JPH09281632A - Photographic spectral sensitizing dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance high sensitivity in the red wavelength region and to reduce residual dye stains after development by using a specified photographic spectral sensitizing dye. SOLUTION: This spectral sensitizing dye to be used for a photographic sensitive material is represented by the formula in which each of Z1 -Z5 is an atomic group necessary to form a 5- or 6-membered N-containing hetero ring and the N-containing hetero ring to be formed by Z1 is embodied by an oxazoline and oxazole ring and the like and each of that by Z2 and Z3 and that by Z4 and Z5 is an oxazolidine and thiazolidine rings and the like; R1 is an optionally substituted alkyl or aryl group, preferably, <=6C optionally substituted alkyl groups; and R2 is an optionally substituted alkyl group, preferably, <=6C alkyl groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a spectral sensitizing dye for photography, and more particularly to a dye useful as a sensitizing dye used in a silver halide photographic light-sensitive material.

[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 manufacturing techniques for such a silver halide photographic light-sensitive material, various types of sensitizing dyes are added to a silver halide photographic emulsion, and in a wavelength region longer than the intrinsic light-sensitive wavelength region of the silver halide, It is generally well known that the sensitivity in a specific wavelength range is extremely effectively increased.

When spectral sensitization is applied to a silver halide photographic emulsion with 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 stain or fog caused by the residual dye administered for spectral sensitization after development. (4) No bad interaction with other photographic additives.

In order to satisfy the above requirements, various types of cyanine dyes and merocyanine dyes have been proposed. Especially, He-Ne laser, red L
For sensitizing dyes for red light sources such as D and red LED, US Pat. Nos. 4,965,183 and 5,116,7
The dyes described in No. 22 and the like have been proposed, and one of the features thereof is that they have little residual color contamination after development processing.

[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 photographic spectral sensitizing dye satisfying the above-mentioned requirements, having high sensitivity especially in the red region and having little residual color contamination after development processing. To provide.

[0007]

As a result of various studies, the present inventors have found that the sensitizing dye represented by the following chemical formula 2 is an excellent dye satisfying the above object.

[0008]

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[Wherein Z _{1 to} Z ₅ are 5 or 6 respectively]
Represents a group of atoms necessary to form a membered nitrogen-containing heterocycle. R
₁ represents a substituted or unsubstituted alkyl or aryl group, and R ₂ represents a substituted or unsubstituted alkyl group. ]

The sensitizing dye of the present invention will be specifically described below. In the formula, Z _{1 to} Z ₅ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Of these, specific examples of the nitrogen-containing heterocycle formed by Z ₁ include:
For example, oxazoline ring, oxazole ring, benzoxazole ring, naphthoxazole ring, thiazoline ring, thiazole ring, thiazine ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, quinoline ring, benzoquinoline ring, There are indolenine ring, benzoindolenine ring, benzimidazole ring, naphthimidazole ring and the like. Further, carbon atoms of these heterocycles include 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 (eg, methoxy group, ethoxy group, n-propoxy group, etc.), hydroxy group, trifluoromethyl group, cyano group, Alkanesulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, etc.), sulfamoyl group (eg, sulfamoyl group,
Substituents such as N, N-dimethylsulfamoyl group, piperidinosulfonyl group, morpholinosulfonyl group) and aryl groups (eg, phenyl group, methoxyphenyl group, etc.) may be attached. Among these, those having 12 or less carbon atoms including a substituent are preferred. Further, specific examples of the nitrogen-containing heterocycle formed by Z ₂ , Z ₃ and Z ₄ , Z ₅ include, for example, an oxazolidine ring, a thiazolidine ring, an imidazolidine ring, etc., and examples of nitrogen substituents of these heterocycles Is an alkyl group (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.), heterocycle Groups (eg, 2-pyridyl group, 2-thiazolyl group, 4-tetrahydropyranyl group, etc.) and the like.
Among these, those having 12 or less carbon atoms including a substituent are preferred. R ₁ is a substituted or unsubstituted alkyl group (eg, 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 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.) and aryl groups (eg, phenyl group, methoxyphenyl group, etc.). Of these, carbon number 6
Subsequent or less substituted or unsubstituted alkyl groups are preferred.
R ₂ is a substituted or unsubstituted alkyl group (for example, R ₁
As described in the example of the substituent). Of these,
Those having 6 or less carbon atoms are preferable.

Specific examples of the sensitizing dye used in the present invention are shown below. However, the sensitizing dye used in the present invention is not limited to these.

[0012]

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[0013]

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[0014]

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[0015]

[Chemical 6]

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

[Chemical 12]

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

[Chemical 21]

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Typical synthetic examples are shown below, but other exemplified compounds can be synthesized in the same manner, for example, 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 Chemical Formula 4 2- [2,2-di (methylthio)] ethenyl-3-ethylbenzothiazolium methanesulfonate 7.87 g to 3-ethylrhodanine 3.23 g and methanol 200 m.
1 was added and triethylamine 6.0 was added while heating under reflux.
7 g was added and the mixture was heated under reflux for 30 minutes. After completion of the reaction, the mixture was allowed to cool and the precipitated crystals were collected by filtration. The obtained crystals were washed with methanol and dried to give 5.76 g of green crystals having a metallic luster and a melting point of 214 ° C. (decomposition). The absorption maximum of the methanol solution was 561 nm.

To 3.95 g of the merocyanine dye obtained above, 9.31 g of methyl paratoluenesulfonate was added to give 90%.
Heated at ° C for 30 minutes. After cooling, the mixture was washed with ethyl ether, and 1.91 g of 3-carboxymethylrhodamine and 100 ml of methanol were added to the ethyl ether insoluble matter, and 3.03 g of triethylamine was added to the mixture while heating under reflux.
Heated to reflux for minutes. The crude crystals that precipitated during warming were collected by filtration, washed repeatedly with methanol and acetone, and dried to obtain 2.90 g of indigo-colored crystals having a melting point of 280 ° C or higher. The absorption maximum value of the N, N-dimethylformamide solution was 605 nm.

The silver halide photographic emulsion in which the sensitizing dye used in the present invention is used is a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide prepared by a conventional method. Etc. may be used.

To add the sensitizing dye of the present invention to these silver halide photographic emulsions, an organic solvent such as methanol, ethanol, acetone, cellosolve, pyridine or dimethylformamide, which is optionally miscible with an aqueous solution or water, is used alone. Alternatively, it can be added as a solution of a mixed solvent. Also,
It is generally preferable to add these sensitizing dyes to the silver halide photographic emulsion immediately after the completion of the second ripening. The amount of addition varies depending on the type of sensitizing dye or the type of silver halide photographic emulsion, but it can be used in a wide range of about 4 to 1,200 mg per 100 g in terms of silver nitrate.

The silver halide photographic emulsion in which the sensitizing dye of the present invention is used is subjected to noble metal sensitization, sulfur sensitization, reduction sensitization and a combination thereof, or addition of a polyalkylene oxide compound or the like. May be.

The silver halide photographic emulsion in which the sensitizing dye of the present invention is used may be spectrally sensitized with other sensitizing dyes, for example, known cyanine and merocyanine dyes, if necessary. Stabilizer, surfactant,
Hardeners, optical brighteners, UV absorbers, filter dyes,
Additives such as anti-irradiation dyes, anti-halation dyes, preservatives, plasticizers, matting agents, color couplers and the like can be contained. Further, when used for a photosensitive material for stabilization processing, it may contain a developing agent or a precursor thereof.

Examples of protective colloids for silver halide photographic emulsions in which the sensitizing dye of the present invention is used include gelatin, gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, soluble starch, water-soluble polymers and the like. Is mentioned.

The support to which the silver halide photographic emulsion containing the sensitizing dye of the present invention is applied is, for example, baryta paper, plastic-laminated paper, synthetic paper, resin film such as cellulose triacetate or polyethylene terephthalate. Can be used. These supports may be provided with an undercoat layer and an antihalation layer, if necessary, by a known method.

[0049]

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 silver chloride emulsion prepared by a conventional method for producing a silver halide photographic emulsion was added with sensitizing dyes 31 and 32 of the sensitizing dyes 31 and 32 for comparison with the sensitizing dyes of the present invention shown in Table 1. 75 mmol / l DM
1.2 ml / g Ag of F solution was added. These emulsions were aged in a bath at 40 ° C. for 45 minutes to stabilize the spectral sensitization effect. 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 thus obtained was wedge-exposed according to the ISO method,
Using D-72 developer (developing solution of Eastman Kodak Company, USA), development was carried out at 20 ° C. for 90 seconds, stopping and fixing, and further washing with water, and after drying, strips having a predetermined black and white image were obtained. . The density was measured using a MACHBETH-TD504 densitometer manufactured by Macbeth Corporation in the United States to evaluate 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 to which no sensitizing dye was added was defined as 100, and the red sensitivity was a ratten gelatin filter No. manufactured by Eastman Kodak Company. 29 was used as the relative value when the sensitivity value of the comparative sensitizing dye 31 was 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.

[0051]

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[0052]

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[0053]

[Table 1]

As is clear from Table 1, the sensitizing dye of the present invention has higher sensitivity than the comparative sensitizing dye, less fog and less residual color stain after processing, and good photographic characteristics. I understand.

[0055]

By using the sensitizing dye of the present invention,
It is possible to obtain a highly sensitive silver halide photographic light-sensitive material with little residual color due to dye contamination.

Claims (1)

[Claims] 1. A spectral sensitizing dye for photography represented by the following chemical formula 1. Embedded image [In the formula, Z _{1 to} Z ₅ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. R ₁ represents a substituted or unsubstituted alkyl or aryl group, and R ₂ is
It represents a substituted or unsubstituted alkyl group. ]