wavelength of Dye2. The reduction potential of the dye referred to herein is, for example, the value of Tani et al., Journal of Physical Chemistry.
It can be measured according to the method described in Istry, Vol. 94, p. 1298, 1990.

The linking group represented by L1 comprises an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably 1 to 20 carbon atoms
Alkylene group (e.g., methylene, ethylene, propylene, butylene, pentylene), an arylene group having 6 to 20 carbon atoms (e.g., phenylene, naphthylene), an alkenylene group having 2 to 20 carbon atoms (e.g., ethenylene), an amide group, Ester group, sulfoamide group, sulfonic ester group, ureido group, sulfonyl group, sulfinyl group,
Thioether group, ether group, carbonyl group, -NRa-
(Where Ra is a hydrogen atom or an alkyl group or an aryl group) and a linking group having 1 to 40 carbon atoms formed by combining one or more heterocyclic divalent groups. In addition, these linking groups may be further substituted by a substituent, and examples of the substituent include the above-mentioned substituent group X. For example, L1 includes the following, which may be further substituted.

[0013]

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N1 and m1 are each an integer from 1 to 5. Preferably it is 1-3. More preferably, both are 1.

R1 and R2 are each an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, n-propyl, n-
Butyl, n-pentyl, n-hexyl, n-heptyl,
n-nonyl, i-propyl, i-butyl, i-pentyl, t-butyl and the like. These may be substituted. Examples of the substituent include the above-described substituent group X.
Preferred substituent groups include a sulfo group, a carboxy group,
An alkoxy group, an alkenyl group, and an amide group. When the substituent is a sulfo group, examples of the counter ion include alkali metals and quaternary ammonium compounds, such as sodium, potassium, pyridinium,
-Ethylpyridinium, triethylammonium and the like. ). R1 and R2 are preferably a methyl group, an ethyl group, a propyl group, a 2-sulfoethyl group,
-Sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group, 2-sulfobenzyl group, 3-sulfo-3-phenylpropyl group, 3-sulfo-2-propenyl group, 2
-Hydroxy-3-sulfopropyl group, particularly preferably a 2-sulfoethyl group, a 3-sulfopropyl group,
-Sulfobutyl group and 3-sulfobutyl group.

V1, V2, V3, V4, V5, V6, V7, V8, V9, V10, V11, V1
2, V13, V14, V15 and V16 each represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms (for example, methyl and ethyl) and a halogen atom (for example,
A chlorine atom, a bromine atom, an iodine atom, a fluorine atom), a nitro group, an alkoxy group having 1 to 20 carbon atoms (eg, methoxy, ethoxy), an aryl group having 6 to 20 carbon atoms (eg, phenyl), 20 heterocyclic groups (for example,
2-pyridyl, 3-pyridyl), aryloxy group having 6 to 20 carbon atoms (for example, phenoxy, 1-naphthoxy, 2-naphthoxy), amide group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano And the like. Preferred are a hydrogen atom, an alkyl group, a halogen atom, an aryl group, an alkoxy group and a sulfo group.

M1, M2, M3, M4, M5 and M6 each represent a methine group. It may have a substituent, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms (eg, methyl and ethyl), a halogen atom (eg, chlorine, bromine, iodine, and fluorine), nitro Group, an alkoxy group having 1 to 20 carbon atoms (eg, methoxy, ethoxy), an aryl group having 6 to 20 carbon atoms (eg, phenyl), 0 carbon atoms
To 20 heterocyclic groups (eg, 2-pyridyl, 3-pyridyl), aryloxy groups having 6 to 20 carbon atoms (eg, phenoxy, 1-naphthoxy, 2-naphthoxy), amide groups, carbamoyl groups, sulfo groups, hydroxy groups Group, carboxy group, alkylthio group, cyano group and the like. Further, a ring may be formed with another methine group, or a ring may be formed with an auxochrome. Preferred are unsubstituted, ethyl-substituted and methyl-substituted methine groups.

Z represents a charge neutralizing ion. Whether a compound is a cation, an anion, or has a net ionic charge depends on its substituents. Typical cations are ammonium and alkali metal ions, while anions can be either inorganic or organic. Examples of the cation include sodium ion, potassium ion, triethylammonium ion, pyridinium ion, and 1-ethylpyridinium ion. Examples of the anion include halogen anion (eg, chloride ion, bromide ion, fluorine ion, Iodine ion), substituted aryl sulfonate ion (eg, paratoluene sulfonate ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, perchlorate ion, tetrafluoroborate ion, acetate ion and the like. . y represents the number required to neutralize each charge.

Specific examples of the compound of the present invention are shown below.
The present invention is not limited to this.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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The compound of the present invention can be synthesized, for example, according to the method described in the following literature. FMHarm
er, Heterocyclic Compounds-Cyanine Dyes and Rel
ated Compounds, John & Wiley & Sons, New York, London
n, 1964, DMSturmer, Heterocyclic Compo
unds- Special Topics in Heterocyclic Chemistry,
Chapter 18, Section 14, Pages 482-515, John & Wiley & S
ons, New York, London, 1977.

Next, the silver halide photographic material of the present invention will be described in detail. The compounds of the present invention can be used alone or in combination with other sensitizing dyes in silver halide photographic materials.

The time at which the compound of the present invention (and the same applies to other sensitizing dyes) is added to the silver halide emulsion of the present invention can be determined by any of the emulsion preparation steps which have been found to be useful. It may be inside. For example, U.S. Pat. Nos. 2,735,766 and 3,628,960
Nos. 4,183,756 and 4,225,666
JP-A-58-184142 and JP-A-60-19674.
No. 9, etc., the stage before silver halide grain formation step and / or before desalting, during the desalting step and / or
Alternatively, the emulsion during the period from desalting to before the start of chemical ripening, as disclosed in JP-A-58-113920, etc., just before or during the process of chemical ripening, or before coating after chemical ripening, At any time before the application, it may be added in the process. Also, U.S. Pat.
As disclosed in US Pat. No. 5,666, JP-A-58-7629, etc., the same compound alone or in combination with a compound having a different structure may be used, for example, during the particle formation step, during the chemical ripening step, or when the chemical ripening is completed. Separately, or may be added dividedly, such as before chemical ripening or during the process and after completion, and may be added by changing the type of compound and compound combination to be added separately. Is also good.

The amount of the compound of the present invention varies depending on the shape and size of the silver halide grains, but it can be used in an amount of 1 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol per mol of silver halide, and is preferably 7.5. An addition amount of × 10 ^{−6 to} 1.5 × 10 ⁻³ mol is more preferable.

The compounds of the present invention can be dispersed directly in the emulsion. These can be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, pytidine, water or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be made to coexist. Further, ultrasonic waves can be used for dissolution. As a method for adding this compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and A method of dispersing a solution in a hydrophilic colloid and adding this dispersion to an emulsion, as described in JP-B-46-24185, etc., is dispersed in a water-soluble solvent, and this dispersion is added to the emulsion. A method in which a methine compound is dissolved in a surfactant as described in U.S. Pat. No. 3,822,135 and the solution is added to an emulsion; a method described in JP-A-51-74624; A method of dissolving with a compound to be dissolved and adding the solution to an emulsion, JP-A-50-80
No. 826, a method of dissolving a methine compound in an acid substantially free of water and adding the solution to an emulsion is used. In addition, the method described in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287, and 3,429,835 may be used for addition to the emulsion.

The compounds of the present invention can be used as various filter dyes, irradiation prevention dyes or antihalation dyes for the purpose of improving sharpness and color resolution. This compound can be incorporated in a coating solution such as a silver halide photographic material layer, a filter layer and / or an antihalation layer by a conventional method. The dye may be used in an amount sufficient to color the photographic layer, and those skilled in the art can easily select this amount appropriately according to the purpose of use. Generally, the optical density is in the range of 0.05 to 3.0. It is preferable to use it.
The timing of addition may be any step before coating. Alternatively, a polymer having a charge opposite to that of the dye ion may coexist in the layer as a mordant, and the dye may be localized in a specific layer by the interaction with the dye molecule. As the polymer mordant, for example, US Pat. No. 2,548,564
Nos. 4,124,386 and 3,625,694
No. 3,958,995, 4,168,976
And No. 3,445,231.

Useful supersensitizers for spectral sensitization in the present invention are described, for example, in US Pat. No. 3,511,664.
3,615,613, 3,615,632, 3,615,641, 4,596,767, 4,945,038, 4,965,182, and 4 , 965, 182 and the like, and a pyrimidylamino compound, a triazinylamino compound, an azolium compound, and the like.

The silver halide which can be used in the silver halide photographic light-sensitive material of the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. .
Preferred silver halides are silver bromide, silver chlorobromide, silver iodochlorobromide, or high silver chloride described in JP-A-2-42. The composition and processing of the light-sensitive material will be described below. The composition and processing described in JP-A-2-42 are preferably used particularly in high silver chloride. The constitution and processing described in JP-A-63-264743 are particularly preferably used for silver chlorobromide.

The silver halide grains may have different phases between the inside and the surface layer, or may consist of a uniform phase. Also, particles whose latent image is mainly formed on the surface (for example, a negative photosensitive material), particles that are mainly formed inside the particle (for example, an internal latent image photosensitive material), or particles that have been previously covered Particles (for example, a direct positive photosensitive material) may be used. Silver halide grains having the above-described various halogen compositions, crystal habits, grain internal structures, shapes and distributions are used in photosensitive photographic materials for various uses.

The silver halide grains in the photographic light-sensitive material may have a regular crystal form such as a cubic, a tetrahedral or a dodecahedron, or an irregular crystal form such as a sphere or a plate. Or a compound having a combination of these crystal forms. It may consist of a mixture of particles of different crystal forms.

In the photographic material of the present invention, the silver halide grains forming the emulsion layer have an aspect ratio of 3 or more and 1 or more.
The case where it is 00 or less is preferable. Here, the expression that the aspect ratio is 3 or more and 100 or less means that silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 3 or more and 100 or less correspond to all silver halide grains in the emulsion. It means that there is at least 50% of the projected area. The aspect ratio is preferably 3 or more and 20 or less, and most preferably 4 or more and 12 or less. Tabular grains are described in Photographic, Science, And, Engineering, Vol. 14, pp. 248-257 (1970), U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, 4,439,520 and GB 2,112,157. In the photographic light-sensitive material of the present invention, its abundance is at least 70%, particularly preferably at least 85%.

The compounds of the present invention are used in photographic materials for the following applications for the purpose of sensitizers, sensitizing dyes, filters, antihalation or irradiation prevention. These dyes are used in addition to the photosensitive emulsion layer. It can be added to desired layers such as an intermediate layer, a protective layer and a back layer. The compounds of the present invention are used in various color and black-and-white silver halide photographic materials. More specifically, a light-sensitive material for color positive, a light-sensitive material for color paper, a light-sensitive material for color negative, a light-sensitive material for color reversal (with or without a coupler), a silver halide photographic light-sensitive material for direct positive, Photographic materials for plate making (eg, lith film, risupe film, etc.), photographic materials for cathode ray tubes and sprays, photographic materials for X-ray recording (especially materials for direct and indirect photography using a screen), used in silver salt diffusion transfer processes Photosensitive material used in the color diffusion transfer process, die, transfer, photosensitive material used in the process, photosensitive material used in the silver dye bleaching method,
Used for photosensitive materials for thermal development.

The silver halide emulsion used in the present invention is:
P, Grafkides, Chimmy, D, Physique, Photography, Paul Montell, 1967, G, F, Deffein, Photographic, Emulsion, Chemistry, The, Focal Press, 19
66, Vui, El, Tsuerikman, Making, And, Coaching, Photographic, Emausion,
It can be prepared by the method described in The Press, Focal Press, 1964.

When silver halide grains are formed, for example, ammonia, rodancali, rodanammon, thioether compounds (eg, US Pat. No. 3,271,1) may be used as a silver halide solvent in order to control the growth of the grains.
Nos. 57, 3,574,628 and 3,704,13
Nos. 0, 4,297,439 and 4,276,374
No. 3,078,098), thione compounds (for example, JP-A-53-144).
No. 319, No. 53-82408, No. 55-77737
And amine compounds (for example, JP-A-54-1007).
No. 17, etc.) can be used. In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, and the like may coexist. As the internal latent image type silver halide emulsion used in the present invention, for example, US Pat.
2,250, 3,206,313, 3,44
7,927, 3,761,276 and 3,9
Examples thereof include a conversion type silver halide emulsion, a core / shell type silver halide emulsion described in JP-A No. 35,014, and a silver halide emulsion incorporating a different metal.

The silver halide emulsion is usually chemically sensitized. Chemical sensitization is described in, for example, H, Freezer, Day, Grandlagen, Der, Photography Schen, Prodesse, Mitt, Silberhalogeneden, Academic, Fairlags, 1968, pages 675-734. You can use the method. That is, a sulfur sensitization method using a compound containing a sulfur capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines), a selenium sensitization method, a reducing substance (for example, Reduction sensitization using stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, noble metal compounds (for example, gold complex salts, and metals of Group VIII of the periodic table such as Pt, Ir, and Pd) Noble metal sensitization method or a combination thereof.

The photographic light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. it can. That is, thiazoles such as U.S. Pat.
No. 942,721, JP-A-59-191032 and the like, and benzothiazolium salts described in
Ring-opened compounds, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles described in US Pat. Mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, the above heterocyclic mercapto compounds having a water-soluble group such as a carboxy group or a sulfone group, thioketone compounds such as oxazolinethione, azaindenes such as tetraaza Indenes (especially 4-hydroxy substitution (1,3,3a,
7) Many compounds known as anti-fogging agents or stabilizers, such as tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acid, acetylene compounds described in JP-A-62-287957, and the like. Can be added.

The silver halide light-sensitive material of the present invention can contain a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler and a compound which disperses the coupler. That is, in the color development processing, aromatic 1
It may contain a compound capable of forming a color by oxidative coupling with a secondary amine developing agent (for example, a phenylenediamine derivative arrow, an aminophenol derivative, etc.). For example,
Magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarin couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (eg, benzoylacetoanilides, pivaloylacetoanilides). And cyan couplers such as naphthol couplers and phenol couplers. These couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group in the molecule. 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 used. In addition to the DIR coupler, a colorless DI in which the product of the coupling reaction is colorless and releases a development inhibitor
R coupling compounds may be included.

The photographic light-sensitive material of the present invention may contain, for example, polyalkylene oxide or derivatives thereof such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or accelerating development. It may contain a salt compound, a urethane derivative, a urea derivative, an imidazole derivative, a 3-pyrazolidone derivative, or the like. In the photographic light-sensitive material of the present invention, as a filter dye, or for various purposes such as prevention of irradiation, other than the methine compound of the present invention,
Various dyes may be included. Such dyes include:
For example, British Patent Nos. 506,385 and 1,177,4
29, 1,311,884, 1,338,79
No. 9, No. 1, 385, 371, No. 1, 467, 214
No. 1,433,102, 1,553,516
JP-A-48-85130 and JP-A-49-114420
No. 52-117123, No. 55-161233
No. 59-11640, JP-B-39-22069
No. 43-13168, No. 62-273527,
U.S. Pat. Nos. 3,247,127 and 3,469,98
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in Nos. 5,078,933 and the like;
U.S. Pat. Nos. 2,533,472 and 3,379,53
No. 3, British Patent No. 1,278,621, JP-A-1-1-1
Other oxonol dyes described in JP-A-34447, JP-A-1-183652 and the like, British Patent No. 575,691
Nos. 680,631, 599,623, 78
6,907, 907,125, 1,045,6
09, U.S. Pat. No. 4,255,326, JP-B-59
Azo dyes described in US Pat.
Azomethine dyes described in U.S. Pat. Nos. 2,865,7 and 0-100116, 54-118247, and British Patent Nos. 2,014,598 and 750,031;
52, anthraquinone dyes described in U.S. Pat. Nos. 2,533,009, 2,688,541 and 2,538,008, British Patent 584,609,
No. 1,210,252, JP-A-50-40625,
No. 51-3623, No. 51-10927, No. 54-
118247, JP-B-48-3286, and 59-3
Arylidene dyes described in JP-A-7303 and the like, JP-B-28-3082, JP-B-44-16594, and JP-B-59-2.
8898 and the like; British Patent Nos. 446,583 and 1,335,422;
Triarylmethane dyes described in JP-A-9-228250 and the like; British Patent Nos. 1,075,653 and 1,15;
No. 3,341, No. 1,284,730, No. 1,47
Merocyanine dyes described in U.S. Pat. No. 2,843,486 described in US Pat.
No. 3,294,539, JP-A-1-291247
And the like.

The following method can be used to prevent such diffusion of the dye. For example, a method of coexisting a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye in a layer as a mordant and localizing the dye in a specific layer by interaction with dye molecules is disclosed in U.S. Pat.
8,564, 4,124,386, 3,62
No. 5,694. Further, a method of dyeing a specific layer using a dye solid insoluble in water is disclosed in
Nos. 6-12639, 55-155350, 55-
155351, 63-27838, 63-19
No. 7943 and European Patent No. 15,601. A method of dyeing a specific layer using metal salt fine particles having a dye adsorbed thereto is disclosed in U.S. Pat. No. 2,719,088.
Nos. 2,496,841 and 2,496,843
And JP-A-60-45237.

The photographic light-sensitive material of the present invention has various types of interfaces for various purposes such as coating aids, antistatic properties, improvement of slipperiness, emulsification / dispersion, prevention of adhesion, and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). Activators may be included. In practicing the present invention, other additives are used together with the silver halide emulsion or other hydrophilic colloid. For example, a discoloration inhibitor, an inorganic or organic hardener, an anti-coloring agent, an ultraviolet absorber, a mordant, a plasticizer, a latex polymer, a matting agent and the like can be mentioned. Specifically, Research Date Closure, Vol. 176, (1
978, XI), D-17643, and the like. In the photographic light-sensitive material used in the present invention, a hydrophilic polymer such as gelatin is used as a protective colloid. The finished silver halide emulsion and the like are coated on a suitable support such as baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic base or glass plate.

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, tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. Exposure time is not limited to exposure time of 1/1000 second to 1 second usually used in cameras, but also exposure shorter than 1/1000 second, for example, exposure of 1/10000 to 1 / 1,000,000 second using a xenon flashlight or a cathode ray tube. 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. Laser light can also be used for exposure. Alternatively, the exposure may be performed using light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like. Photographic processing of photosensitive materials made using the present invention is described, for example, in Research Disclosure, Vol. 176, pp. 28-30 (RD1764).
Any of the known methods and known processing solutions as described in 3) can be applied. This photographic processing may be either photographic processing for forming a silver image (black-and-white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

The silver halide photographic light-sensitive material carrying magnetic recording which may be used in the present invention is disclosed in JP-A-6-35118.
No. 6-17528, Invention Association Open Technical Report 94-60
23. A thin layer support of a pre-heat-treated polyester described in 23, for example, a polyethylene aromatic dicarboxylate-based polyester support, having a thickness of 50 μm to 300 μm, preferably 50 μm to 200 μm, and more preferably 80 μm.
m to 115 μm, particularly preferably 85 μm to 105 μm
At a temperature not lower than 40 ° C. and not higher than the glass transition temperature.
Heat treated (annealed) for 0 hour
Irradiation described in JP-A Nos. 43-2604 and 45-3828, JP-B-48-5043, JP-A-51-13.
No. 1576 etc., surface treatment such as corona, USP
No. 5,326,689 and an undercoat layer described in US Pat. No. 2,761,791 is provided if necessary.
6, ferromagnetic particles described in JP-A-6-59357 may be applied. The above magnetic layer is described in JP-A-4-124.
The stripe shape described in JP-A Nos. 642 and 4-124645 may be used. Further, as required, Japanese Patent Application Laid-Open No. 4-625
No. 43 is subjected to an antistatic treatment, and a silver halide emulsion is finally coated. The silver halide emulsions used herein are described in JP-A-4-16693, JP-A-3-41436, and JP-A-3-41436.
No. 41437 is used. The silver halide photographic light-sensitive material thus produced is preferably produced by the production control method described in JP-B-4-86817, and the production data is preferably recorded by the method described in JP-B-6-87146. Thereafter or before that, according to the method described in JP-A-4-125560, the film is cut into a narrower film than the conventional 135 size, and the perforations are reduced per small format screen so as to match the smaller format screen. Punch two holes per side. The film thus produced is the cartridge package of JP-A-4-157559, the cartridge shown in FIG. 9 of the embodiment of JP-A-5-210202, or the film cartridge described in US Pat. No. 4,221,479, US Pat. No. 4,834,306. , 4,
834,366, 5,226,613, 4,8
Use in a cartridge described in No. 46,418.
The film cartridge or film cartridge used here is disclosed in US Pat. No. 4,848,693, US Pat.
A type capable of accommodating a tongue, such as No. 355, is preferable from the viewpoint of light shielding properties. Further, a cartridge having a lock mechanism such as USP 5,296,886 or USP 5,
No. 347,334 are preferable, and a cartridge having a double exposure prevention function is preferable. Further, as described in JP-A-6-85128, a cartridge in which the film is easily mounted by simply inserting the film into the cartridge may be used. The film cartridge thus produced can be used for photography, development processing, and various ways of enjoying photographs by using a camera, a developing machine, and laboratory equipment described below. For example, a camera of a simple mounting type described in JP-A-6-8886 and JP-A-6-99908, and a camera described in JP-A-6-57398 and 6-10
No. 1135, an automatic winding camera,
No. 05690, a camera capable of taking out and changing the type of film in the middle of shooting, and information on shooting described in JP-A-5-293138 and JP-A-5-283382, for example,
A camera capable of magnetic recording on a film for panorama photography, high vision photography, and normal photography (magnetic recording capable of selecting a print aspect ratio), a camera having a double exposure prevention function described in JP-A-6-101194, 5
The function of a film cartridge (patrone) can be sufficiently exhibited by using a camera having a function of displaying a use state of a film or the like described in -150577. The film photographed in this way is disclosed in JP-A-6-222514,
The processing is carried out by an automatic developing machine described in JP-A-6-222545, or before, during or after the processing.
No. 5,123,054, and JP-A-5-19364.
The aspect ratio selection function described in the reference number may be used. At the time of development processing, if it is a cine type development, see JP-A-5-1194.
Splicing is performed by the method described in No. 61. At the time of or after the development processing, the wafer is subjected to the detachment and detachment processing described in JP-A-6-148805. After processing in this way,
Film information may be converted to print through back printing and front printing on color paper by the method described in JP-A-2-184835, JP-A-4-186335, and JP-A-6-79968. Further, JP-A-5-11
It may be returned to the customer together with the index print and return cartridge described in JP-A Nos. 353 and 5-232594.

Further, at least one layer of
A blue-sensitive silver halide emulsion layer containing a yellow color coupler, a green-sensitive silver halide emulsion layer containing a magenta color coupler, and a red-sensitive silver halide emulsion layer containing a cyan color coupler, and A color light-sensitive material having at least one silver halide emulsion layer that gives a sodium bicarbonate effect to the entire red-sensitive silver halide emulsion layer is preferably used. Details of such a light-sensitive material are described in JP-A-7-159950.

[0049]

Next, the present invention will be described based on examples, but the present invention is not limited to these examples.

(1) Preparation of Emulsion An aqueous solution containing gelatin having an average molecular weight of 15,000 (water 12
1.9M AgNO ₃ aqueous solution and 1.9M KBr aqueous solution were added at 25 ml / min by a double jet method for 70 seconds while stirring and maintaining at 30 ° C. 00 ml, gelatin 7.5 g and KBr 4.5 g). Nuclei of tabular grains were obtained. 400 ml of this emulsion was used as seed crystals, and 650 ml of an inert gelatin aqueous solution (gelatin 20 g, KBr 1.2 g) was added thereto.
Was added to the mixture, and the mixture was heated to 75 ° C. and aged for 40 minutes. Then, an AgNO ₃ aqueous solution (containing 1.7 g of AgNO ₃ ) was added to 1
Over 30 seconds, followed by NH ₄ NO ₃ (50 wt%)
7.0 ml of an aqueous solution and 7.0 ml of NH ₃ (25 wt%) were added, and the mixture was aged for 40 minutes.

Next, the emulsion was adjusted to pH 7 with HNO ₃ (3N) and KBr
After adding 1.0 g, a 1.9 M AgNO ₃ aqueous solution 366.
5 ml and an aqueous solution of KBr, followed by an aqueous solution of 1.9 M AgNO ₃
Emulsion 1 was obtained by adding 3.6 ml of an aqueous solution of KBr (33.3 mol% of KI) and 160.5 ml of a 1.9 M aqueous solution of AgNO ₃ and an aqueous solution of KBr while maintaining the pAg at 7.9.

Emulsion 1 thus obtained is a triple structure grain having a region having the highest silver iodide content in the intermediate shell, and has an average aspect ratio of 2.8 and a tabular grain having an aspect ratio of 3 or more. The ratio to the total projected area was 26%. The coefficient of variation of the particle size was 7%, and the average of the particle size was 0.98 μm in sphere equivalent diameter. Emulsion 1 was desalted by an ordinary flow curation method, and a sensitizing dye was added to 1 mol of silver, and gold, sulfur and selenium sensitization was optimally performed in the presence of the sensitizing dye.

(2) Preparation of Coated Samples (3) Samples 101 and 102 were prepared by coating an emulsion layer and a protective layer as shown in Table 1 on a triacetyl cellulose film support provided with an undercoat layer.

[0054]

[Table 1]

These samples were exposed to sensitometric exposure (1/100 second) and subjected to the following color development processing. Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Water washing 2 minutes 10 seconds 24 ° C 1200 ml 20 liters Fixed 4 minutes 20 seconds 38 ° C. 25 ml 30 liters Washing 1 1 minute 05 seconds 24 ° C. Countercurrent piping system from (2) to (1) 10 liters Washing 2 1 minute 00 seconds 24 ° C. 1200 ml 10 liters Stabilizing 1 minute 05 seconds 38 ° C. 25 ml 10 liters Drying 4 minutes 20 seconds 55 ° C. The replenishment rate is 35 mm width and 1 m length. (Color developing solution) Mother liquor (g) replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 potassium bromide 1.4 0.7 potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2- Methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.05 (Bleaching solution) Mother liquor (g) Replenisher (g) Sodium ferric ethylenediaminetetraacetate 3 Water salt 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water to 1.0 liter 1.0 liter pH 6.0 5.7 (Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate (70%) 170.0 ml 200.0 ml 1.0 liter with addition of water 1.0 liter pH 6.7 6.6 (stabilizing solution) Mother liquor (g) replenisher (g) formalin 2.0 ml 3.0 ml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediaminetetraacetic acid disodium salt 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.8-8.0 5.8-8.0

The density of the treated sample was measured with a green filter, and the fresh sensitivity and fog were evaluated. Sensitivity is defined as the reciprocal of the exposure that gives a density 0.2 higher than the fog density,
The sensitivity of each sample was expressed as a relative value with the value of sample 101 as 100. Table 2 shows the results of the emulsion and methine compound used for each sample and the sensitivity of each sample.

[0057]

[Table 2]

[0058]

Embedded image

Table 2 shows that the compounds of the present invention have higher fresh sensitivity than the comparative compounds.

Example 2 A tabular silver bromide emulsion was prepared and evaluated in the same manner as in Emulsion D of Example 5 of JP-A-8-29904. As in Example 1, the compound of the present invention was a comparative compound. It was found that the fresh sensitivity was higher than that of.

Example 3 An octahedral silver bromide internal latent image type direct positive emulsion and a hexagonal tabular silver bromide internal latent image type direct positive were prepared in the same manner as in Emulsions 1 and 5 of Example 1 of JP-A-5-313297. When an emulsion was prepared and evaluated, it was found that the compound of the present invention had higher fresh sensitivity than the comparative compound as in Example 1.

Example 4 A tabular silver chloride emulsion was prepared and evaluated in the same manner as in Emulsion A of Example 1 of JP-A-8-122954. As in Example 1, the compound of the present invention was compared with the comparative compound. It was found that the fresh sensitivity was high.

[0063]

By using the methine compound of the present invention, a highly sensitive silver halide photographic material can be obtained.

Claims (5)

[Claims] 1. A silver halide photosensitive material comprising at least one silver halide emulsion containing a compound represented by the following general formula (1). Formula (1) (Dye1)-(L1- [Dye2] n1) m1 In the formula, Dye1 and Dye2 are methine chromophores;
At least one of Dye2 is a cyanine chromophore containing a benzoxazole nucleus, and Dye1 has a stronger adsorption power to silver halide grains than Dye2. L1 represents a linking group. n
1 and m1 are each an integer from 1 to 5. 2. The compound represented by the general formula (1) among the silver halide light-sensitive materials according to claim 1, wherein
And Dye2 are oxacarbocyanine chromophores, respectively. 3. The compound represented by the general formula (1) among the silver halide light-sensitive materials according to claim 2, wherein
A silver halide light-sensitive material, characterized in that the reduction potential of is more noble than the reduction potential of Dye 2. 4. The compound represented by the general formula (1) among the silver halide light-sensitive materials according to claim 3, wherein
Wherein the maximum absorption wavelength in the silver halide emulsion is longer than the maximum absorption wavelength of Dye 2. 5. The silver halide light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2). . General formula (2) In the formula, R ₁ and R ₂ each represent an optionally substituted alkyl group. V1, V2, V3, V4, V5, V6, V7, V8, V9, V10, V11, V12, V13, V1
4, V15 and V16 each represent a hydrogen atom or a substituent. M
1, M2, M3, M4, M5, M6 each represent a methine group. L1 represents a divalent linking group which may be substituted. Z represents a charge neutralizing ion. y represents the number required to neutralize the charge.