JPH03126027A - Light absorptive dye for photography - Google Patents

Abstract

PURPOSE:To obtain excellent irradiation prevention, halation prevention and filter effects by using a specific dye. CONSTITUTION:The dye expressed by formula I is used. In the formula I, Z denotes the atom group necessary for forming a benzene ring or naphthalene ring; R1 denotes alkyl group. R2 denotes a sulfo-substd. alkoxy group or alkyl- substd. amino group substd. with at least one sulfo group. R3 denotes hydrogen, halogen atom, alkyl group, alkoxy group or hydroxy group. R4 denotes hydrogen or sulfo-substd. alkoxy group; n denotes 1 or 2. The dye expressed by the formula I is required to have >=2 sulfo groups in its molecular structure. The excellent irradiation prevention, halation prevention and filter effects are exhibited with the smaller amt. of the dye to be used in this way.

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.

(B) Prior Art In silver halide photographic light-sensitive materials, harmful reflections, scattering, and diffused light in the light-sensitive emulsion layer are absorbed, or from the interface between the emulsion layer and the support base and the back surface of the support. It is well known that by absorbing undesired reflected light from images, rays and halation can be prevented and the sharpness of the finished photographic image can be improved.

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.

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 Of course, changes over time such as discoloration and fading must not occur during emulsion production and storage, 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, 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, an object of the present invention is to provide a photographic light-absorbing dye that satisfies the above conditions and has excellent irradiation, halation and filter effects.

(D) Structure of the Invention As a result of various studies, the present inventors have discovered that the dye represented by the following general formula is an excellent dye that satisfies the above object.

General Formula In the above general formula, Z represents an atomic group necessary to form a benzene ring or a naphthalene ring, and these rings may include a sulfo group, a carboxy group, a lower alkyl group (e.g.
methyl, ethyl, propyl, butyl, pentyl, etc.)
It may have a substituent such as a hydroxy group, a lower alkoxy group (eg, methoxy, propoxy, etc.), or a halogen atom (eg, chlorine, bromine, etc.). R1 represents an alkyl group (for example, a lower alkyl group as mentioned above as a substituent in 2), but these lower alkyl groups may further include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, a cyan group, a methoxy group, or an ethoxy group. (which may be substituted with a lower alkoxy group such as For example, N, N-
Bis-sulfoethylamino, N,N-bis-sulfopropylamino, N-methyl-N-sulfopropylamino,
N-cyanoethyl-N-sulfopropylamino, N-methoxyethyl-N-sulfoethylamino, N-ethyl-
N-sulfobenzylamino, etc.). R3 represents hydrogen, a halogen atom, a lower alkyl group, a lower alkoxy group which may be substituted with a sulfo group, or a hydroxy group.

R4 represents hydrogen or a sulfo-substituted alkoxy group. n
represents 1 or 2. However, the dye represented by the above general formula shall have at least two or more sulfo groups in its molecular structure. Furthermore, these sulfo groups may be in the form of alkali metal salts such as sodium and potassium salts, ammonium salts, and organic ammonium salts such as triethylamine, tributylammonium, and pyridinium.

Although the silver halide photographic material colored with the dye of the present invention represented by the above general formula has a high molecular extinction coefficient in the target wavelength region, it has a high molecular extinction coefficient in other wavelength regions. has almost no unnecessary side absorption, and also provides excellent anti-irradiation, anti-halation, and filter effects with a small amount of use, without causing any negative effects on photographic properties such as fog or desensitization. can be demonstrated.

In addition, since the dye is completely and quickly decolorized from the photosensitive material after the development process, the finished photographic image will not only contain the residual dye contained for the above purpose, but also color contamination due to the recoloring of the decolorized dye. Furthermore, no re-dying due to coloring of the developing solution was observed.

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 stable without being affected by external conditions such as moist heat during the production of the photographic emulsion or during subsequent storage. It has the advantage of being

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.

Typical examples of the dyes of the present invention represented by the general formula are listed below, but the scope of the present invention is not limited thereto.

(Margin below) dye 5 dye 6 dye 7 dye 8 03 dye 1 dye 2 dye 3 dye 4 dye 9 dye 10 dye 11 dye 12 dye 13 dye 14 (Margin below) Next, typical examples of dye synthesis methods will be specifically described.

Synthesis of Dye 1 8.4 g of anhydro-2-methyl-1-(3'-sulfopropyl)spiroC3H-indolium-3.4'-tetrahydropyran] hydroxide and 2-methyl-4-(N,N -Bis-2'sulfoethyl)aminobenzaldehyde disodium salt 7.91g was added to 1g of acetic anhydride.
Add to a solution of 30ml and 13Qml of acetic acid, and heat under reflux for 1 hour.
I did it for an hour.

After distillation under reduced pressure, ethanol was added, and the precipitate was collected by filtration and recrystallized with aqueous ethanol to obtain 8.9 g (7) of the desired product.

Melting point: 300° C. or higher, H2O λ max: 552 nm Other dyes 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, it can be added as an aqueous solution or a solution of methanol, ethanol, cellosolves, glycols, dimethylformamide, dimethylsulfoxide, pyridine, etc. , dimethyl sulfoxide, pyridine, etc., or as a mixed solution of these organic solvents and water, it can be added to emulsion layers, backing layers, subbing layers, intermediate layers, protective layers, and ultraviolet absorbing layers. be able to.

The amount of these dyes used varies depending on the photographic layer to which they are applied, but is generally applied in an amount of 5 to 1,000 square meters per 1 d of area of the light-sensitive 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.

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 amino groups or ammonium groups, stabilizers and their precursors, surfactants, hardeners, ultraviolet absorbers, optical brighteners, developing agents, and Additives such as precursors thereof can be included. When silver halide photographic emulsions are used in color light-sensitive materials,
Color couplers and their dispersants can also be included.

In addition to gelatin, protective colloids for silver halide photographic emulsions include gelatin derivatives such as phthalated gelatin and malonated gelatin, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and plasticizers for dimensional stability. 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 supports such as baryta paper, resin-coated paper, synthetic paper, natural or synthetic polymeric films such as cellulose triacetate-based or polyester-based. .

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

Example 1 After adding 1.55 g of gelatin to 25 ml of water and swelling it,
The gelatin was dissolved by heating to 40°C. Add to this gelatin solution an aqueous solution of the dye of the present invention and the comparative dye described below (],,,]
0XIO-' mole/2.0 ml of water, a hardening agent, and a surfactant were added, and further water was added to bring the total volume to 40 ml. Next, this colored solution was applied onto the undercoated polyester film base at a coating amount of 80 g/rrl,
It was heated at 40° C. for 24 hours and cut into a rectangle of 8.0×11.5 cd to prepare a sample. The sample was heated to 30.0°C.
72 developer for 5 seconds and 15 seconds, then immerse it in running water for 1
The sample was washed with water for 0 seconds, and the water droplets that adhered to the sample were sucked up with filter paper and dried to obtain a treated sample. The optical density and density change at 2 m ax at 400 to 700 nm of the sample and the treated sample were measured using a dual wavelength/tuple beam self-recording spectrophotometer (UV-3000) manufactured by Shimadzu Corporation. The results obtained are shown in Table-1.

(Leaving space below) Comparative dye A Comparative dye B Comparative dye C Comparative dye table-1 -b Decolorization rate (%) = -X 100 a: Absorbance at λmax of sample before treatment b: After treatment ′ Clearly from Table-1 As such, the dye of the present invention is compared to comparative dye A.
It can be clearly seen that the optical density before treatment and the decolorization rate after treatment are superior to that of -C.

Example 2 A 1% aqueous solution of dye was added to a 10% aqueous gelatin solution, and 80
The optical density was adjusted to 1.0 when a coating layer of g/rrf was prepared, and 5 ml of 10% saponin aqueous solution was added to 150 ml of gelatin aqueous solution, and 1.
A film was hardened in the same manner as in Example 1 using the colored gelatin aqueous solution obtained by adding 5 ml, and the optical density was 1.
0 coating layer is obtained.

A pure silver bromide emulsion was coated on the second coating 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 0.02. (However, base concentration 0.02) Composition of developer Metol 3g Sodium sulfite 45g Hydroquinone
12g sodium carbonate (monohydrate)
Add 80g of water to make a total volume of 11.

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.
The photosensitive material had no adverse effects on photographic properties such as fog or desensitization, and had an extremely excellent antihalation effect.

Claims (1)

[Claims] A photographic light-absorbing dye represented by the following general formula. General formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ Represents an alkyl-substituted amino group substituted with one sulfo group. R_3 represents hydrogen, a halogen atom, an alkyl group, an alkoxy group, or a hydroxy group. R_4 represents hydrogen or a sulfo-substituted alkoxy group. n is 1 or 2
represents. However, the dye represented by the general formula has 2 molecules in its molecular structure.
or more sulfo groups. )