JPS5852575B2 - silver halide photographic emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic emulsion spectrally sensitized with a novel merocyanine dye, and particularly to a silver halide photographic emulsion with increased spectral sensitivity in the blue and green wavelength regions. be.

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, such as yamerocyanine dyes, are added to silver halide photographic emulsions, and they are used to produce specific rays at wavelengths longer than the specific sensitivity wavelength range of the silver halide. It is generally well known that the sensitivity in the wavelength range can be extremely effectively increased.

Among these, although various types of merocyanine dyes have been studied so far, the reality is that there are only a few that satisfy photographic properties including sensitization.

In other words, when applying the spectral sensitization method using merocyanine dyes to silver halide photographic emulsions, it is necessary not only to impart a spectral sensitization effect and increase sensitivity, but also to satisfy the following requirements. Must be.

(1) The spectral sensitization region is appropriate.

(2) There should be no adverse interaction with other additive chemicals for photography, and the photosensitive material should have stable photographic properties even during storage.

(3) It is required that no staining or fogging due to residual dyes administered for spectral sensitization be left after the development process.

Accordingly, a first object of the present invention is to provide a spectrally sensitized silver halide photographic emulsion which has high sensitivity in the blue and green wavelength ranges and is free from staining and fog caused by residual dyes.

A second object of the present invention is to provide a spectrally sensitized silver halide photographic emulsion that exhibits little decrease in sensitivity when the manufactured photographic material is aged.

A third object of the present invention is to provide a spectrally sensitized silver halide photographic emulsion in which the sensitivity wavelength edge approaches the sensitivity maximum and has high safety against safe light.

As a result of various studies, the present inventors have found that the above objects can be effectively achieved by incorporating at least one of the novel merocyanine dyes represented by the following general formula into a silver halide photographic emulsion. .

In the general formula, D represents an atomic group necessary to form a 5- or 6-membered heterocycle.

Specific examples of heterocycles containing D include, for example, oxazole ring, benzoxazole ring, naphthoxazole ring, benzisoxazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenasoline ring, selenazole ring, benzoselenium ring. Zole ring, naphthoselenazole ring, pyridine ring, quinoline ring, benzo (
f, l There are quinoline rings, indolenine rings, benzimidazole rings, naphthimidazole rings, pyrrole rings, pyrrolidine rings, tetrazole rings, etc., and these heterocycles, fused benzene rings, and naphthalene rings are alkyl groups (preferably methyl, aryl group (lower alkyl group such as ethyl)
For example, phenyl group), hydroxy group, alkoxy group (
OX which may have a substituent such as a halogen atom, preferably a lower alkoxy group such as methoxy or ethoxy), a carboxy group, an alkoxycarbonyl group (preferably a lower alkoxycarbonyl group such as methoxycarbonyl or ethoxycarbonyl), Hydrogen atom, carboxy group, alkoxycarbonyl group (preferably methoxycarbonyl,
(lower alkoxycarbonyl group such as ethoxycarbonyl)
, Y represents a hydrogen atom or an alkyl group (preferably a methyl group), and 2 represents a carbamoyl group, a cyano group, a sulfo group, a carboxy group, an alkoxycarbonyl group (preferably a lower alkoxycarbonyl group as described in X) ).

R1 is an alkyl group (for example, methyl, ethyl, propyl, butyl, etc.), a lower alkyl group, β-hydroxyethyl,
Hydroxyalkyl group such as γ-hydroxypropyl, β
-Alkoxyalkyl groups such as methoxyethyl and γ-methoxypropyl, acyloxyalkyl groups such as β-acetoxyethyl, γ-acetoxypropyl, and β-penzoyloxyethyl, carboxyalkyl groups such as carboxymethyl and β-carboxyethyl, and methoxycarbonyl Alkoxycarbonyl alkyl groups such as methyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl, sulfoalkyl groups such as β-sulfoethyl, γ-sulfopropyl, δ-sulfobutyl, aralkyl groups such as benzyl, phenethyl, sulfobenzyl, etc.), alkenyl groups (e.g.
R2 represents an alkyl group (alkyl group as mentioned in R1, cycloalkyl group such as cyclohexyl), alkenyl group (e.g. allyl), aryl group (e.g. phenyl, carboxyphenyl, sulfonyl group), phenyl, anisyl, tolyl, halogen-substituted phenyl, etc.), R3 represents a hydrogen atom, an alkyl group (e.g., a lower alkyl group such as methyl, ethyl, a substituted alkyl group such as β-hydroxyethyl, carboxymethyl, etc.),
Represents an aryl group (eg, phenyl, tolyl, carboxyphenyl, etc.).

(2), m and n each represent 1 or 2.

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

Next, a representative example of the synthesis of the novel merocyanine dye used in the present invention will be described.

Synthetic heavy gelycin ethyl ester chlorine salt of dye example (6) 14. Of and β-(β-
After adding 22.8 f of chloroethylsulfonyl) propionic acid ethyl ester to 300 mA' of dioxane and further adding 30.3 P of triethylamine, the bath temperature was 100-11.
The mixture was heated and stirred at 0°C for 5 hours.

After cooling to room temperature, insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure.

13.59 g of phenyl thiocyanate was added to the obtained light brown viscous liquid and heated at a bath temperature of 100 to 110° C. for 5 hours.

After approximately cooling, 300 mJ of ethanol was added and stirred to separate a solid.

The solid was collected by filtration and washed with ethanol.

When recrystallized with methanol and dried, the melting point is 133.0.
26.2 f of white needles of 1-[β-(β-ethoxycarbonylethylsulfonyl)ethyl]-3-phenyl-2-thiohydantoin at ~134.0°C were obtained.

This thiohydantoin intermediate 1. x5ii' and 2-acetanilide vinyl-1-methylpyrrolinium iosito 1
．． 11S' with 50 ml of ethanol and 0 triethylamine
．． 911 was added, and the mixture was heated under reflux for 30 minutes.

After cooling to room temperature, the precipitated crystals were collected by filtration and washed with ethanol.

When recrystallized with ethyl acetate and dried, the melting point was 196.0.
~197.0'C orange powder of exemplary dye (6) 0.72
was gotten.

Synthesis of dye example (L6) Nigericin ethyl ester hydrochloride 28. Of and β-bi0
Add 32.6f of ``Rusulfonylprobionamai'' to 200mJ of dioxane, and then add 40.4f of triethylamine.
After adding f, the mixture was heated and stirred at a bath temperature of 100 to 110°C for 5 hours.

After cooling to room temperature, insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure.

The residue was recrystallized from ethanol and then from ethyl acetate.

White powder of β-[β-(ethoxycarbonylmethylamino)ethylsulfonyl]propionamide having a melting point of 86.0 to 87.0°C after drying 34. '1 was obtained.

This amide 26.6y and ethyl inthiocyanate 8
．． 71 was mixed and heated at a bath temperature of 100 to 110°C for 5 hours.

Ethanol 100mA after cooling! was added and stirred, and a solid separated.

The solid was collected by filtration, washed with ethanol, and dried to give 1-(β-(β-carbamoylethylsulfonyl)ethyl, l-3-4-f-2-thio Almost white powder of hydantoin 22.1
'was gotten.

This thiohydatoin intermediate 1.53f and 2-acetanilidevinyl-3-allyl-α-naphthoxacillium-
p-4 luenesulfoner) 2.70f to 50% ethanol
ml and 1.50 P of triethylamine were added, and the mixture was heated under reflux for 30 minutes.

After cooling to room temperature, the precipitated crystals were collected by filtration and washed with ethanol.

Exemplary dye (16) with a melting point of 229.0°C (decomposed) when recrystallized with pyridine, washed with methanol, and dried.
0.65P of bright red-orange crystalline powder was obtained.

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

The absorption maximum values (nm) of methanol solutions of the representative examples of the dyes used in the present invention are as follows.

Pigment example 470 75 75 85 10 67 480 * 1 71 70 85 69 428 * 1 50 68 75 95 75 70 70 510 ゞ 270 70 70 70 490.510 * 1 87 935 () 3 * T 71 75 75 74 Aquarium. 2. Dimethylformamide solution The silver halogenide photographic emulsion used in the present invention can be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. produced by a conventional method. In order to add the dye to these silver halogenide photographic emulsions, an aqueous solution or an organic solvent optionally miscible with water such as methanol, ethanol, acetone, cellosolve, pyridine, dimethylformamide, etc. may be added alone or in combination. It can be added as a solution in a solvent.

Although these dyes may be added to the silver halide photographic emulsion at any time during the emulsion manufacturing process, it is generally preferable to add them immediately after the second ripening.

The amount added varies depending on the type of dye or the type of silver halide photographic emulsion, but it can be used in a wide range of about 4 to 1200 parts per 1002 silver nitrate.

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 or the like.

The silver halide photographic emulsion of the present invention may be color sensitized by using other sensitizing dyes, for example, known cyanine and merocyanine dyes, as required, and furthermore, by a known method, stabilizers, surfactants, etc. Additives such as agents, hardeners, brighteners, UV absorbers, preservatives, matting agents, plasticizers, etc. may be included.

When the silver halide photographic emulsion of the present invention is used in a light-sensitive material for color photography, it may contain a color coupler or a dispersant thereof.

Furthermore, when used in a photosensitive material for stabilization processing, a developing agent may also be included.

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 derivatives, 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 a nolation prevention layer, if necessary, by a known method.

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

Example A pure silver bromide emulsion prepared by the double-jet method was subjected to a second ripening by the sulfur sensitization method, and then the emulsion was divided into several portions and treated with sensitizing dyes in the amounts shown in Table 1 below. solution was added.

This emulsion was aged at about 40°C for 45 minutes to stabilize the color sensitization effect, then a predetermined amount of coating aid and hardener was added, and then coated on a polyethylene-laminated paper support and dried. and cut it into Strisobus.

A portion of this strip was aged for 2 days at 50° C. and 80% relative humidity.

These samples were exposed to light using a sensitometer having a light source with a color temperature of 5400°, and the white light sensitivity was measured.

Further, exposure was performed to obtain a spectrum using a diffraction grating type spectrograph having a tungsten** light source at 2666°.

Subsequently, each sample was developed using D-72 developer (developed by Eastman Kodak, USA) at 20°C for 90 seconds, stopped, fixed, and washed with water. After drying, a prescribed black and white image was formed. I got Motsu Strips.

This is MACBETH manufactured by Macbeth Corporation in the United States.
Density was measured using a TD-504 densitometer to obtain white light sensitivity.

The optical density reference point used to determine the sensitivity was [Cub 1
．． l+0.30].

The results obtained are shown in Table 1 as relative values.

*White light sensitivity is expressed as a relative value with the value of the original emulsion without dye added as 100.

As is clear from Table 1 above, it can be seen that the novel merocyanine dye used in the present invention exhibits a sufficient spectral sensitizing effect.

In addition, almost no staining due to residual dye was observed after development.

This can be understood from the fact that the fog values of the dye-added samples did not change compared to the blank fog values.

Furthermore, almost no change in sensitivity or fog was observed in the samples aged at 50° C. and 80% relative humidity for 2 days.

Claims (1)

[Scope of Claims] 1. A silver halide photographic emulsion containing at least one compound represented by the following general formula. General formula (in the formula, represents the atomic group necessary to form a 5- or 6-membered heterocycle. It represents a carbamoyl group, a cyano group, a sulfo group, a carboxy group, an alkoxycarbonyl group. R1 represents an alkyl group, a 7/l/kenyl group, R2 represents an alkyl group, an alkenyl group, an aryl group, and R3 represents a hydrogen atom, an alkyl group. group, aryl group. l, m and n each represent l or 2). 2. The silver halide photographic emulsion according to claim 1, wherein the heterocycle containing D is selected from an oxazole ring, a benzoxazole ring, a naphthoxazole ring, a thiazoline ring, a pyridine ring, and a pyrrolidine ring.