JPH03282449A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having high sensitivity in a near IR region and hardly lowering the sensitivity or causing fog during storage by incorporating a specified sensitizing dye. CONSTITUTION:At least one kind of tricarbocyanice dye represented by formula I is incorporated into a silver halide photographic emulsion. In the formula I, Z1 is a group of atoms required to form a thiazole, benzothiazole or naphthothiazole ring, Z2 is a group of nonmetallic atoms required to form a 5- or 6-membered ring contg. a methylene chain, each of Y1-Y4 is H or satd. hydrocarbon, adjacent two of Y1-Y4 may form a 5- or 6-membered ring contg. a methylene chain, Y1-Y4 are not simultaneously H, each of R1-R4 is alkyl or alkenyl, X is an acid anion and n is 1 or 2. High spectral sensitivity is obtd. in a near IR region and the sensivity and fog are hardly changed.

Description

[Detailed Description of the Invention] [Field of Industrial Application] What is the present invention? - It relates to a silver halide photographic light-sensitive material, and more specifically to a silver halide photographic light-sensitive material that is spectrally sensitized in the near-infrared region with a certain cyanine dye.

[Prior art]

Photographic materials are required to have high sensitivity in different specific wavelength ranges depending on their intended use.

As one of the manufacturing techniques for such light-sensitive materials, various types of cyanine dyes and merocyanine dyes are added to silver halide photographic emulsions, and they are used to produce specific sensitivity at wavelengths longer than the specific sensitivity wavelength range of silver halide. It is generally well known that sensitivity in the wavelength region of

Among these, although various types of dyes in the near-infrared region have been studied, the reality is that there are only a few that satisfy photographic properties including sensitization. In other words, when applying spectral sensitization in the near-infrared region to silver halide photographic emulsions using dyes, it is necessary not only to provide a spectral sensitization effect and increase sensitivity, but also to satisfy the following requirements. It must be something that does.

(1) The spectral deposition sensitivity range is appropriate. (2) No adverse interactions with other photographic additives. (3) Stable photographic properties must be maintained during storage of the photosensitive material. (
4) No contamination or capriole due to residual dye added for spectral sensitization after development.

etc. are required.

[Purpose of the invention]

Therefore, a first object of the present invention is to provide a spectrally sensitized silver halide photographic material that has high sensitivity in the near-infrared region and is free from staining and capri due to residual dyes.

A second object of the present invention is to provide a spectrally sensitized silver halide photographic light-sensitive material that exhibits less deterioration in sensitivity and less fog when the produced light-sensitive material is stored.

[Structure of the invention]

The present inventors have obtained various results, including at least one of the novel tricarbocyanine dyes represented by the following general formula.
It has been found that this can be effectively achieved by incorporating these into a silver halide photographic emulsion.

In the general formula, Zl represents an atomic group necessary to form a thiazole, benzothiazole, or naphthothiazole ring. These thiazole rings, condensed benzene rings, and naphthalene rings include alkyl groups (preferably lower alkyl groups such as methyl and ethyl), aryl groups (e.g. phenyl groups), hydroxy groups, and alkoxy groups (preferably methoxy and ethoxy groups). (lower alkoxy groups such as), carboxy groups, alkoxycarbonyl groups (preferably alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl), and halogen atoms (e.g., fluorine, chlorine, bromine, iodine, etc.). You can also fake it. Z2 is 5 containing a methylene chain
Or represents a group of nonmetallic atoms necessary to form a 6-membered ring. This ring may have a substituent such as a lower alkyl group (eg, methyl group, etc.). R1 and R2 may be the same and each represents an alkyl group [e.g., lower alkyl group such as methyl, ethyl, propyl, butyl, hydroxyalkyl group such as β-hydroxyethyl, γ-hydroxypropyl, β-methoxyethyl , alkoxyalkyl groups such as γ-methoxypropyl, β-acetoquinethyl, γ
- Acyloxyalkyl groups such as acetoxypropyl, β-pensoyloxyethyl, galboxyalkyl groups such as carboxymethinobe β-carboquinethyl, alkoxy heptalyponyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl, etc. It represents an alkyl group, a sulfoalkyl group such as β-sulfoethyl, γ-sulfopropyl, -sulfobutyl, an aralkyl group such as benzyl, phenethyl, sulfobenzyl, etc.), and an alkenyl group (for example, allyl).

X is an acid anion (for example, an alkyl sulfate ion such as methyl sulfate or ethyl sulfate, a thiocyanate ion, a toluenesulfonate ion, a halogen ion such as chlorine, bromine, or iodine,
perchlorate ion, etc.), and does not exist when the dye has a bequine structure.

n represents 1 or 2. Yl, Y2, Ys, Y4
hydrogen atom, saturated hydrocarbon group (e.g. cyclobutyl,
[cyclopentyl, cyclobutyl, cycloheptyl, etc.] or two that are brought into instant contact each other to form a five- or six-membered ring containing a methylene chain. However, Yl, Y2, Ys, and Y4 are never hydrogen atoms at the same time.

Next, typical examples of dyes used in the present invention will be listed.

(11) (12) 0s (8) [13] (14) (16) 03 (17) (18) (20) Next, a typical example of the synthesis of the novel cyanine dye used in the present invention will be described. state

Synthesis of dye example (1): 2.45 f of 2-anilinovinyl-3-ethyl-5,6,7,8-tetrahydro-β-naphthoxacillium-P-)luenesulfonate and 4 g of acetic anhydride. were mixed and heated to a bath temperature of 150-155°C for 15 minutes. After cooling, the reaction product was washed with ethyl ether, and 3-ethyl-2-(3
,5,5-)rifthyl-2-cyclohexene-1-ylidene)methyl-benzothiazolium iodide 2.13t
, pyridine 5- is added and heated, triethylamine 1.
67r was added and heated under reflux for 5 minutes. After the reaction and washing with ethyl ether, the crude dye was recrystallized twice with ethanol and dried to obtain 1.63P of green crystalline powder with a melting point of 218.0°C (decomposed). Maximum absorption value of methanol solution is 73
It was 2 nm.

Other dyes used in the present invention can also be easily synthesized according to the above synthesis example.

The maximum absorption value (nm) of the representative methanol solution used in the present invention is as follows.

Dye (1) 732nm (2) 758n
m(3) 751 nm (4) 711n
m(5) 725 nm (6) 736n
m(7) 729nm (8) 751nm
(9) 730nm (10) 729n
m (11) 731 nm (12) 74
7nm (13) 738nm (14) 7
25nm (15) 758nm (16)
723nm (17) 708nm (18)
747 nm (19) 758 nm (20)
745 nm The silver halide photographic emulsion used in the present invention may be any of silver chloride, silver bromide, chlorobromide scissors, silver iodobromide, silver chloroiodobromide, etc. produced by a conventional method. The dye used in the present invention can be added to these silver halide photographic emulsions using an aqueous solution or an organic solvent miscible with water such as methanol, ethanol, acetone, cellosolve, pyridine, dimethylformamide, etc. It can be added as a solution in a mixed solvent. ! However, when to add these dyes to silver halide photographic emulsions,
Although it may be added at any time during the emulsion manufacturing process, it is generally preferable to add it immediately after the second ripening is completed.

The amount added varies depending on the type of dye or the type of silver halide photographic emulsion, but it is calculated as 100% in terms of silver nitrate.
It can be used in a wide range of about 4 to 1,200 cm per 2 parts.

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

The silver halide photographic emulsion of the present invention 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 like stabilizers, surfactants, hardeners, optical brighteners, UV absorbers, filter dyes, anti-irradiation dyes, anti-halation dyes, preservatives, plasticizers, capping agents, color couplers etc. can contain agents.

Furthermore, when used in photosensitive materials for stabilization processing.

It can contain a developing agent and its precursor.

Protective colloids for the silver halide photographic emulsion of the present invention include, in addition to gelatin, gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose deconductors, soluble starch, and water-soluble polymers.

Examples of the support used in the present invention include baryta paper, plastic-laminated paper, synthetic paper, and resin films such as cellulose triacetate and polyethylene terephthalate. These supports can also be provided with a subbing layer and an antihalation layer by a known method, if necessary.

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

Example: To a silver chloride emulsion prepared by a conventional silver halide photographic emulsion manufacturing method, 0.01% solutions of the sensitizing dye used in the present invention and the following comparative sensitizing dye were added in terms of silver nitrate. Added 3-per-2. This emulsion was aged in a bath at 40° C. for 45 minutes to stabilize the spectral sensitization effect. Then stabilizer,
After adding a predetermined amount of a surfactant and a hardening agent, it is coated on a paper support laminated on polyethylene and dried.
It was aged overnight at 5°C. Next, it was cut to an appropriate size to obtain a test sample [Fresh]. A portion of this test sample was aged for 3 days at 50° C. and 80% relative humidity (Thermo). Color temperature of these test samples is 5,40
Light wedge exposure was performed using a photosensitive needle with a light source at 0° and a dark red filter (5C-70 manufactured by Fuji Photo Film Co., Ltd.) attached to the light source. After exposure, each sample was incubated at 20°C using D-72 developer (developed by Eastman Kodak, USA).
The film was developed for 90 seconds, stopped, fixed, and washed with water. After drying, an IJ tube with a predetermined black and white image was obtained. This is MACB manufactured by Macbeth Corporation in the United States.
The concentration was measured using an ETH-TD-504 densitometer to obtain the sensitivity and turnip IJk. The optical density reference point that determined the sensitivity was [Cub! J+0.30).

The sensitivity is shown in Table 1 as a relative value, with the fresh sensitivity of comparative dye F being 1.0.

(Sensitizing dye hole for comparison) (Same D) (Same E) ■ (Same B) (Same F) O3 O3 Table-1゜As is clear from the above Cloth-1, the novel cyanine dye used in the present invention It can be seen that it has high spectral sensitivity in the near-infrared region.

Furthermore, almost no change in sensitivity or capri was observed in the sample aged for 3 days at 50° C. and 80% relative humidity.

Claims (1)

[Claims] (1) At least one sensitizing dye represented by the following general formula
A silver halide photographic material comprising: General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z_1 represents the atomic group necessary to form a thiazole, benzothiazole, naphthothiazole ring,
Z_2 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring containing a methylene chain. Y_1, Y_2, Y_3, and Y_4 are hydrogen atoms, saturated hydrocarbon groups, or two adjacent ones that together form a 5- or 6-membered ring containing a methylene chain. However, Y_1, Y_2
, Y_3, and Y_4 are never hydrogen atoms at the same time. R_1 and R_2 may be the same and each represents an alkyl group or an alkenyl group. X represents an acid anion, and n represents 1 or 2. ]