JPH03125137A - Light absorptive dye for photography - Google Patents

Abstract

PURPOSE:To exhibit excellent irradiation, halation and filter effects by dosing a specific dye between photosensitive emulsion layers or between the emulsion layer and a base or into filter layers. CONSTITUTION:The light absorptive dye for photography expressed by formula I is used. In the formula I, Y denotes the atom group necessary for forming a benzene ring or naphthalene ring; Z denotes the atom group necessary for forming 4- to 7-membered cycloalkane rings. R1 denotes an alkyl group; R2 denotes a sulfo-substd. alkoxy group or an alkyl-substd. amino group substd. with at least one sulfo group. R3 denotes hydrogen, halogen atom, alkyl group, etc.; R4 denotes hydrogen or sulfo-substd. alkoxy group; m denotes 1 or 2. The dye expressed by the formula I has at least three sulfo groups in its molecular structure. The excellent prevention of the irradiation and halation and the filter effect are sufficiently exhibited with the smaller amt. of use 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 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).

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, it has been found 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, Y 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.
It may have a substituent such as a hydroxy group (methyl, ethyl, propyl, butyl, pentyl, etc.), a lower alkoxy group (eg, methoxy, propoxy, etc.), or a halogen atom (eg, chlorine, bromine, etc.). Z represents an atomic group necessary to form a 4- to 7-membered cycloalkane ring (eg, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, etc.). R1 represents an alkyl group (for example, a lower alkyl group as mentioned above as a substituent for Y, but these lower alkyl groups may further include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, a cyano group, a methoxy 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-sulfopropylamino. ethylamino, 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. m is 1
or 2. However, the dye represented by the above general formula shall have at least three sulfo groups in its molecular structure. Furthermore, these sulfo groups are sodium,
It may be in the form of an alkali metal salt such as potassium, an ammonium salt, an organic ammonium salt such as triethylamine, tolylbutylamine, or pyridine.

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 provide excellent irradiation with a small amount of use without causing any negative effects on photographic properties such as fog or desensitization. It can fully exhibit prevention, antihalation 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. 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 photosensitive emulsion or during subsequent storage. It has the advantage of being

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

(Margin below) C, H.

1 (CH2) 4 Oa- Next, typical examples of dye synthesis methods will be specifically described.

Synthesis of dye (3) Anhydro-3,3-pentamethylene-2-methyl-1
-(3-sulfopropyl)-5-sulfo-38-indolium hydroxide triethylammonium salt 6.4
g, 2-methyl-4-(N.

N-bis(2-sulfoethyl)]aminobenzaldehyde 5.0g acetic anhydride 80.0ml and acetic acid 120.0g
ml mixture was heated to reflux for 2 hours. While hot, the precipitated crystals were collected by filtration. After washing with acetic acid, it was dissolved in methanol and collected by filtration. 2.1 g of sodium acetate was added to the filtrate, and the mixture was heated under reflux for 5 minutes. While hot, the precipitated crystals were collected by filtration, washed with methanol, and then dried. 4゜4g of dark purple crystalline powder with a melting point of 300℃ or higher
I got it.

The maximum absorption wavelength of the aqueous solution was 559 nm, and the maximum absorption wavelength of the methanol solution was 567 nm.

Synthesis of dye (13); anhydro-3,3-pentamethylene-2-methyl-1
-(3-sulfopropyl)-3H-indolium hydroxide 5.3 g, 2-methyl-4-(N,N-bis-(
7.0 g of 2-sulfoethyl)) aminocinnamaldehyde disodium salt.

A mixture of 100.0 ml of acetic anhydride and 100.0 ml of acetic acid was heated under reflux for 2.5 hours. Insoluble matters are removed by filtration when hot.
The filtrate was concentrated under reduced pressure. 400 ml of methanol/ethanol (1:1) was added to the residue, and the mixture was heated under reflux for 5 minutes. The precipitated crystals were collected by filtration, washed with the same mixed solvent, and dried. 3.0 g of dark purple crystalline powder with a melting point of 238.0° C. (decomposed) was obtained. Maximum absorption wavelength of aqueous solution is 554 nm (broad)
, and the absorption maximum wavelength of methanol solution is 624.57
It was 1 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 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, into emulsion layers, backing layers, subbing layers, intermediate layers, storage/setting layers, and ultraviolet absorbing layers. It can be made to exist.

The amount of these dyes to be used varies depending on the photographic layer to which they are applied, but generally they are applied in an amount of 5 to 1.000 square meters per 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. Further, by a known method, basic mordants such as polymers containing amino groups or ammonium groups, polymers containing nitrogen-containing heterocycles, stabilizers and their precursors, surfactants, hardeners, ultraviolet absorbers, fluorescence enhancers, etc. whitening agent,
Additives such as 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 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: 1.55 g of gelatin was added to 15.0 ml of water to swell it, and then heated to 40.0° C. to dissolve the gelatin. Add to this gelatin solution an aqueous or methanol solution of the dye of the present invention and a comparative dye (2.0 x 10-4 mol/2.0 m of solvent).
1), a hardening agent, and a surfactant were added, and water was further added to bring the total volume to 40.0 ml. Next, this colored gelatin solution was coated on the undercoated polyester film base in an amount of 85 g, heated at 50.0°C for 24 hours, and 8. 0XI1. A sample was cut into a rectangle of 5 cnf.

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, the attached water droplets were absorbed with filter paper, and the sample was dried to obtain a processed sample. . λ at 400-700 nm for samples and processed samples
Optical density and density change at max were measured using a three-wavelength tuple beam self-recording spectrophotometer (UV-
3000). The results obtained are shown in Table-1.

(Leaving space below) Table 1 ■ 03 -b Decolorization rate (%) = × 100 a: Absorbance at λmax of the sample before treatment b: After treatment As is clear from Table 1, the dye of the present invention has a It is clear that in addition to the high concentration, the dye has excellent decolorizing properties.

Example 2: A 1% aqueous solution of the dye of the present invention was added to a 10% aqueous gelatin solution, and the optical density was adjusted to approximately 1.0 when a coated layer of 85 g/nf was formed. Using a colored gelatin aqueous solution obtained by adding 5 ml of 1.5 ml of 10% formalin to 150 ml of the aqueous solution, a hardened coating layer having an optical density of approximately 1.0 was obtained by the same operation as in Example 1. A pure silver bromide emulsion was coated on top of this coating layer, and a developer solution having the following composition was used to develop the silver bromide emulsion at 20°C.
After developing for 0 seconds, it was fixed, washed with water, and dried 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, the same as the base density.

Developer composition Metol 3g Sodium sulfite 45g Hydroquinone
12g sodium carbonate (monohydrate)
80g potassium bromide 2g
Add 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, and has no adverse effects on photographic properties such as fogging or desensitization. It was a photosensitive material that had a ration prevention effect.

Claims (1)

[Claims] A photographic light-absorbing dye represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y represents the atomic group necessary to form a benzene ring or naphthalene ring, and Z is necessary to form a 4- to 7-membered cycloalkane ring. R_1 represents an alkyl group, R_2 represents a sulfo-substituted alkoxy group or an alkyl-substituted amino group substituted with at least one sulfo group. R_3 represents hydrogen, a halogen atom, an alkyl group, an alkoxy group, or Represents a hydroxy group. R_4 represents hydrogen or a sulfo-substituted alkoxy group. m represents 1 or 2. However, the dye represented by the general formula has at least three sulfo groups in its molecular structure. )