JPH01239548A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the irradiation and the halation of the sensitive material by providing a hydrophilic colloid layer contg. at least one kind of specified dyestuffs in the sensitive material. CONSTITUTION:The hydrophilic colloid layer contg. at least one kind of the dyestuffs shown by formula I is provided in the sensitive material. In the formula, R1 and R2 may be the same or different with each other, and are each alkyl group which may be substd., Z1 and Z12 are each a nonmetal atomic group necessary for forming a benzocondensed ring or a naphthocondensed ring which is substd., respectively, R1, R2, Z1 and Z2 are each a group capable of forming a cyclicimide group in a dyestuff molecule, R3-R6 are the same or different with each other, and are each alkyl group which may be substd., L is methine group which may be substd., X is an anion. Thus, the irradiation and the halation of the sensitive material are prevented.

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 a photographic emulsion layer, a right color layer is provided on the photographic light-sensitive material, which is farther from the support than the photographic emulsion layer (I!I).

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.

Light that is scattered when passing through the photographic emulsion layer or after being transmitted is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material on the opposite side of 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,
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 emulsions (h), such as in a multilayer color light-sensitive material, an antihalation layer may be placed between these layers.

Decrease in 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 are often composed of hydrophilic colloids, and therefore, in order to color them, a water-soluble dye is usually contained in the layer.This dye must satisfy the following conditions. is necessary.

(I) Must have appropriate spectral absorption according to the purpose of use.

(2) Absorbance is sufficiently high.

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

(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, the coloring should not be left behind 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 method of exposing such a photographic light-sensitive material is to scan the original image, and then expose the silver rodanide photographic material based on the image to expose the 111i! of the original image. An image forming method using a so-called scanner method is known, which forms a negative image or a positive image corresponding to the image.

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

This semiconductor laser is small, inexpensive, easy to change, has a longer lifespan than other I (e-Ne lasers, argon lasers, etc.), and emits light in the infrared region, so it is sensitive to the infrared region. The use of a photosensitive material having the above-mentioned method has the advantage that a bright safelight can be used, resulting in improved handling and 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 dye 94 for infrared absorption, and (b) JP-A-55-21094 and JP-A-55-21095.
2-carbamoyl-1- specified in No. 55-21096 and Research Disclosure No. 22338.
It has been described that infrared dyes can be formed from naphthol couplers and color developing agents in hydrophilic colloid layers.

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

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

Furthermore, since the infrared dye formed from the above (b) 2-carbamoyl-1-su7)-l and a color developing agent is water-insoluble, when it is incorporated into the hydrophilic colloid skin, it is difficult to use oil. A soluble solvent is required, resulting 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 due to their water insolubility.

Therefore, conventional dyes meet the above-mentioned conditions required for them.
There is no dye that can satisfy all of (I) 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 (I) to (6).
It is an object of the present invention to provide a silver halide photographic material having a hydrophilic colloid layer colored with a water-soluble photographic light-absorbing dye, which satisfies the above requirements and has excellent eradication and halide prevention and filter effects.

(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 provide a hydrophilic dye containing at least one of the dyes represented by the following - Monna CI). It has been found that this can be achieved by a silver halide photographic material characterized by having a colloid layer.

General formula (I) In the formula, R1 and R2 may be the same or different and may be substituted or unsubstituted alkyl groups (lower alkyl groups having 1 to 5 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group). zl and Z2 each represent a nonmetallic atomic group necessary to form a benzo-fused ring or a naphtho-fused ring having a substituent. Substituents on the chain ring include sulfo group, carboxyl group, hydroxyl group, halogen atom, cyano group,
Substituted amino group (for example, substituted or unsubstituted alkyl group having 1 to 5 carbon atoms bonded to the ring via a divalent linking group (for example, methyl group, ethyl group, propyl group, butyl group, etc. (fR-substituted The group represents a sulfo group, a carphokimido group, etc.), and the divalent linking group is, for example, -〇-1-NHCO-1-NH8O□-1-NHCoo-1
-NHCONH-1-COO-1-CO-1-SO2-
etc.

However, R1, R2, zl and Z2 represent groups that enable the dye molecule to have a small group.

1'L5, 几4, R5, and R6 may be the same or different, and may be substituted or unsubstituted alkyl groups (lower alkyl groups having 1 to 5 carbon atoms (e.g., methyl group, ethyl group,
A propyl group, a butyl group, etc.) are preferable, and a rainbow substituent group (eg, a sulfo group, a carboxyl group, a hydroxyl group, etc.) may be present.

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.

Y represents a non-gold atom group capable of forming a cyclic imide, and the cyclic imide group is preferably a 5-membered ring, such as a succinic imide group, a phthalimide group, an orthobenzosulfimide group, or a maleimide group. etc. can be given.

Although the silver halide photographic light-sensitive material colored with the dye of the present invention shown in the above-mentioned hole (I) has a high molecular extinction coefficient in the target wavelength region, other In the wavelength range of , there is almost no unnecessary sub-absorption, and furthermore,
It does not cause negative effects on photographic properties such as capri and desensitization, and can sufficiently exhibit excellent irradiation prevention, Halley silane prevention and filter effects with a small amount of use.

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 germs such as moist heat during the preparation of the photographic emulsion or during subsequent storage. It has the advantage of being stable without any problems.

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.

RN(C2H5)3 The dye represented by the general formula (I) has an absorption maximum of 730
~850 am, and the Journal of the
Chemical Society [J, Chem, 8oc.

189 (I933)], US Pat. No. 2,895,955, and the following synthesis examples.

Synthesis example 1. (Synthesis of Exemplary Compound 2) -2,3,3-)dimethyl-5-succinimide-1-
To a mixture of (3-sulfopropyl)indolenine (3.89) and methanol (80), add triethylamine (2°8) and glutaconaldehyde di'anil salt (riIt) (1.72), stir well, and add anhydrous vinegar*1.5 - was added and stirred at room temperature overnight.

After the reaction, the solvent of the reaction solution was distilled off under reduced pressure, and column chromatography was performed to obtain the desired product. (Development: Chloroform-methanol mixture Wm) Dark green metallic luster crystal Yield i: 3.9f Methanomil
753 nmλmax Water 747 nm λmax Synthesis Example 2 (Synthesis of Exemplary Compound 5) 1-(2-succinimideethyl)-2,3,3-trimethylindolenium-5-sulfonate 3°641
After adding 80 g of methanol and 2.8 g of triethylamine and stirring for a while, add 1.72 g of glutaconaldehyde cyanyl hydrochloride and stirring well, and then add 1.5 g of acetic anhydride.
rn1. was added and stirred overnight at room temperature.

After the reaction, the reaction solution was distilled off under reduced pressure and subjected to column chromatography to obtain the desired product. (Development: Chloroform-methanol) Dark green metallic luster crystal Yield: 2.92 Methanol
750 nm λmax Water λmax 747 nm In order to add the dye of the present invention represented by the above-mentioned pattern (I) into a silver halide photographic emulsion or a protective colloid solution, an aqueous solution, methanol, ethanol, selonol, glycols, dimethyl It can be added to the emulsion layer, backing layer, subbing layer, intermediate layer, preservation layer, and ultraviolet absorbing layer as a solution of formamide, etc., or as a mixed bath solution of these organic solvents and water. can.

The amount of these dyes used varies depending on the photographic layer to be applied, but in general, the amount of dye used is 10 to 10% on the surface of the light-sensitive material.
,000■.

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, by a known method, a basic mordant such as a polymer containing an amino group or an ammonium group, a polymer containing a nitrogen heterocycle, a stabilizer, and its precursor [precursor, surfactant, hardening agent, ultraviolet absorber, Additives such as optical brighteners, 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.

Protective colloids for silver halide emulsions include, in addition to gelatin, gelatin derivatives such as phthalated gelatin and malonated gelatin, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and plasticizers with poor dimensional stability, such as latex. 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 be described in more detail with reference to Examples.

(E) Effect of the invention Example 1 1.551 n of gelatin to 15.01 n of water! , and then swelled at 40.0° C. to dissolve the gelatin.

To this gelatin solution, an aqueous solution (2,0XIO-'mol/2.0 ml of water) of the dye of the present invention and a comparative dye (described later), a hardening agent, and a surfactant were added, and water was further added to obtain a panoramic view of 40
．． I set it to 0-. Next, apply this coloring solution onto the undercoated polyester film base in an amount of 80? /lr
? I applied it to make it look like this.

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

Each sample was immersed in D-72 developer at 30°C for 5 seconds and 15 seconds, then washed under running water for 10 seconds, and the adhering water droplets were absorbed with a door paper and dried to obtain a processed sample. .

The optical humidity 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 results obtained are shown in Table-1.

Comparative Dye A ■0 As is clear from Table 1, the dye of the present invention has a high optical density before treatment, and has an optical density of 780 nm compared to the comparative dye.
It can be seen that the temperature at

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.

Furthermore, when looking at the coated samples of Comparative Dyes A and D, surface roughness due to aggregation of the dyes was observed, but such a 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
In addition to the Chizelatin aqueous solution, 80 tan? FJ"4 was inserted so that the optical density at 780 nm was 1.0 when used as a coating layer, and 5tRt of 10% saponin aqueous solution was added to 150mg of gelatin aqueous solution, and 1.5% of 10% formalin was added. The same operation as in Example 1 was carried out using the colored aqueous gelatin solution, and the optical density was 1.0.
A hardened coating layer was obtained.

A pure silver bromide emulsion was coated on this coating layer, and a developer having the following composition was used at 20°C for 90 seconds (composition of the developer) Metol 32 Sodium sulfite 452 Hydroquinone 122 Sodium carbonate (I hydrate) 802 Potassium bromide 21 Add water to bring the total amount to 16.

After development, it was fixed, washed with water, and dried according to a conventional method.

The optical density of the obtained treated film was determined by the method described in Example 1.
The concentrations of the samples obtained using 5 and 7) after treatment were all 0.01.

In addition, each sample 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 storage of the sample, and has no adverse effects on photographic properties such as capri or desensitization. It was a photosensitive material that had an extremely excellent antihalation effect.

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 , represents a group of nonmetallic atoms necessary to form a benzo-fused ring or a naphtho-fused ring each having a substituent. However, R_1, R_2, Z^1, and Z^2 are ▲ formulas in which at least one dye molecule is present. , chemical formulas, tables, etc.▼
This represents a group capable of having a cyclic imide group represented by the following. 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. Y represents a group of nonmetallic atoms that can form a cyclic imide. n is 1 or 2, and 1 when the dye forms an inner salt.
It is. )