JPH0273247A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the irradiation and the halation of the subject material, and to improve the filter effect of the photosensitive material by incorporating a specified dyestuff in the photosensitive material. CONSTITUTION:The dyestuff shown by formula I and having absorption maximum at an infra-red wavelength region is incorporated in the hydrophilic colloidal layer of the photosensitive material. In the formula, R1-R6 are each an (un)substd. alkyl, Z<1> and Z<2> are each an atomic group necessary for forming a prescribed condensed ring, L is an (un)substd. methine, X is an anion, (n) is 1 or 2. The dyestuff shown by the formula is composed of a compd. shown by formula II, and is stable without being affected on moist and hot environments, etc. during the preparation of an emulsion or the preservation of the emulsion after the preparation thereof, and is rapidly decolored and eluted from the photosensitive material by developing it.

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 to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer. It is something.

(B) Prior Art In silver halide photographic materials, the photographic emulsion layer or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a filter layer.

When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

When passing through the photographic emulsion layer, or after passing through the photographic emulsion layer, the scattered light is reflected at the interface between the emulsion layer and the support, or at the surface of the photographic material opposite to the emulsion layer, and enters the photographic emulsion layer again. Between the photographic emulsion layer and the support, for the purpose of preventing blurring of images, that is, halation, caused by
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer.

Such a colored layer is called an antihalation layer.

When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, an antihalation layer may be placed between the layers.

Decreased image sharpness due to light scattering in the photographic emulsion layer (
In order to prevent this phenomenon (generally called irradiation), the photographic emulsion layer is also colored.

These layers to be colored often consist of hydrophilic colloids, and therefore, for their coloring, water-soluble dyes are usually included in the layers.

This dye needs to satisfy the following conditions.

(1) It must have appropriate spectral absorption according to the purpose of use.

(2) Absorbance is sufficiently high.

(3) Photochemically inert. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

(4) (Photographic emulsion) No changes over time, such as discoloration or fading, should occur during coating solution preparation, emulsion production, or storage.

(5) (Photographic emulsion) When added to a coating solution, it should not increase viscosity and cause coating failure.

(6) In the photographic processing process, no harmful coloration remains on the photographic material after being bleached or dissolved and removed.

In order to satisfy such conditions, many dyes that absorb visible light or ultraviolet light have been proposed.

Triarylmethane and oxonol dyes are widely used for the above-mentioned image improvement purposes, particularly in photographic elements sensitized to wavelengths below 700 nm.

On the other hand, in recent years, antihalation and antiirradiation dyes that absorb in the infrared region have been used for recording materials sensitized in the infrared region, for example, photographic materials used as recording materials that record the output of near-infrared lasers. development was requested.

For example, one of the exposure methods for such photographic light-sensitive materials is to scan an original image, and then expose the silver halide photographic light-sensitive material based on the image to form a negative or positive image corresponding to the image on the original image. A so-called scanner-only image forming method is known.

A semiconductor laser is most preferably used as the recording light source for this scanner type.

This semiconductor laser is small, inexpensive, easy to modulate, has a longer lifespan than other lasers such as 1e-Ne lasers and argon lasers, and emits light in the infrared region. When used, a bright safelight can be used, which has the advantage of improving handling workability.

Regarding such dyes for photographic light-sensitive materials that are sensitive to the infrared region, (a) JP-A-50-100116 and JP-A-61-1745.
40 and 62-3250@, the use of specific indoaniline dyes as dyes for infrared absorption, and (b) JP-A-55-21094 and JP-A-55-21095.
2-carbamoyl-1- specified in No. 55-21096 and Research Tissue Roger No. 22338.
An infrared dye is formed from a naphthol coupler and a color developing agent in a hydrophilic colloid layer.

However, the indoaniline dyes mentioned in (a) above have poor stability over time, insufficient decolorization during photographic processing, and low absorbance, so it is difficult to use a large amount of dye in order to achieve sufficient effects. However, these methods have the disadvantage of causing desensitization or increased fog because they require a dye of m or are not photochemically inert.

Furthermore, when some indoaniline dyes are added to coating solutions (photographic emulsions), their viscosity increases, often making coating impossible.

In addition, since the infrared dye formed from 2-carbamoyl-1-naphthol and a color developing agent in (b) above is water-insoluble, when it is incorporated into the hydrophilic colloid layer, an oil-soluble solvent is required. This has resulted in undesirable phenomena such as an increase in film thickness and a decrease in film strength.

Furthermore, these dyes have the disadvantage that they are difficult to dissolve and decolorize during photographic processing because of their water insolubility.

Therefore, conventional dyes meet the above-mentioned conditions required for them.
There is no option that satisfies all of (1) to (6), and therefore there has been a desire for a dye for photographic materials that takes advantage of the characteristics of semiconductor lasers having excellent performance as described above.

(C) Purpose of the Invention Therefore, the purpose of the present invention is to meet the above-mentioned conditions (1) to (6).
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 water-soluble photographic light-absorbing dye, which has excellent irradiation, antihalation, and filter effects that satisfy the following requirements.

(D) Structure of the Invention As a result of various studies on water-soluble dyes, the present inventors have unexpectedly found that the object of the present invention is to obtain a hydrophilic dye containing at least one of the dyes represented by the following general formula [I]. It has been found that this can be achieved by a silver halide photographic material characterized by having a colloid layer.

General formula (I) 3R5 R, R2 (X)n-1 In the formula, R1, R2, R3, R4, R5 and Re may be the same or different, and each represents a substituted or unsubstituted alkyl group (having 1 carbon number -5 lower alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) are preferred,
It may have a substituent (for example, a sulfo group, a carboxyl group, a hydroxyl group, etc.).

L represents a substituted or unsubstituted methine group, and X represents an anion.

Examples of the anion represented by X include halogen ion, P-toluenesulfonate ion, and methylsulfate ion.

n is 1 or 2, and is 1 when the dye forms an internal salt.

Zl and Zl each represent a group of nonmetallic atoms necessary to form a benzo-fused ring or a naphtho-fused ring which may have a substituent, and examples of the substituent of the ring include a sulfo group and a carboxyl group. , hydroxyl group, halogen atom, 1 cyano group, substituted amino group (e.g. dimethylamino group, diethylamine group, xamoyl group, or substituted or unsubstituted carbon number 1 bonded to the ring directly or via a divalent linking group)
-5 alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group (substituents include sulfo group, carboxyl group, hydroxyl group, etc.)), and divalent linking groups include, for example, -0 -1N HCO-, NH30z
, -NH-COO-, -N (C0NH-1-co
o--co-1SO2- etc. are failed.

However, in Zl and Zl, the dye molecule has at least a bohydroxamoyl group.

R represents 1 or an alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.).

Although the silver halide photographic light-sensitive material colored with the dye of the present invention represented by the above general formula (I) has a high molecular extinction coefficient in the target wavelength region, other In the wavelength range, there is no unnecessary sub-absorption such as dot/V, and it also provides excellent anti-irradiation, anti-halation, and filter properties with a small amount of use, without causing any negative effects on photographic properties such as fog or desensitization. The effect can be fully demonstrated.

In addition, after the development process, the dye is completely and quickly decolored and eluted from the photosensitive material, so the finished photographic image contains
Not only the residual dye contained for the above-mentioned purpose, but also color contamination due to recoloring of the decolorizing dye, and re-dying due to coloring of the developing processing solution cannot be avoided.

Furthermore, the dye of the present invention does not undergo changes such as discoloration or fading during the preparation of the dye solution, and is not affected by external conditions such as moist heat during the preparation of the photographic emulsion or during subsequent storage. It has the advantage of being very stable.

Furthermore, when the dye of the present invention was added to a (photographic emulsion) coating solution, no increase in viscosity was observed and no coating abnormality was observed.

Representative examples of the dyes of the present invention represented by the general formula (I) will be listed below, but the scope of the present invention is not limited thereto.

(Left below) The dye represented by the general formula [I] has an absorption maximum of 730
~850 nm, Journal of the Chemical Society (J, Chem, Soc.

189 (1933)) and U.S. Patent 2,895,955
@It can be synthesized with reference to the specification and the following synthesis examples.

Synthesis Example 1 (Synthesis of Exemplified Compound 1) 2.3.3-Trimethyl-5-carbohydroxamoyl-1-(3-sulfopropyl)indolenine 0.73 and methanol 20d mixed solution with triethylamine 0.5
rni, glutaconaldehyde cyanyl hydrochloride 0.34
After stirring thoroughly, 0.3 d of acetic anhydride was added, and the mixture was stirred overnight at room temperature.

After the reaction, the solvent was removed from the reaction solution under reduced pressure, and column chromatography was performed to obtain the desired product.

(Development: chloroform methanol mixed solvent) Dark green metallic luster crystal Yield: 0.23 g λmax 756
nmλmax 755 n... To add the dye of the present invention represented by the general formula (I) to a silver halide photographic emulsion or a protective coid solution, use an aqueous solution, methanol, ethanol, cellosolves, glycols, dimethylformamide, etc. Also, as a solution of
A mixed solution of these organic solvents and water can be added to and present in an emulsion layer, backing layer, subbing layer, intermediate layer, protective layer, or ultraviolet absorbing layer.

The usage ω of these dyes varies depending on the photographic layer to which they are applied, but generally it is 10 to 1.000 per area of the photosensitive material.
It is applied so that it weighs 111g.

Examples of silver halide photographic emulsions in which the dyes of the present invention are used include emulsions of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like.

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, basic mordants such as polymers containing amine groups or ammonium groups, polymers containing nitrogen-containing heterocycles, stabilizers and their precursors, surfactants, hardeners, ultraviolet absorbers, and optical brighteners can be prepared by known methods. Additives such as agents, developing agents and their precursors can be included.

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 viridine, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and plasticizers and latex for dimensional stability. Polymers etc. can be added.

Further, the silver halide photographic emulsion in which the dye of the present invention is used can be coated on a support such as baryta paper, resin coated paper, synthetic paper, natural or synthetic polymer film such as cellulose triacetate or polyester. can.

The present invention will now be described in more detail with reference to Examples.

(E) Effect of the Invention Example 1 1.55 y of gelatin was added to 15.0 d of water to swell it, and then heated to 4C10° C. to dissolve the gelatin.

To this gelatin solution, an aqueous solution (2.0 x 10" mol/water 2.0d) of the dye of the present invention and a comparative dye (to be described later), a hardening agent, and a surfactant were added, and water was further added to make T 40.0.
7! I made it. Next, this @ color solution was applied onto a subbed polyester film base so that the coating m was 809/m.

Each sample thus obtained was heated at 50° C. for 1 day.

Each sample was immersed in a 30'C D-72 developer for 5 seconds and 15 seconds, then washed under running water for 10 seconds, adhering water droplets were sucked up with filter paper, and dried to obtain a treated sample.

The optical densities and density changes of the samples and treated samples at 600 to 900 nm were measured using a Shimadzu dual wavelength/double beam self-recording spectrophotometer (UV-3000).The obtained results are shown in Table 1.

Comparative Dye A Comparative Dye B ■e (Hereinafter in the margin) Comparative Dye C As is clear from Table 1, the dye of the present invention has a high optical density before treatment, and the density at 780 nm is higher than that of the comparative dye. I know it's expensive.

Furthermore, since the residual color rate is low, it can be seen that the dye of the present invention has excellent decolorization and dissolution properties.

Further, when looking at the coated samples of Comparative Dyes A and D, surface roughness due to aggregation of the dyes was observed, but this phenomenon did not occur with any of the dyes of the present invention.

Example 2 A 1% aqueous solution of the dye of the invention 2.3.4.5.7 was added to 10%
In addition to the gelatin aqueous solution, the 10% saponin aqueous solution was adjusted so that the optical a degree at 780 nm was 1.0 when the coating layer was 80 g/TIt, and the 10% saponin aqueous solution was added to the gelatin aqueous solution 15
5rnl for 0d, 1.5 m of 10% formalin!
Using the colored gelatin aqueous solution obtained by adding 2, the same operation as in Example 1 was carried out to obtain a hardened coating layer with an optical density of 1.0.

A pure 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.

(Developer composition) Metol 3J Sodium sulfite 45I; J Hydroquinone
129 Sodium carbonate fcum (monohydrate)
80g potassium bromide
Add 2g of water to make Zenyu 1! shall be.

The optical a degree of the obtained treated film was determined by the method described in Example 1, and it was found that the dyes of the present invention (2, 3, 4,
The concentration of the sample obtained using 5, 7) after treatment was exactly o, ooi.

In addition, each paper stock containing the dye of the present invention does not undergo changes over time such as discoloration or fading during the preparation of an aqueous solution, preparation of a coating solution, or sample storage, and has no adverse effects on photographic properties such as fog or desensitization, and is extremely stable. It was a photosensitive material with excellent antihalation effects.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material characterized by having a hydrophilic colloid layer containing at least one dye represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 may be the same or different and represent a substituted or unsubstituted alkyl group, and Z^1 and Z^2 are , represents a group of nonmetallic atoms necessary to form a benzo-fused ring or a naphtho-fused ring, each of which may have a substituent. However, Z^1 and Z^2 indicate that the dye molecule contains at least one
It has a carbohydroxamoyl group represented by ▼. R represents H or an alkyl group. R_3, R_4, R_5 and R_6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group. L represents a substituted or unsubstituted methine group, and X represents an anion. n is 1 or 2, and 1 when the dye forms an inner salt.
It is. )