JPH04242239A - Photographic spectrally sensitizing dye - Google Patents

Abstract

PURPOSE:To provide an extremely excellent dye as the sensitizing dye to be used for the silver halide photographic sensitive material. CONSTITUTION:This photographic spectrally sensitizing dye is represented by formula I in which Z is an atomic group necessary to form a 5- or 6-membered N-containing hetero ring; R is alkyl, aralkyl, or alkenyl: and n is 1 or 2, thus permitting this sensitizing dye to effectively enhance the sensitivity of the silver halide photosensitive emulsion and to extremely reduce fog and stains of the photographic sensitive material.

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 dye represented by Chemical Formula 1 is an excellent dye that satisfies the above objects.

In Formula 1, Z represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and R represents an alkyl group, an aralkyl group, or an alkenyl group. n is an integer 1
Or represents 2. To explain in more detail, examples of the 5- or 6-membered nitrogen-containing heterocycle formed by Z include the following. Thiazoline nucleus (e.g., thiazoline, 4-methylthiazoline, etc.), thiazole nucleus (e.g.,
thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, etc.), benzothiazole nuclei (e.g. benzothiazole, 5-fluoro Benzothiazole, 4-
Chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole 5-Bromobenzothiazole, 5-Yo-
Dobenzothiazole, 5-phenylbenzothiazole,
5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzo Thiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-methylenedioxybenzothiazole, 5-acetamidobenzothiazole ,5,
6-dimethylbenzothiazole, 5-hydroxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, etc.), naphthothiazole nuclei (e.g. naphtho[1 ,2-d]thiazole,
naphtho[2,3-d]thiazole, naphtho[2,1-d]
] Thiazole, 5-methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 5-
methoxynaphtho[2,3-d]thiazole, 8,9-dihydronaphtho[1,2-d]thiazole, etc.), oxazoline nuclei (e.g., oxazoline, 4,4-dimethyloxazoline, etc.), oxazo- nucleus (e.g. oxazole, 4-methyloxazole, 4-ethyloxazole,
5-methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, etc.), benzoxazole nuclei (e.g., benzoxazole, 5-fluorobenzoxazole, 5-chlorobenzoxazole, 5
-bromobenzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzo Oxazole, 5
-Carboxybenzoxazole, 6-chlorobenzoxazole, 6-methylbenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzo Oxazole, 5-chloro-6-methylbenzoxazole, 5,6-methylenedioxybenzoxazole, benzisoxazole
), naphthoxazole nuclei (e.g. naphtho [1,
2-d]oxazole, naphtho[2,1-d]oxazole, naphtho[2,3-d]oxazole, etc.), selenazoline nucleus (e.g. selenazoline), selenazole nucleus (
For example, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxy benzoselenazole, etc.), naphthoselenazole core (e.g., naphtho[1,2-d]selenazole, naphtho[2,1-d]selenazole, etc.), 3,3-dialkylindolenine core (
For example, 3,3-dimethylindolenine, 3,3,5-
trimethylindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-chloroindolenine, etc.), imidazole nuclei (e.g. 1-alkyl-4-phenylimidazole, 1- Alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole
1-alkyl-5,6-dichlorobenzimidazole
1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-alkylnaphtho[1,2-d]imidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole
1-aryl-5-chlorobenzimidazole, 1
-aryl-5,6-dichlorobenzimidazole, 1
-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-arylnaphtho[1,2-d]imidazole, the aforementioned alkyl group is a carbon atom 1 to 8, for example, unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl, and hydroxyalkyl groups (for example, 2-hydroxyethyl, 3-hydroxypropyl, etc.) are preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl groups represent phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) substituted phenyl, and the like. Pyridine nucleus (e.g.
2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.), quinoline nucleus (e.g., 2-quinoline, 4-quinoline, 3-methyl-2-quinoline, 5-ethyl -2-quinoline, 6-methyl-2-
Quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-
Chloro-2-quinoline, 6-ethoxy-4-quinoline,
8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, isoquinoline, 3,4-dihydro-1-isoquinoline, etc.), 1-alkyl tetra Sol nucleus (e.g. 1
-methyltetrazole, 1-ethyltetrazole), 1
Examples include -aryltetrazole nucleus (for example, 1-phenyltetrazole), pyrrolidine nucleus, and the like. R
Examples of the alkyl group include lower alkyl groups such as methyl, ethyl, propyl, butyl, hydroxyalkyl groups such as β-hydroxyethyl and γ-hydroxypropyl, and alkoxyalkyl groups such as β-methoxyethyl and γ-methoxypropyl. , acyloxyalkyl groups such as β-acetoxyethyl, γ-acetoxypropyl, β-benzoyloxyethyl, carboxyalkyl groups such as carboxymethyl, β-carboxyethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl, etc. Alkoxycarbonylalkyl group, β
- Sulfoalkyl groups such as sulfoethyl, γ-sulfopropyl, δ-sulfobutyl, etc., as aralkyl groups,
For example, benzyl, phenethyl, sulfobenzyl, etc.
Examples of alkenyl groups include allyl.

Representative examples of the sensitizing dyes represented by formula 1 of the present invention will be listed below, but the scope of the present invention is not limited thereto.

[0008]

[Case 2]

[0009]

[Chemical formula 3]

0010

[C4]

[0011]

[C5]

0012

[C6]

[0013]

[C7]

[0014]

[Chemical formula 8]

[0015]

[Chemical formula 9]

[0016]

[Chemical formula 10]

[0017]

[Chemical formula 11]

[0018]

[Chemical formula 12]

[0019]

[Chemical formula 13]

[0020]

[Chemical formula 14]

[0021]

[Chemical formula 15]

[0022]

[Chemical formula 16]

[0023]

[Chemical formula 17]

[0024]

[Chemical formula 18]

[0025]

[Chemical formula 19]

[0026]

[C20]

[0027]

[C21]

[0028]

[C22]

[0029]

[C23]

[0030]

[C24]

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 2 10.7 g of pyridine-3-aldehyde, 11.7 g of N-acetylglycine, and 8.2 g of sodium acetate were mixed.
30.6 g of acetic anhydride was added to this, and the mixture was heated and stirred at 100 to 105°C for 2 hours. After cooling, 300 ml of water was added, stirred well, and the precipitated crystals were collected by filtration and washed with water. Recrystallization was performed with acetonitrile, and after drying, 9.6 g of light brown needle crystals of 2-methyl-4-(3-pyridylmethylene)-5-oxazolinone with a melting point of 172.0 to 172.5°C were obtained. 1H-
NMR (250 MHz, CDCl3 /TMS) δ; 2
．． 41 (3H, s), 7.27 (1H, s), 7.52
(1H, m), 8.61 (2H, d, J=5Hz), 9
．． 17 (1H, s). Oxazolinone thus obtained1.
88g of 2-acetanilide vinyl-3-ethylbenzothiazolium iodide 4.50g and acetonitrile 30g
ml, and further added 3.03 g of triethylamine and heated under reflux for 30 minutes. After cooling, the precipitated crude dye was collected by filtration and washed with acetonitrile. Melting point after drying: 234.0℃
(Decomposition) 3.00 g of blue-purple crystalline powder was obtained. The maximum absorption value of the methanol solution was 556 nm. 1H
-NMR (250MHz, CDCl3 /TMS) δ;
1.38 (3H, t, J=7Hz), 3.97 (2H,
q, J = 7Hz), 5.70 (1H, d, J = 13Hz
), 5.82 (1H, d, J = 13Hz), 6.83 (
1H, s), 6.90-7.70 (6H, m), 8.5
2 (1H, d, J = 3.8Hz), 8.60 (1H, d
, J=5.9Hz), 9.04(1H,s,).

Synthesis Example 2: Synthesis of Chemical Formula 5 To 1.88 g of 2-methyl-4-(3-pyridylmethylene)-5-oxazolinone was added anhydro-4-anilidevinyl-3-(4-sulfobutyl)benzoselenazolium hydroxy. 4.35 g of carbon dioxide, 10 ml of acetic anhydride, and 3.03 g of triethylamine were added, and the mixture was heated and stirred at 100° C. for 15 minutes. After cooling, the precipitated crude dye was collected by filtration and washed with acetonitrile. After drying, 3.70 g of a blue-purple powder of triethylammonium salt of Chemical Formula 5 with a melting point of 209.0° C. (decomposed) was obtained. The maximum absorption value of the methanol solution was 556 nm.

The silver halide photographic emulsion in which the sensitizing dye of the present invention shown by formula 1 is used can be prepared using silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloride, etc. produced by a conventional method. Any metal such as silver bromide may be used. To add the sensitizing dye of the present invention to these silver halide photographic emulsions, methanol, ethanol, acetone,
It can be added alone or as a mixed solvent of organic solvents such as cellosolve, pyridine, dimethylformamide, etc., and 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 is calculated as 10% in terms of silver nitrate.
A wide range of approximately 4 to 1200 mg per 0 g can be used.

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.

[0036]

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 A 0.025% methanol solution of the sensitizing dye of the present invention was added to a silver chloride emulsion prepared by a conventional method in an amount of 1.2 ml per g of silver halide, calculated as silver nitrate. 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. Then,
Test samples were obtained by cutting them into appropriate sizes, and each sample was exposed to light according to the ISO method using D-72 (Eastman, USA).
The strips were developed for 90 seconds at 20° C. using Kodak Co., Ltd. developer formulation), stopped and fixed, and then washed with water. After drying, strips with a predetermined black and white image were obtained. This is the American Macbeth
Density was measured using a Macbeth RD-914 densitometer manufactured by Corporation, and the sensitivity and fog were determined. 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, the residual coloring (stain) of the sample after the development process was determined by comparing the unexposed sample to D-7.
Using a developer containing no metol or hydroquinone from the 2 developer formulation, immerse at 20°C for 30 seconds, fix for 30 seconds, wash with water for 30 seconds, and after drying visually evaluate the results. ) The evaluation was divided into five stages.

[0038]

[Table 1]

[0039]

As is clear from the Examples, the sensitizing dye of the present invention is excellent in terms of sensitivity, fog, and stain.

Claims (1)

[Claims] [Claim 1] A photographic spectral sensitizing dye represented by the following formula 1. [Formula 1] In Formula 1, Z represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and R is an alkyl group, an aralkyl group,
It represents an alkenyl group, and n represents an integer 1 or 2.