JPH03274546A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent irradiation and halation and to make improvement in a spectral filter effect, decolorability, elutability, and photographic characteristics by providing hydrophilic colloidal layers contg. at least one kind of specific dyes. CONSTITUTION:This photosensitive material has the hydrophilic colloidal layers contg. at least one kind of the dyes expressed by formula I. In the formula I, Z1 denotes the atom group necessary for forming pyridine, pyridazine and pyrazine ring; Z2 denotes the atom group necessary for forming benzene and naphthalene ring. R1 denotes a hydrogen atom, alkyl group, aryl group and heterocyclic group; R2 denotes a sulfoalkyl group; m denotes 1 or 2; n denotes 3 to 6. The dye molecules have at least two acid substituents. The irradiation and halation are improved in this way and the improvement in the spectral filter effect, decolorability, elutability, and photographic characteristics is made.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to a silver halide photographic light-sensitive material, and more particularly, it has a hydrophilic colloid layer colored with a novel light-absorbing dye, and is particularly suitable for photographic processing. The invention relates to a silver halide photographic light-sensitive material in which irradiation prevention and halation are prevented using a dye that is easily decolorized and removed during the process, and a silver halide photographic light-sensitive material provided with a filter layer.

(B) Prior Art In silver halide photographic light-sensitive materials, harmful reflections, scattering, and diffused light in the light-sensitive emulsion layer can be absorbed, or the interface between the emulsion layer and the support base and the back surface of the support can be absorbed. It is well known to prevent irradiation and halation and improve the sharpness of finished photographic images by absorbing unwanted reflected light from.

Furthermore, when there are multiple photographic emulsion layers such as on top of the emulsion layer or in a 9-layer color photographic light-sensitive material, a colored layer (filter layer) is provided between them to control the spectral composition that should be incident on the photographic emulsion layer. Control is also well known.

In order to prevent irradiation and halation, dyes applied to the light-sensitive emulsion layer, between the emulsion layer and the support, to the backing layer of the support, or into the filter layer should be used during solution preparation or during exposure to light. Of course, during emulsion production and storage, changes over time such as discoloration and fading must not occur, but photographic properties such as fogging and desensitization must not be adversely affected.

In addition, during the development process, it is necessary to completely and quickly decolorize or
Alternatively, it must be eluted and removed from the photographic material. Preferably, the dye is of a bleaching type, and the bleached dye is eluting and does not color the processing solution. Furthermore, it must have spectral absorption characteristics that meet the respective purposes, and must have anti-irradiation, anti-halation, and spectral filter effects.

However, to date, quite a large number of dyes have been proposed, but they have different decolorizing properties, dissolution properties, photographic properties, etc.

The reality is that there are few that satisfy the above conditions.

(C) Purpose of the Invention Therefore, the purpose of the present invention is: It is an object of the present invention to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer colored with a photographic light-absorbing dye that satisfies the above-mentioned conditions and has excellent irradiation, antihalation, and filter effects. .

(D) Structure of the Invention As a result of various studies conducted by the present inventor, the object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one dye represented by the following general formula. found that this can be achieved by

In the general formula, 21 represents an atomic group necessary to form a pyridine, pyridazine, or pyrazine ring, and the cholera ring is an alkyl group (e.g., 2 methyl, ethyl, propyl, butyl, pentyl, etc.), an aryl group (e.g., phenyl, methethyl, etc.), aralkyl groups (e.g. benzyl, phenethyl, etc.)
, hydroxy group.

Alkoxy groups (e.g. methoxy-1-ethoxy, propoxy, butoxy, etc.), halogen atoms (e.g.

(chlorine, bromine, etc.), cyano group, carboxy group, alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), 21-ro group, sulfo group, acyl group (e.g., acetyl, benzoyl, etc.), etc. You can leave it there. z2 represents an atomic group necessary to form a benzene-2-naphthalene ring, and these rings may have a substituent as described above for Z. R7 is a hydrogen atom. ．． (These groups may be further substituted with an alkyl group, an alkoxy group, a halogen atom, etc.)
and heterocyclic groups (e.g., pyridyl.

quinol, furyl, thienyl, thiazolyl, indolyl, etc.), and R2 represents a sulfoalkyl group (eg, sulfoethyl, sulfopropyl, sulfobutyl, etc.).

m represents 1 or 2, and n represents 3-6. The dye represented by the above general formula has at least two acid substituents (eg, sulfo group, carboxy group) at the center of the four-molecule structure.

The dye represented by the above general formula can take the form of an alkali metal salt (eg, potassium, strium, etc.) or an ammonium salt (eg, triethylammonium pyridinium, etc.).

Although the silver halide photographic material colored with the dye of the present invention represented by the above general formula has a broad absorption band in the target wavelength range, it has almost no absorption band in other wavelength ranges. There is no side absorption, and the dye of the present invention has
All have high molecular extinction coefficients, and exhibit excellent anti-irradiation, anti-halation, and filter effects with a small amount of use, without causing negative effects on photographic properties such as fog or desensitization. be able to. Furthermore, after the development process, the dye is quickly and completely decolored and eluted from the photosensitive material.

In the finished photograph, not only does the dye contained for the above purpose remain, but there is also no color contamination caused by the recoloring of the decolorized dye, and furthermore, there is no re-dying caused by the coloring of the developing solution. Furthermore, the dye of the present invention does not undergo any changes such as discoloration or fading during the preparation of the dye solution, and is stable without being affected by external conditions such as moist heat during the production of the photosensitive emulsion or during subsequent storage. It has the advantage of being

Next, among the dyes represented by the above general formula of the present invention.

Here are some typical examples.

(Margin below) Dye (5) SOL SO9 SO1 Dye (9) SOL (Margin below) Next, two typical examples of dye synthesis methods will be specifically described.

Synthesis of dye (3) Anhydro-33-pentamethylene-2-methyl-1-
(3-Sulfopropyl)-5-sulfo-3H-indolium hydroxide, triethylammonium salt IL5g
and 3-formyl-2-phenylpyrazolo (1,5-a
) Mix 4.4 g of pyridine.

Add 100 mA' of acetic acid and 50 ml of acetic anhydride to this! was added and heated and stirred at 90 to 100°C for 2 hours. After cooling to room temperature, the precipitated crude dye was collected by filtration. After washing with acetone, it was recrystallized with ethanol. After drying, 6.5 g of a red-orange crystalline powder with a melting point of 299.0° C. (decomposed) was obtained. The maximum absorption values of the aqueous solution were 485 and 507 mm.

Synthesis of dye (I4); anhydro-3,3-pentamethylene-2-methyl-1
-(3-Sulfopropyl)-5-sulfo-3H-indolium hydroxide, triethylammonium salt 10.
5g and 3.7g of 3-(2-methylpyrazolo(1,5-a)pyridin-3-yl)acucholein were mixed, 1ml of acetic acid H1)mI and 1ml of acetic anhydride were added, and the mixture was heated to 90~
The mixture was heated and stirred at 100°C for 15 minutes.

After cooling to room temperature, the crude dye produced was collected by filtration. After washing with acetone and ethanol, the product was dried to obtain 5.2 g of a golden-colored dark green crystalline powder with a melting point of 259.0°C (decomposed). The maximum absorption values of the aqueous solution were 550 and 585 mm.

The dye represented by the general formula of the present invention can also be easily synthesized according to the above synthesis example.

In order to add the dye of the present invention represented by the above general formula into a silver halide photographic emulsion or a protective colloid solution, an aqueous solution, methanol or ethanol may be used.

Cellosolves, glycols, dimethylformamide,
Emulsion layers, backing layers, subbing layers, intermediate layers, and protective layers as solutions of dimethyl sulfoxide, pyridine, etc., or mixed solutions of these organic solvents and water.

It can be added and present in the ultraviolet absorbing layer.

The amount of these dyes used varies depending on the applied photographic layer, but is generally 5 to 1 per 1rd area of the photosensitive material, OHm
It is applied so that it becomes g.

Examples of silver halide photographic emulsions in which the dye of the present invention can be used include silver chloride, silver bromide, and silver chlorobromide.

There are emulsions such as silver iodobromide and silver chloroiodobromide.

Further, the silver halide photographic emulsion in which the dye of the present invention is used is spectrally sensitized with a commonly used cyanine or merocyanine dye. Furthermore, an amino group,
Or basic mordants such as polymers containing ammonium groups or polymers containing nitrogen-containing complexes, stabilizers and their precursors, surfactants, hardeners, ultraviolet absorbers, optical brighteners, developing agents and their precursors. It is also possible to include additives such as esters and the like. When a silver halide photographic emulsion is used in a color light-sensitive material, it can also contain a color coupler or a dispersant thereof.

In addition to gelatin, protective colloids for silver halide emulsions include gelatin derivatives such as phthalated gelatin and malonated gelatin, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and plasticizer latex for dimensional stability. Polymers etc. can be added.

Furthermore, the silver halide in which the dye of the present invention is used can be synthesized from baryta paper or resin-coated paper, and applied to a support such as a natural or synthetic polymer film such as cellulose triacetate or polyester.

Next, the present invention will be described in more detail with reference to Examples.

Example 1 1.55 g of gelatin was added to 15.0 m7 of water to swell it, and then heated to 40.0°C to dissolve the gelatin. To this gelatin solution were added an aqueous solution (2,0XIO-' moles/2.0 ml of water) of the dye of the present invention and a comparative dye (to be described later), a hardener, and a surfactant, and then water was added to bring the total volume to 20.
The volume was reduced to 0 ml. Next, this colored gelatin solution was applied in an amount of 85 g onto a subbed polyester film base.
/rr! The sample was coated so as to have the following properties, heated at 511.0°C for 24 hours, and cut into a rectangle of 8.0 x 11.5 nm to prepare a sample.

The sample was immersed in D-72 developer solution at 30.0°C for 5 seconds and 15 seconds, then washed under running water for 10 seconds, and the adhering water droplets were removed by filtering and dried to obtain a processed sample. . Materials and processed samples are Macbeth transmission densitometer TD-
504 was used to measure 5 points, and the average value was taken as the respective concentration. The results obtained are shown in Table-1.

(The following is a blank space) Table 1 As is clear from Table 1, the dye used in the present invention has a higher initial concentration and a lower concentration after treatment than the comparative dyes, that is, it has excellent decolorizing properties. I understand that.

Example 2: Add 1% aqueous solution of Dye 1 to 10% gelatin aqueous solution and add 85g
The optical density was adjusted so that the optical density was approximately 10 when a coating layer of /rd was added.
l/7 phosphorus at 1.5mA! In addition, using the colored aqueous gelatin solution obtained, a hardened coating layer having an optical density of approximately 1.11 is obtained by the same operation as in Example 1. A quasi-silver bromide emulsion was coated on this coated layer and developed at 20° C. for 90 seconds using a developer having the composition shown below, followed by fixing, washing with water, and drying according to a conventional method.

When the optical density of the obtained treated film was measured using the method performed in Example 1, the post-processing density of each sample containing the dye of the present invention was all 0.03, the same as the base density. .

Bonding of developer Metol 3g Sodium sulfite 45g Hydroquinone 12g Sodium carbonate (monohydrate) potassium bromide Add water to make a total volume of 7I.

In addition, each sample containing the dye of the present invention does not undergo changes over time such as discoloration or fading during preparation of an aqueous solution, preparation of an emulsion, or storage.
It was a photosensitive material that had an extremely excellent antihalation effect without adversely affecting photographic properties such as fog or desensitization.

Claims (1)

[Claims] (1) Silver halide photographic light-sensitive material characterized by having a hydrophilic colloid layer containing at least one dye represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z_1 represents an atomic group necessary to form a pyridine, pyridazine, or pyrazine ring, and Z_2 represents an atomic group necessary to form a benzene or naphthalene ring. R_1 is a hydrogen atom, an alkyl group, an aryl group, or a heterocycle. represents a formula group, and R_2 represents a sulfoalkyl group. m
represents 1 or 2, and n represents 3-6. However, the dye molecule shall have at least two acid substituents. )