JPH02259638A - Dye for photography - Google Patents

Abstract

PURPOSE:To obtain a significant antihalation effect without adversely affecting photographic characteristics such as fog and desensitization by using a silver halide photographic sensitive material colored with a specified dye. CONSTITUTION:A dye represented by formula I is used. In the formula I, R1 is alkyl or aralkyl, R2 is H, alkyl or alkoxy, R3 is sulfoalkyl or sulfoaryl and R4 is alkyl, aryl, carboxy or alkoxycarbonyl. The dye has a high molecular absorption coefft. and can produce significant anti-irradiation, antihalation and filter effects without adversely affecting photographic characteristics such as fog and desensitization even when used in a small amt.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to photographic dyes, and more particularly to dyes useful as light-absorbing dyes used in silver halide photographic light-sensitive materials. Technical silver halide photographic materials absorb harmful reflections, scattering, and diffused light in their light-sensitive emulsion layers, or absorb undesired light reflected from the interface between the emulsion layer and the support paste and from the back surface of the support. By absorbing
It is well known to prevent artifacts and Halley scenes to improve the sharpness of finished photographic images. Please note that when there are multiple photographic emulsion layers, such as in a multilayer color photographic light-sensitive material, a colored layer (filter layer) is provided on top of the emulsion layer or between them, so that the spectral composition that should be incident on the photographic emulsion layer can be changed. It is also well known that it is possible to control irradiation and irradiation by applying it to the photosensitive emulsion I#, between the emulsion layer and the support, or to the backing layer of the support. It goes without saying that dyes administered into layers must not undergo changes over time such as discoloration or fading during solution preparation, photosensitive emulsion manufacturing, or storage, but they must not cause any adverse effects on photographic properties such as fog or desensitization. Do not let this happen.

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 1c.Furthermore, it has spectral absorption characteristics that meet the respective purposes, and is suitable for preventing irradiation and halogenation. For example, a return film that can be handled in a bright room, that is, a light-sensitive material, must have the effect of preventing dust and spectral filtering. As described in Japanese Patent Publication No. 59-177536, it is known to use a dye that mainly absorbs light in the wavelength range of about 500 mm to about 600' nm.

However, to date, there have been quite a large number of 500nm to 600nm
Although dyes having absorption gold in m have been proposed, the reality is that there are only a few that satisfy the above conditions such as decolorization, dissolution, and photographic properties (Q. Purpose of the Invention Therefore, the purpose of the present invention is to It is an object of the present invention to provide a photographic light-absorbing dye that satisfies various conditions and has excellent anti-irradiation and filtration prevention and filter effects.

(2) 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 objects.

In the above general formula, R1 is an alkyl group (for example, a lower alkyl group such as methyl, ethyl, propyl, butyl, a hydroxyalkyl group such as hydroxyethyl or hydroxypropyl, a plucoxyalkyl group such as methoxyethyl or ethoxyethyl, or a cyanoethyl group). , cyanoalkyl groups such as cyanopropyl, carboxyalkyl groups such as carboxymethyl, carboxyethyl, carboxypropyl, alkoxycarbonyl groups such as methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl,
Sulfoalkyl groups such as sulfoethyl, sulfopropyl, sulfobutyl, etc.), aralkyl groups (e.g. Eva, Hensyl,
Fenel, chlorobenzyl, methylbenzyl, methoxybenzyl, nitrobenzyl, sulfobenzyl, sulfo-7
OR8 representing a hydrogen atom, an alkyl group (such as enethyl, etc.)
For example, a lower alkyl group as mentioned in R8), an alkoxy group (e.g., a lower alkoxy group such as methoxy, ethoxy, propoxy, butoxy, etc.) t-0RII is a sulfoalkyl group (e.g., as mentioned in R1) , a sulfoaryl group (for example, sulfophenyl, disulfophenyl, etc.). ) R4 is an alkyl group (for example, a lower alkyl group as described in R8 above), an aryl group (for example, phenyl, tolyl, methoxyphenyl, chlorophenyl, cyanophenyl, nitrophenyl, carboxyphenyl, sulfophenyl, etc.), a carboxy group, represents an alkoxycarbonyl group (eg, as mentioned above for R1). However, the sulfo group, carboxy group, etc. in the dye molecule may form a salt such as an alkali metal salt (eg, sodium, potassium, etc.) or ammonium salt.

Although the silver halide photographic material colored with the dye of the present invention represented by the above general formula has a wide absorption band in the target wavelength range, it has almost no absorption band in other wavelength ranges. There is no side absorption, and all the dyes of the present invention have high molecular extinction coefficients, and do not cause any adverse effects on photographic properties such as blur, fog, or desensitization. It is possible to fully exhibit the prevention and filtering effect of halesh sealing. In addition, after the development process, the dye is completely and quickly decolorized and eluted from the photosensitive material, so the finished photographic image not only retains the dye contained for the above purpose.
No color contamination due to recoloring of the decolorizing dye, or further contamination due to coloring of the developing solution, was observed. Furthermore, the dye of the present invention does not undergo any 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, examples of dyes represented by the above general formula of the present invention will be given.

Dye 3 Dye 4 Dye 5 08K 30, to So, to ■ -il)-
Methanol IC1 wj was added to 1.20 g of 1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinoline, and further 0.61 ff-i of triethylamine was added, followed by heating under reflux for 1 hour. After cooling, a solution of 6482 Iv of vinegar-brewed potassium dissolved in 27 yd of ethanol was added and allowed to float for about 5 minutes, followed by crystallization. After washing with ethanol, it was dried to obtain powder 2.3I with a melting point of 213° C. (decomposed). The maximum absorption value of the water bath liquid was 511 nm.

Other dyes represented by the general formulas of the present invention can also be easily synthesized according to the above synthesis examples. 5-virazolones, which are one of the intermediate raw materials for dye synthesis of the present invention, are described, for example, in the Journal of Medie-Inml
Chamlstry #c volume 7 page 493 (1964)
, Journal fer Praktlshe Ch.
It can be obtained by a condensation reaction of a β-keto acid ester and a hydrazine derivative, with reference to the method described in Emie Vol. 139, p. 148 (1934).

On the other hand, 6-(acroreiny-3-yl)-1,su3.4
-Tetrahydroquinoline derivatives can be prepared by converting 1.2.3.4-tetrahydroquinolines with a suitable alkylating agent (e.g.
0 obtained by reacting 3-dimethylaminoacrolein with phosphorus oxyoxide after altylation with alkyl iodide, alkyl P-)luenesulfonic acid ester, benzyl halide, sultone, etc. To add dyes to silver halide photographic emulsions or protective colloid solutions, dyes can be added as an aqueous solution or as a solution in methanol, ethanol, Selonlubs, glycols, dimethylformamide, dimethyl sulfoxide, pyridine, etc., or in combination with these organic solvents and water. It can be added to and present in the emulsion layer, backing layer, subbing layer, intermediate layer, protective layer, and ultraviolet absorbing layer as a mixed solution with.

The amount of these dyes used varies depending on the photographic layer to be applied.
In general, the area of a photosensitive material is 1rI? 5~1.000 per
■It is applied so that it becomes.

Examples of silver halide photographic emulsions in which the dye of the present invention is used include silver chloride, silver bromide, silver chlorobromide, silver iodobromide,
There are emulsions such as silver chloroiodobromide.

Further, the silver halogenide photographic emulsion in which the dye of the present invention is used is spectrally sensitized with commonly used cyanine, merocyanine dyes, and the like. 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, fluorescent Additives such as brighteners, developing agents and their precursors may 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 gelatin, 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 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.0 Example 1 1.5 IM' of gelatin was added to 15.0 d of water to swell it, and then heated to 40.0°C to dissolve the gelatin.

To this gelatin solution, an aqueous solution (2.0 x 10-' mol/2.0 Ll of water) of the dye of the present invention and a comparative dye described below, a hardener, and a surfactant were added, and water was further added to bring the total amount to 20.
I set it to 0d.

Next, apply this coloring solution onto a subbed polyester film base at a coating amount of 801/rr? 8.0X11.5 by heating at 50.0℃ for 24 hours.
- It was cut into a rectangle and used as a sample.

The sample was immersed in a D-72 developer at 30.0° C. for 15 seconds, then washed under running water for 10 seconds, and the remaining water droplets were sucked up with filter paper and dried to obtain a treated sample.

The optical density of the sample and the treated sample was measured using a dual wavelength/double beam self-recording spectrophotometer UV-3000 manufactured by Shimadzu Ura Seisakusho.

The results obtained are shown in Table-1.

comparison dye person Table-1 *The residual color rate was determined by the following formula.

When absorbance at absorption maximum wavelength before treatment = absorbance after treatment at absorption maximum wavelength before treatment = b, residual color rate = -X 100 As is clear from Table 1, the dye of the present invention has an absorbance of 〇Example 2 A 1% aqueous solution of dye was added to a 10% aqueous gelatin solution, and 85
1/lr? The optical density was adjusted to 1.0 when applied as a coating layer, and 10% saponin aqueous solution was mixed with 150 MI of gelatin aqueous solution, 5d, and 10% formalin t1.5.
dAdd the obtained colored gelatin in water using g,
A hardened coating layer having an optical density of 1.0 at absorption maximum 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 of the following composition was used to develop the film at 20°C.
After developing for 1 minute and 30 seconds, it was fixed, washed with water, and dried according to a conventional method.

When the optical densities of the processed films obtained using the method used in Example 1 were measured, the densities after processing at the absorption thickest wavelength of each sample containing the dye of the present invention before processing were all 0.01. Met.

Composition of developer: Metol 31 Sodium sulfite 45jl Hydroquinone 12! iSodium carbonate (monohydrate) 80I Potassium bromide
21 Add water to bring the total volume to t-i.

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 an emulsion, or storage.
The photographic material had no adverse effects on photographic properties such as capri and desensitization, and had an extremely excellent effect of preventing halosing.

Claims (1)

[Claims] (1) Photographic dye represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents an alkyl group or an aralkyl group. R_2 represents a hydrogen atom, an alkyl group, or an alkoxy group. R_3 represents a sulfoalkyl group, a sulfoaryl group. R_4 represents an alkyl group, an aryl group, a carboxy group,
Represents an alkoxycarbonyl group. )