JPH01196040A - Light absorbent dye for photography - Google Patents

Abstract

PURPOSE:To prevent irradiation and halation and to obtain the effect of a spectral filter by using a specific dye. CONSTITUTION:The dye expressed by the formula I is used. In the formula I, R1, R2 may be the same or different and respectively denote a substd. or unsubstd. alkyl group and may bond to each other to form a ring. R3 denotes an alkyl group substd. by at least one sulfo group or aryl group substd. by at least one sulfo group; R4 denotes a substd. or unsubstd. alkyl group, substd. or unsubstd. aryl group, carboxy group, alkoxycarbonyl group; n denotes 1-4 integer. The irradiation and halation are thereby prevented and the sufficient filter effect is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to photographic light-absorbing dyes, and more particularly to dyes useful as light-absorbing dyes used in silver halide photographic light-sensitive materials.

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

In addition, if there are multiple photographic emulsion layers on top of the emulsion layer or in a multilayer color light-sensitive material, a colored layer (
It is also well known that the spectral composition incident on a photographic emulsion layer can be controlled by providing a filter layer).

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 may be used during solution preparation or It goes without saying that the photosensitive emulsion must not undergo any changes over time such as discoloration or fading during production and storage, but it must also not have any adverse effects on photographic properties such as fog or desensitization.

In addition, during the development process, it is necessary to completely and quickly decolorize or
The compound 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 the effects of preventing irradiation, preventing halide radiation, and acting as a spectral filter.

However, although a considerable number of dyes have been proposed to date, the reality is that there are few that satisfy the above conditions, such as decolorization properties, dissolution properties, and photographic properties.

(C) Object of the Invention Accordingly, the object of the present invention is to provide a photographic light-absorbing dye that satisfies the above conditions and has excellent irradiation, norsin, and filter effects.

(D) Structure of the Invention As a result of various studies, it has been found that the dye represented by the following general formula is an excellent dye that satisfies the above object.

R(ゝR2 In the above general formula, R1s ``2 may be the same or different, and each represents a substituted or unsubstituted alkyl group (
For example, methyl, ethyl, n-propyl, 5-propyl, n-'butyl, t-butyl, 2-hydroxyethyl,
2-methoxyethyl, 2-ethylsulfonamidoethyl, 2-methylthioethyl, etc.), and may also be bonded to each other to form a ring (e.g., pyrrolidine, pyrrolidinone, piperidine, piperazine, sulfoline, etc.) . R3 is an alkyl group substituted with at least one sulfo group (Lid, 2-sulfoethyl, 3-sulfopropyl, 2-hydroxy-3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, etc.) or at least one Sulfo group-substituted aryl tsc example Id, 3
-sulfophenyl, 4-su/L/ho7! 2/I/, 4-
/ Rollo 3-sulfophenyl, 4-methyl-2-sulfophenyl, 3-methoxy-4-sulfophenyl, 2.5
-Disulfophenyl.

etc.) t-express. R4 is a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, carboxymethyl, benzyl, etc.), a substituted or unsubstituted aryl group (e.g., phenyl) , 2-methylphenyl, 3-chlorophenyl, 4-methoxyphenyl, 4-cyanophenyl, 4-carboxy7enyl, 4-ethoxycarbonylphenyl,
3-sulfophenyl, 3.5-disulfophenyl, etc.),
Carboxy group, Al; represents an oxycarbonyl group (eg, methoxyfulbonita, ethoxycarbonyl, n-propoxycarbonyl, etc.). n = represents an integer from 1 to 4. The dye represented by the above general formula is an alkali metal salt (
For example, potassium, sodium, etc.) and ammonium salts (
For example, at may be 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 all of the dyes of the present invention have high molecular extinction coefficients, so they can be used as an excellent irradiation dye in small amounts without causing any adverse effects on photographic properties such as capri or desensitization. It can fully exhibit the prevention, haleyshiron prevention and filter effects.

In addition, after the development process, the dye is rapidly and completely decolorized and eluted from the photosensitive material, so the finished photographic image contains not only residual dyes contained for the above purpose but also due to the recoloring of the decolorized dye. No color contamination or re-dying due to coloring of the processing solution is observed. In addition, the dye of the present invention does not undergo changes such as discoloration or fading during the preparation of the dye solution, and is stable without being affected by external conditions such as heat during the production of the photosensitive emulsion or during subsequent storage. It has the advantage of being

Next, typical examples of the dyes represented by the above-mentioned formula of the present invention will be listed.

dye 1 Next, typical examples of dye synthesis methods will be specifically described.

Synthesis of dye 3; 1.1-dimethylhydrazine 19.4F, acetoni/I
/7 Seton 41. ! Dissolve M' in benzene 200-
Add a small amount of 50% acetic acid to this, being careful not to generate heat. Thereafter, the mixture is heated under reflux for 5 hours while distilling off the water produced. After distilling off benzene, p, 150.0-16
A light purple-brown fraction 39.6 F is obtained which distills at 0.0°C.

Dimethylformamide 85.0- was added to phosphorus oxychloride 66.0- while stirring while keeping the temperature below 20°C. Drop a small amount of Of. After dropping, continue stirring at the same temperature for 5 minutes,
A small amount of 39.6 f of 1-dimethylamino-2,5-dimethylpyrrole obtained above was added dropwise over about 30 minutes. After dropping, stir at the same temperature for 15 minutes. Next 35-40
℃ and continue stirring for an additional 30 minutes. After that, pour the reaction solution onto 450 g of ice water and 40% hydroxide)
Make it strong alkaline with IJum aqueous solution. The precipitated oil is extracted twice with 300 g of benzene. Combine the extracts and dry with sodium sulfate. After distilling off the benzene, the residual liquid is distilled under reduced pressure. b, p, 110.0-112.0℃/
28.7 ft of almost colorless fraction of 4 mHf is obtained.

3-formyl-1-dimethylamino-2,5 obtained above
-dimethylvirol 27.2f and 3-methyl-1-(4
-sulfophenyl)-5-pyrazolone 41.6 f to 2
After adding 400 g of -methoxyethanol and further adding 22.4 fk of sodium acetate trihydrate, the mixture was heated under reflux for 1 hour. After distilling off the solvent, add 350 °C of hot ethanol to the residue, stir well, and collect the precipitated dye t-F. Wash with ethanol and dry to obtain an ocher crystalline powder with a temperature of 300°C or higher. 61.2ft-gain. Maximum absorption value of aqueous solution 420 nm.

Other dyes represented by the general formulas of the present invention can also be easily synthesized according to the above synthesis examples.

In order to add the dye of the present invention represented by the above-mentioned formula into a silver norogenide photographic emulsion or a protective colloid solution, it can be added as an aqueous solution or a solution in methanol, ethanol, selonlubes, glycols, dimethylformamide, dimethylsulfoxide, pyridine, etc. In addition, a mixed solution of these organic solvents and water can be added to an emulsion layer, a backing layer, a subbing layer, an intermediate layer, a protective layer, or an ultraviolet absorbing layer.

The amount of these dyes used varies depending on the photographic layer to be applied.
In general, it is coated in an amount of 5 to 1.0009 particles per 1 area of the photosensitive material.

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.

(9) 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, fluorescent Additives such as brighteners, developing agents, and their precursors can be included. When a silver halide photographic emulsion is used as 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 photographic emulsions include gelatin derivatives such as ditalated gelatin and malonated gelatin, and polyvinyl alcohol.

-Water-soluble poly-1, such as polyvinylpyrrolidone or
polymers, and plasticizers for dimensional stability, latex polymers, etc.

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

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

Example 1: After adding 1.5 fM'i of gelatin to 15.0 mj of water to swell it, it was heated to 40.0°C to dissolve the gelatin.

Add to this gelatin solution an aqueous solution of the dye of the present invention and a comparative dye (
2,OX 10-' mol/2.0 m of water), a hardening agent, and a surfactant were added, and water was further added to make the total amount 120.0-'. Next, this colored gelatin solution was coated on the undercoated polyester film base so that the coated amount was 859 cm, and heated at 50.0°C for 24 hours. OX
It was cut into a 11,5- rectangle to prepare a sample.

Sample t-ao, 5 seconds and 15 minutes in D-72 developer at 0°C.
After being immersed for a second, the sample was washed under running water for 10 seconds, and the adhering water droplets were sucked up with a piece of paper and dried to obtain a treated sample. Samples 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.

Comparative dye E Comparative dye F Comparative dye G Table-1 *Represents base concentration.

As is clear from Table 1, the dye of the present invention not only has a high initial density, but also a large difference in density after treatment.

In other words, it is clear that the dye has excellent decolorization and dissolution properties.

Example 2; In addition to t-10% gelatin aqueous solution of dye, s
The optical density was adjusted to approximately 1.0 when the coated layer was 7trr, and the colored material was obtained by adding 1.5% of formalin to 150% of gelatin aqueous solution and 1.5% of formalin to 150% of gelatin aqueous solution. A hardened coating B having an optical density of approximately 1.0 is obtained by the same operation as in Example 1 using an aqueous gelatin solution.

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.

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

Composition of developer Metol 3f Sodium sulfite 451 Hydroquinone 12f Sodium carbonate (monohydrate)
80f Potassium bromide 2f Add water to make a total volume of 1 t.

In addition, each sample containing the dye of the present invention does not undergo changes over time such as discoloration or fading during aqueous solution preparation, emulsion preparation, or storage, and has no adverse effects on photographic properties such as capri or desensitization, and has extremely excellent properties. It was a photosensitive material with anti-halation effect.

Claims (1)

[Claims] 1. A photographic light-absorbing dye represented by the following general formula. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 may be the same or different,
Each represents a substituted or unsubstituted alkyl group, and may also be bonded to each other to form a ring. R_3 represents an alkyl group substituted with at least one sulfo group or an aryl group substituted with at least one sulfo group. R_4 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a carboxy group, or an alkoxycarbonyl group. n represents an integer from 1 to 4. )