JPH03282454A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance anti-irradiation, antihalation and filter effects by forming a hydrophilic colloidal layer contg. at least one kind of specified dye. CONSTITUTION:A hydrophilic colloidal layer contg. at least one kind of dye represented by formula I is formed. In the formula I, Z is a group of atoms required to form a benzene or naphthalene ring, each R1 and R2 is alkyl, L is methine and n is 1 or 2. The dye represented by the formula I has one or more sulfo groups in the molecular structure. Significant anti-irradiation, antihalation and filter effects can be satisfactorily produced with a small amt. of the dye.

Description

DETAILED DESCRIPTION OF THE INVENTION (M) Industrial Application Field The present invention relates to a photographic light-absorbing dye, and more particularly to a dye useful as a light-absorbing dye for use 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 improve the sharpness of finished photographic images by preventing irradiation and halos by absorbing undesirable 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 the photographic emulsion layer can be controlled by providing a filter layer).

In order to prevent irradiation and halogenation, dyes that are administered to the SC optical emulsion layer, between the emulsion layer and the support, or to the backing layer of the support, or to neutralize the filter layer, should be prepared in solution. During the production and storage of photosensitive emulsions,
It goes without saying that changes over time such as color fading should not occur, but photographic properties such as capri and desensitization should 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 decolorizing type, and the decolorized dye is eluting and does not cause coloring. In addition, it must have spectral absorption characteristics that meet the respective purposes, and must have the effects of preventing radiation, preventing radiation, and acting as a spectral filter.

However, although quite a large number of dyes have been proposed up to now, the reality is that there are only a few that satisfy the above conditions in terms of decolorizing properties, dissolution properties, photographic properties, etc.

(C) Purpose of the invention Therefore, one object of the present invention is to satisfy the above conditions.

It is an object of the present invention to provide a photographic light-absorbing dye having an illumination effect, a filter effect, and a filter effect.

(D) Structure of @Tomo As a result of various studies, the present inventors have found that the dye represented by the following formula is an excellent dye that satisfies the above objectives.

In the above formula, 2 represents an atomic group necessary to form a benzene ring or a 7talene ring, and these rings may include a sulfo group, a carboxy group, a lower alkyl group (e.g.
(methyl, ethyl, propyl, 7'fk, pentyl group, etc.), droxy group, ta alkoxy group (fl is methoxy, ethoxy group, etc.), halogen atom (e.g., chlorine,
It may have a substituent such as bromine, etc.). R1,8
2 represents an alkyl group (for example, a lower alkyl group as described as the substituent for 2 above, and these lower alkyl groups may further include a sulfo group, a carboxy group, or a hydroxy group).

It may be substituted with a halogen atom, a cyano group, a lower alkoxy group such as methoxy or ethoxy group, or the like. ). L represents a methine group, and n represents 1 or 2.

However, the dye represented by the above formula has at least one sulfo group in its molecular structure. Furthermore, when it has two or more sulfo groups, it may be in the form of metal salts such as sodium and potassium salts, ammonium salts, and organic ammonium salts such as triethylammonium, tributylammonium and pyridinium.

Although the silver halide photographic light-sensitive material colored with the dye of the present invention represented by the above-mentioned formula has a high molecular extinction coefficient in the target wavelength region, it has a high molecular extinction coefficient in other wavelength regions. There is almost no unnecessary side absorption, and in addition, it does not cause any negative effects on photographic properties such as fogging or desensitization, and provides excellent eradication prevention with a small amount of use.
It is possible to fully demonstrate the prevention and filtering effect.

In addition, since the dye is completely and quickly decolorized from the photosensitive material after the development process, the finished photographic image contains not only the residual dye contained for the above purpose but also the color due to the restoration of the decolorized mulberry. No contamination or even 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 photographic emulsion or during subsequent storage. It has seven advantages.

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 are given below, but the scope of the present invention is not limited thereto.

dye 1 dye 2 dye 3 dye 4 dye 8 dye 9 dye 10 dye 5 dye 6 dye 7 80sH-N(CzHs)s dye 11 dye 12 dye 13 dye 14 Dye? 115 dye 16 Next, typical examples of dye synthesis methods will be specifically described.

Synthesis of dye 1 Anhydro-2-methyl-1-(3'-sulfopropyl A
/) Spiro[3H-indolium-3,4'tetrahydropyran]triethylammonium hydroxide 10.
1Of and 6-formyl-1-(3-suen-hoprovir)-
1,2,3,4-tetrahydroquinoline calicum salt6.
130mg of acetic acid and 130mg of acetic anhydride in 43F! i and heated under reflux for 1 hour.

Acetic acid and acetic anhydride were distilled off under reduced pressure, 20 GTId of ethanol and 3.93 f of potassium acetate were added, heated under reflux for 15 minutes, and then allowed to stand at room temperature. The precipitated crystals were collected and recrystallized with aqueous ethanol to obtain the desired product with a temperature of 8.87F.

Yama O Melting point 269℃ ~ [decomposition], 2M1aX 59 Q
dyes represented by other general formulas 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 formula into a silver halide photographic emulsion or a protective colloid solution, it can be added as an aqueous solution or a solution in methanol, ethanol, cellosolves, glycol solution, dimethylformamide, dimethylsulfoxide, pyridine, etc. , Also, as a mixed solution of these @solvents and water, emulsion layers, backing layers, subbing layers, middle li
It can be added and present in the J layer, protective layer, and ultraviolet absorbing layer.

The amount of these dyes used varies depending on the photographic layer to which they are applied, but generally they are applied so that the area of the light-sensitive material is 5 to 1000 η.

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.

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 heptalated gelatin and malonated gelatin, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and plasticizers for dimensional stability. agents, latex polymers, etc. Furthermore, 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-F or polyester. be able to.

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

Example 1 Gelatin i, s s t @ 25xt of water was added to swell it, and then heated to 40°C to dissolve gelatin. Add to this gelatin solution an aqueous solution of the dye of the present invention and a comparative dye (1,
0x10 mol/7) C2-Om), a hardening agent, and a surfactant were added, and water was further added to bring the total amount to 4°. Next, miJ! Apply so that the voltage is 80V,
Heat at 40°C for 24 hours.

The sample was cut into a rectangular shape of 8, OX 11.5 al.

The sample was immersed in D-72 developer at 30.0°C for 5 seconds and 15 seconds, then washed under running water for 10 seconds, and the remaining water droplets were sucked up with a filter, dried, and the treated sample was removed. did. λm from 400 to 700 nm for samples and processed samples
The optical density and density change in ax were measured using a dual wavelength/double beam self-recording spectrophotometer (UV-3000) manufactured by Shimadzu Corporation. The results obtained are shown in Table-1.

Comparative Dye A Comparative Dye B Table-1 0sNa SOsNa 80sNa A: Absorbance b at λmat of sample before treatment = After treatment I As is clear from Table-1, the dye of the present invention is 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 I% aqueous solution of dye added to tlO tisgelatin aqueous solution, 80
The optical density was adjusted to 1°0 when the coating layer was t/wl, 10-saponin aqueous solution was mixed with gelatin aqueous solution 15G-Swt, and 10-thiformin was mixed with 1.5-
In addition, using the colored gelatin aqueous solution obtained, a hardened coating layer having an optical density of 1.0 is obtained by the same operation as in Example 1. A pure silver bromide emulsion is coated on top of this coating layer,
After developing for 90 seconds at 20° C. using a developer having the composition shown below, 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. (However, base concentration 0.02) Composition of developer Metol 3 Sodium sulfite 452 Hydroquinone
12 is sodium carbonate (monohydrate)
Add 802 water to make a total volume of 1 t.

In addition, each dye sample of the present invention does not undergo changes over time such as discoloration or fading during preparation of an aqueous solution, preparation of an emulsion, or storage.
It was a photosensitive material that had no adverse effects on the photographic properties of Capri, GG, etc., and had an extremely excellent anti-rage effect.

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by having a hydrophilic colloid layer containing at least one dye represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z represents the atomic group necessary to form a benzene ring or naphthalene ring. B_1, B_2 represent an alkyl group, L represents a methine group. , n represents 1 or 2, provided that the dye represented by the general formula has one or more sulfo groups in its molecular structure.)