JPH04241346A - Sliver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To effectively increase sensitivity and to suppress fog and stain by incorporating a sensitizing dye stuff represented by a specified formula. CONSTITUTION:One or more of sensitizing dyestuffs represented by formulae I-III are incorporated. In the formulae I-III, Z is a group of atoms required to form a benzene or naphthalene ring, each of R1-R5 is alkyl, aralkyl, etc., and n is 1 or 2. The sensitizing dyestuffs are superior spectral sensitizing dyestuffs for photography having a spectral sensitizing effect and increasing sensitivity because they have a proper spectral sensitization region, maintain stable photographic characteristics during storage, leave no stain or fog after development and have no adverse interaction with other photographic additives.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. 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 for use in silver halide photographic light-sensitive materials.

0002

2. Description of the Related Art Silver halide photographic materials are required to have high sensitivity in different specific wavelength ranges depending on their intended use. As one of the technologies for such silver halide photographic light-sensitive materials, various types of cyanine dyes and merocyanine dyes are added to silver halide photographic emulsions. It is generally well known that the sensitivity in a specific wavelength range can be extremely effectively increased in the wavelength range.

When applying spectral sensitization to silver halide photographic emulsions using dyes, it is necessary not only to simply impart a spectral sensitizing effect and increase sensitivity, but also to satisfy the following requirements. . (1) The spectral sensitization region is appropriate. (2) Stable photographic properties must be maintained during storage of the photosensitive material. (3) No staining or fogging due to residual dye administered for spectral sensitization should be avoided after development. (4) No adverse interactions with other photographic additives. etc. are required. However, although a considerable number of sensitizing dyes have been known to date, the reality is that there are only a few that satisfy the above-mentioned requirements in terms of sensitization and photographic properties.

0004

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an excellent photographic spectral sensitizing dye that satisfies the above requirements.

[0005]

[Means for Solving the Problems] As a result of various studies, the present inventors have discovered that the dyes represented by Chemical Formulas 1, 2, and 3 are excellent dyes that satisfy the above objects.

In formulas 1, 2, and 3, Z represents an atomic group necessary to form a benzene ring or a naphthalene ring, and these rings are lower alkyl groups (for example, methyl, ethyl, propyl, butyl, pentyl group, etc.), hydroxyl group, lower alkoxy group (e.g., methoxy, ethoxy, propoxy group, etc.), halogen atom (e.g., chlorine, bromine, iodine, etc.), sulfo group, carboxy group, cyano group, etc. It may have a substituent. R1 ~R
5 is an alkyl group (e.g., lower alkyl group such as methyl, ethyl, propyl, butyl, hydroxyalkyl group such as β-hydroxyethyl, γ-hydroxypropyl,
Alkoxyalkyl groups such as β-methoxyethyl and γ-methoxypropyl; acyloxyalkyl groups such as β-acetoxyethyl, γ-acetoxypropyl and β-benzoyloxyethyl; carboxyalkyl groups such as carboxymethyl and β-carboxyethyl; methoxy Alkoxycarbonylalkyl groups such as carbonylmethyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl, β-
sulfoalkyl groups such as sulfoethyl, γ-sulfopropyl, δ-sulfobutyl, etc.), aralkyl groups (e.g., benzyl, phenethyl, sulfobenzyl, etc.), alkenyl groups (e.g., allyl, etc.), aryl groups (e.g., phenyl, tolyl, etc.), methoxyphenyl, chlorophenyl, carboxyphenyl, sulfophenyl, naphthyl, etc.), and n represents 1 or 2.

Representative examples of the sensitizing dyes represented by Chemical Formulas 1, 2 and 3 of the present invention will be listed below, but the scope of the present invention is not limited thereto.

[0008]

[C4]

[0009]

[C5]

0010

[C6]

[0011]

[C7]

0012

[Chemical formula 8]

[0013]

[Chemical formula 9]

[0014]

[Chemical formula 10]

[0015]

[Chemical formula 11]

[0016]

[Chemical formula 12]

[0017]

[Chemical formula 13]

[0018]

[Chemical formula 14]

[0019]

[Chemical formula 15]

[0020]

[Chemical formula 16]

[0021]

[Chemical formula 17]

[0022]

[Chemical formula 18]

[0023]

[Chemical formula 19]

[0024]

[C20]

[0025]

[C21]

[0026]

[C22]

[0027]

[C23]

Next, a typical synthetic example of the dye represented by chemical formula 1 of the present invention will be described. Synthesis Example 1: Synthesis of Chemical Formula 4 1-Ethyl-2,5-dimethylspiro[3H-indolium-3,4'-tetrahydropyran]iodide 3.7
2 g and 3.07 g of 5-acetanilidomethylene-3-ethylrhodanine were added with 100 ml of ethanol and 7.0 ml of triethylamine, and heated under reflux for 1 hour. After cooling, the precipitated crystals were collected by filtration and washed with ethanol to obtain 3.15 g of the desired product. Melting point 209-210℃, λmax (MeOH
): 509nm

Synthesis Example 2: Synthesis of Chemical Formula 13 1-ethyl-5-methoxy-2-methylspiro[3H-
Indolium-3,4'tetrahydropyran] 3.88
g and 5-acetanilidemethylene-3-ethyl-2-thio-1,3-oxazolidine-2,4-dione 2.91
g, 100 ml of ethanol and 7.0 ml of triethylamine
1 was added thereto, and the mixture was heated under reflux for 3 hours. After cooling, the precipitated crystals were collected by filtration and washed with ethanol to obtain 2.40 g of the desired product. Melting point 9
3-95°C, λmax (MeOH): 472nm

Synthesis Example 3: Synthesis of Chemical Formula 19 4.90 g of 2-(2-anilinovinyl)-1-ethyl-5-methoxyspiro[3H-indolium-3,4'-tetrahydropyran]iodide and 1- 100 ml of ethanol and 7.0 ml of triethylamine were added to 2.51 g of carboxymethyl-3-phenyl-2-thiohydantoin, and the mixture was heated under reflux for 1 hour. After distilling off the solvent under reduced pressure, silica gel chromatography (developing solvent CHCl3/M
eOH: 20/1) to obtain 2.78 g of the desired product. Melting point 300℃ or higher, λmax (MeOH):
510nm

Silver halide photographic emulsions using the sensitizing dyes of the present invention represented by chemical formulas 1, 2, and 3 are as follows:
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, etc. produced by a conventional method may be used. To add the sensitizing dye of the present invention to these silver halide photographic emulsions,
It can be added alone or as a mixed solvent of organic solvents such as methanol, ethanol, acetone, cellosolve, pyridine, dimethylformamide, etc. which are arbitrarily miscible with an aqueous solution or water, and it can also be added as a dispersed solid particle. These sensitizing dyes may be added to the silver halide photographic emulsion at any time during the emulsion formulation process, but it is generally preferable to add them immediately after the second ripening. The amount added 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 1200 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 has been subjected to noble metal sensitization, sulfur sensitization, reduction sensitization, sensitization in combination thereof, or addition of a polyalkylene oxide compound. Good too. The silver halide photographic emulsion in which the sensitizing dye of the present invention is used may be spectrally sensitized by using other sensitizing dyes, such as known cyanine and merocyanine dyes, if necessary, and further by a known method. Additions such as stabilizers, surfactants, hardeners, optical brighteners, UV absorbers, filter dyes, anti-irradiation dyes, anti-halation dyes, preservatives, plasticizers, matting agents, color couplers etc. can contain agents. Furthermore, when used in a photosensitive material for stabilization processing, a developing agent or its precursor can be included.

Examples of the support coated with the silver halide photographic emulsion using the sensitizing dye of the present invention include baryta paper, plastic laminated paper, synthetic paper,
Resin films such as cellulose triacetate and polyethylene terephthalate can be used. These supports can also be provided with an undercoat layer and an antihalation layer, if necessary, by a known method.

[0034]

EXAMPLES The present invention will be explained in detail below based on Examples, but the present invention is of course not limited thereto.

Example 1 The sensitizing dyes 6, 7, 11, 15, 17, and 20 of the present invention and the comparative dyes 24 and 25 were added to a silver chloride emulsion prepared by a conventional method. 1.025% methanol solution per gram of silver halide, each calculated as silver nitrate.
2 ml was added. This emulsion was aged at 40° C. for 45 minutes to stabilize the spectral sensitization effect. After that, predetermined amounts of a stabilizer, a surfactant, and a hardening agent were added, and then coated on a paper support laminated with polyethylene, dried, and left at 40° C. overnight. Next, test samples were obtained by cutting them into appropriate sizes, and each sample was exposed to light based on the ISO method using D-72 (
20 using American Eastman Kodak developer formulation)
The strips were developed for 90 seconds at .degree. C., stopped, and fixed, and then washed with water and dried to obtain strips with a predetermined black and white image. This is Macbeth manufactured by Macbeth Corporation in the United States.
Density was measured using an RD-914 densitometer to obtain sensitivity and fog. The optical density reference point for determining the sensitivity was a point of 0.75. Furthermore, the sensitivity was expressed as a relative value, with the sensitivity of the unadded sample to which no sensitizing dye was administered as 100. In addition, to remove residual coloration (stain) of the sample after development, immerse the unexposed sample (dye amount: 3.6 ml) at 20°C for 30 seconds using a developer containing no metol or hydroquinone from the D-72 developer formulation. Fix for 30 seconds, wash with water 3
0 seconds, and after drying, the visual judgment was 5 (excellent) to 1 (
The evaluation was divided into 5 grades (poor). The dyes used for comparison are as follows.

[0036]

[C24]

[0037]

[C25]

[0038]

[Table 1] * Sensitivity is not required due to full-scale fogging.

[0039]

As is clear from the Examples, the sensitizing dyes of the present invention are superior to the comparative dyes in terms of sensitivity, fog, and stain.

Claims (1)

[Claims] 1. A silver halide photographic material containing at least one sensitizing dye represented by the following formulas: 1, 2, or 3. [Formula 1] [Formula 2] [Formula 3] In Formula 1, Formula 2, and Formula 3, Z represents an atomic group necessary to form a benzene ring or a naphthalene ring, and R1 to R5
represents an alkyl group, an aralkyl group, an alkenyl group, or an aryl group. n represents 1 or 2.