JPH11174616A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material which has high sensitivity and little causes fog and is improved in residual color after processing. SOLUTION: In a silver halide photosensitive material having at least one layer of a silver halide emulsion on a support, at least one kind of compound expressed by the following is contained in the emulsion layer. Wherein Z indicates an atom group needed for forming a 5 or 6-member nitrogen contained heterocycle. L indicates a tetravalent group in which a substitutional or non- substitutional methine group is connected to make a conjugated double bond of an even number 6 or less. R1 indicates a substitutional or non-substitutional alkyl group, or an aryl group, and R2 indicates a hydrogen atom, a substitutional or non-substitutional alkyl group, an aryl group or a heterocyclic group. q and r respectively indicate 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a silver halide photographic material having high sensitivity, low fog, and improved residual color after processing.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are required to have high sensitivity in different specific wavelength ranges depending on the purpose of use. As one of the techniques for producing such a silver halide photographic light-sensitive material, various types of dyes are added to a silver halide photographic emulsion as sensitizing dyes,
It is generally well known that the sensitivity in a specific wavelength range is extremely effectively increased in a wavelength range longer than the photosensitive wavelength range inherent to silver halide.

When spectral sensitization is applied to a silver halide photographic emulsion by using a dye, it must satisfy not only the spectral sensitizing effect and the increase in sensitivity but also the following requirements. . (1) The spectral sensitization range is appropriate. (2) Stable photographic characteristics are maintained during storage of the photosensitive material. (3) No contamination or fog due to the residual dye applied for spectral sensitization after development processing. (4) No bad interaction with other photographic additives.

In order to satisfy the above requirements, various types of dyes have been conventionally proposed. For example,
For sensitizing dyes corresponding to a red light source such as a He-Ne laser, a red LD, and a red LED, see US Pat.
No. 722 has been proposed, and one of the features is that the residual color contamination after development processing is small.

[0005] However, even these sensitizing dyes do not completely satisfy the above requirements, and further improvement is required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent silver halide photographic material which satisfies the above-mentioned requirements and has a high sensitivity particularly in the red region and has little residual color contamination after development processing. To provide.

[0007]

As a result of various studies, the present inventors have found an excellent silver halide photographic light-sensitive material satisfying the above objects by the following means.

A silver halide photographic material having at least one silver halide emulsion layer on a support, characterized in that the emulsion layer contains at least one compound represented by the following general formula (3). Silver halide photographic light-sensitive material.

Embedded image [In the formula, Z represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L represents a tetravalent group in which a substituted or unsubstituted methine group is linked to form an even number of 6 or less conjugated double bonds. R ₁ represents a substituted or unsubstituted alkyl group or aryl group, and R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.
q and r each represent 0 or 1. ]

The compound of the present invention represented by the above general formula (3) is particularly preferably a compound represented by the following general formula (4).

Embedded image [Wherein Z, R ₁ , R ₂ , and q have the same meanings as in Chemical Formula 3, respectively.
L ₁ , L ₂ , L ₃ and L ₄ each represent a substituted or unsubstituted methine group. ]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. In the formula, Z represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. Specific examples of these nitrogen-containing heterocycles include, for example, oxazoline ring, oxazole ring, benzoxazole ring, naphthooxazole ring, thiazoline ring, thiazole ring, thiazine ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring,
Examples include a naphthoselenazole ring, a quinoline ring, a benzoquinoline ring, an indolenine ring, a benzoindolenine ring, a benzimidazole ring, and a naphthoimidazole ring. Among them, an oxazoline ring, an oxazole ring and a benzoxazole ring are particularly preferred. Further, a carbon atom of these heterocycles may be a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, n
-Propyl group, n-butyl group, t-butyl group, n-amyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, n-propoxy group, etc.), hydroxy group, trifluoromethyl group, cyano group, Alkane sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, etc.), sulfamoyl group (for example, sulfamoyl group,
Substituents such as an N, N-dimethylsulfamoyl group, a piperidinosulfonyl group, a morpholinosulfonyl group and the like, and an aryl group (eg, a phenyl group and a methoxyphenyl group) may be attached. Among these, those having 12 or less carbon atoms including a substituent are preferred.

Specific examples of R ₁ include alkyl groups (for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-amyl group, β-hydroxyethyl group, γ- Hydroxypropyl group, β-acetoxyethyl group, γ-acetoxypropyl group, β-methoxyethyl group, γ-methoxypropyl group, carboxymethyl group,
β-carboxyethyl group, γ-carboxypropyl group,
δ-carboxybutyl group, ω-carboxypentyl group,
Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, β-methoxycarbonylethyl group, γ-methoxycarbonylpropyl group, δ-methoxycarbonylbutyl group, β-sulfoethyl group, γ-sulfopropyl group, γ-
Sulfobutyl group, δ-sulfobutyl group, benzyl group, phenethyl group, p-carboxybenzyl group, p-sulfophenethyl group, allyl group, propargyl group, etc., aryl group (eg, phenyl group, methoxyphenyl group, etc.)
Etc. Among these, those having 12 or less carbon atoms including a substituent, among which 6 or less carbon atoms substituted with a group imparting water solubility (for example, a carboxyl group or a sulfo group) are preferred. Is particularly preferred.

Specific examples of R ₂ include a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, n-amyl group, β-hydroxyethyl group, γ-hydroxypropyl group, β-acetoxyethyl group, γ-acetoxypropyl group, β-methoxyethyl group, γ-methoxypropyl group Carboxymethyl group, β-carboxyethyl group, γ-carboxypropyl group, δ-carboxybutyl group, ω-carboxypentyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, β-methoxycarbonylethyl group, γ
-Methoxycarbonylpropyl group, δ-methoxycarbonylbutyl group, β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, benzyl group, phenethyl group, p-carboxybenzyl group, p
-Sulfophenethyl group, allyl group, propargyl group, etc., aryl group (eg, phenyl group, methoxyphenyl group, etc.), heterocyclic group (eg, 2-pyridyl group,
-Thiazolyl group, 4-tetrahydropyranyl group, etc.). Among these, those having 12 or less carbon atoms including a substituent, among which 6 or less carbon atoms substituted with a group imparting water solubility (for example, a carboxyl group or a sulfo group) are preferred. Is particularly preferred.

L is a tetravalent group in which an optionally substituted methine group is connected so as to form an even number of 6 or less conjugated double bonds (for example, = CH-CH =, = CH-CH = C
H-CH =, = CH-CH = CH-CH = CH-CH =
Etc.). Examples of the substituent of these methine groups include an alkyl group which may be substituted (for example, a methyl group, an ethyl group, a benzyl group), an aryl group (for example, a phenyl group), an alkoxy group (for example, a methoxy group, An ethoxy group), an aryloxy group (eg, a phenoxy group), an alkylthio group (eg, a methylthio group,
Examples thereof include an ethylthio group, an arylthio group (eg, a phenylthio group), a substituted amino group (eg, a piperidino group), and a halogen atom (eg, a chlorine atom or a bromine atom). Further, the methine chain substituents may form a ring as a 5- or 6-membered ring,
Examples of such a ring include the following:

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Q and r each represent 0 or 1.

L ₁ , L ₂ , L ₃ and L ₄ represent a methine group which may be substituted, and specific examples of the substituent of these methine groups include a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group) Group, benzyl group, etc.), aryl group (eg, phenyl group), alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), alkylthio group (eg, methylthio group,
Examples thereof include an ethylthio group, an arylthio group (eg, a phenylthio group), a substituted amino group (eg, a piperidino group), and a halogen atom (eg, a chlorine atom or a bromine atom).

Next, specific examples of the compound used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.

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The following are typical synthesis examples. Other exemplified compounds can be prepared in the same manner, for example, in Frances M.H.
amer “Cyanine Dyes and Related Compounds” (196
4, published by Interscience Publishers), etc., and can be easily synthesized with reference to a conventionally known method.

Synthesis of Formula 22 Anhydro-2- (4-acetanilide-1,3-butadienyl) -3- (2-sulfoethyl) benzoxazolium hydroxide
1.91 g of -carboxymethyl-2-thioxo-5-thiazolidinone and 160 ml of acetonitrile were added, and 3.03 g of triethylamine was added while stirring at room temperature.
Allowed to react for minutes. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2.02 g of dark purple crystals having a melting point of 272 ° C (decomposition). The maximum absorption value of the methanol solution was 591.5 nm.

Embedded image Synthesis of anhydrous 2- (4-ethoxy-)
3-methyl-1,3-butadienyl) -3- (2-sulfoethyl) benzoxazolium hydroxide 3.37
1.91 g of 3-carboxymethyl-2-thioxo-5-thiazolidinone and 40 ml of DMF were added to g, and 3.03 g of triethylamine was added thereto while stirring at room temperature, followed by a reaction for 30 minutes. After completion of the reaction, 400 ml of diethyl ether
The precipitated crystals were collected by filtration. The obtained crystals were recrystallized from ethanol to obtain 1.97 g of dark green crystals having a metallic luster with a melting point of 155 ° C. (decomposition). The maximum absorption value of the methanol solution was 607.5 nm.

The silver halide photographic emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like produced by a usual method.

In order to add the compound used in the present invention to these silver halide photographic emulsions, an organic solvent such as methanol, ethanol, acetone, cellsolve, pyridine, dimethylformamide or the like which is arbitrarily miscible with an aqueous solution or water can be used. Alternatively, it can be added as a solution of a mixed solvent. The time when these compounds are added to the silver halide photographic emulsion is generally preferably immediately after the completion of the second ripening. The addition amount varies depending on the type of the sensitizing dye or the type of the silver halide photographic emulsion.
It can be used in a wide range of approximately 4 to 1200 mg per gram.

The silver halide photographic emulsion used in the present invention may have been subjected to noble metal sensitization, sulfur sensitization, reduction sensitization, sensitization in combination thereof or addition of a polyalkylene oxide compound or the like. .

The silver halide photographic emulsion used in the present invention may be spectrally sensitized by using other sensitizing dyes, for example, known cyanine and merocyanine dyes, if necessary.
Stabilizers, surfactants, hardeners by known methods,
Additives such as fluorescent brighteners, ultraviolet absorbers, filter dyes, anti-irradiation dyes, anti-halation dyes, preservatives, plasticizers, matting agents, color couplers and the like can be included. Further, when used for a photosensitive material for stabilization processing, it may contain a developing agent or a precursor thereof.

Examples of the protective colloid of the silver halide photographic emulsion used in the present invention include gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, soluble starch, and water-soluble polymers, in addition to gelatin.

As the support on which the silver halide photographic emulsion used in the present invention is coated, for example, baryta paper, plastic-laminated paper, synthetic paper, resin films such as cellulose triacetate and polyethylene terephthalate can be used. These supports may be provided with an undercoat layer and an antihalation layer, if necessary, by a known method.

[0057]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 A sensitizing dye of the present invention was added to a silver chloride emulsion prepared by a conventional method for producing a silver halide photographic emulsion.
0.05% DMF of sensitizing dyes 37 and 38 in comparison with 5
The solution was added at 1.2 ml / g Ag. These emulsions
The spectral sensitization was stabilized by aging for 45 minutes in a bath at 0 ° C. Thereafter, predetermined amounts of a stabilizer, a surfactant, and a hardener were added, and then the mixture was applied to a polyethylene-laminated paper support, dried, and aged at 35 ° C. overnight. Then, it was cut into an appropriate size to obtain a test sample. Each sample obtained in this manner was subjected to wedge exposure based on the ISO method, and D
Developing was performed at 20 ° C. for 90 seconds using a -72 developer (Eastman Kodak Co., Ltd., developing solution), stopped, fixed, washed with water, and dried to obtain strips having a predetermined black-and-white image. The density was measured using a MACHBETH-TD504 densitometer manufactured by Macbeth Corporation in the United States to evaluate the sensitivity, fog and residual color. The reference point of the optical density at which the sensitivity was determined was [fog + 0.70]. The white light sensitivity is a relative value when the sensitivity of a sample not added with no sensitizing dye is 100, and the red sensitivity is a ratten gelatin filter No. 1 manufactured by Eastman Kodak Company. 29, and are shown as relative values when the sensitivity value of sensitizing dye 37 for comparison is set to 100. For the residual color, the hue of the unexposed portion was visually evaluated.
"5" represents the best quality and "1" represents the worst quality. The results are shown in Table 1.

[0059]

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[0061]

[Table 1]

Example 2 Sensitivity, fog and residual color were evaluated in the same manner as in Example 1 except that sensitizing dyes 22, 24 and 27 of the present invention and sensitizing dye 39 were used in comparison. did. The results are shown in Table 2.

[0063]

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[0064]

[Table 2]

As is clear from Tables 1 and 2, the silver halide photographic light-sensitive material of the present invention has high sensitivity, has little residual color contamination after processing, and has good photographic characteristics.

[0066]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, little fog and improved residual color after processing can be obtained.

Claims (2)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that the emulsion layer contains at least one compound represented by the following general formula 1. Embedded image [In the formula, Z represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L represents a tetravalent group in which a substituted or unsubstituted methine group is linked to form an even number of 6 or less conjugated double bonds. R ₁ represents a substituted or unsubstituted alkyl group or aryl group, and R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.
q and r each represent 0 or 1. ] 2. The silver halide photographic material according to claim 1, wherein the compound represented by the general formula 1 is a compound represented by the following general formula 2. Embedded image [Wherein Z, R ₁ , R ₂ , and q have the same meanings as in Chemical Formula ₁ , respectively.
L ₁ , L ₂ , L ₃ and L ₄ each represent a substituted or unsubstituted methine group. ]