JPH02251842A - Light absorptive dyestuff for photography - Google Patents

Abstract

PURPOSE:To prevent irradiation and halation while satisfying various photographic characteristics and to have the effect of a spectral filter by incorporating a specific dyestuff into hydrophilic colloidal layers. CONSTITUTION:The dyestuff expressed by formula I is incorporated into the hydrophilic colloidal layers. In the formula I, R1 and R2 denote a sulfoalkyl group; L1 to L3 denote a methine group; Z1, Z3 independently denote the nonmetal atom group necessary for forming indole and benzindole nuclei; m, n denote 0 to 3 integer; X<+> denotes an alkaline metal salt, such as Na or K. While this dyestuff has a broad absorption band in a desired wavelength region, the deystuff has substantially no side absorption in the other wavelength region and has a high molecular light absorption coefft. The excellent prevention of the irradiation and halation and the filter effect are sufficiently obtd. in this way with the smaller amt. of the dyestuff to be used without generating the adverse influence on the photographic characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a light-absorbing dye for photolithography, and more particularly to a dye useful as a light-absorbing dye for use in silver halide photographic light-sensitive materials.

(Prior art) In a silver halide photographic light-sensitive material, the light-sensitive emulsion J-
By absorbing harmful reflections, scattering, and diffused light within the emulsion layer, or by absorbing undesirable reflections from the emulsion layer/support paste interface and the backside of the support. It is well known to improve the sharpness of finished photographic images.

In addition, when there are multiple photographic emulsion layers such as on an emulsion layer or in a single-layer color photographic light-sensitive material, a colored layer (filter layer) is provided between them to control the spectral composition that should be incident on the photographic emulsion layer. It is also well known that

In order to prevent irradiation and halide staining, 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 prepared in solution. It goes without saying that changes over time such as discoloration or fading should not occur during the production or storage of photosensitive emulsions.
Photographic properties such as fog or 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 decoloring type, and the decolorized dye is eluting and does not color the processing solution. Furthermore, it has spectral characteristics that match each purpose,
It must have anti-irradiation, anti-halation and spectral filter effects. However, although a large number of dyes have been proposed to date, the reality is that there are only a few that satisfy the above conditions in terms of decolorizing properties, dissolution properties, photographic properties, etc.

(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 radiation and filter effects.

(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 % Formula % In the above general formula, R1 and 82 are the same as each other, 1,
represents a sulfoalkyl group (preferably a sulfoalkyl group having 2 to 6 carbon atoms). Ll, R2 and Ls represent methine groups. R2 is (however, R4, R
6 each independently represents an alkyl group or an aryl group having 1 to 6 carbon atoms, or a group of nonmetallic atoms necessary to form a 5- or 6-membered carbocyclic ring when taken together. It may have a substituent. Zl and z
2 is the non-gold necessary to independently form indole and benzindole nuclei! +! Represents a group of atoms. m and n are the number of sulfo groups that the indole nucleus and benzindole nucleus have,
Integers 0 to 3 are shown (however, m and n are never 0 at the same time).

Xφ represents an alkali metal salt such as Na, an ammonium salt, an organic ammonium salt such as triethylamine, tributylamine, or pyridine.

The silver halide photographic material colored with the dye of the present invention represented by the above general formula has the following properties in the target wavelength range:
Despite having a wide absorption band, there is almost no unnecessary side absorption in other wavelength regions, and all of the dyes of the present invention have high molecular extinction coefficients, causing problems such as fogging and desensitization. It is possible to sufficiently exhibit excellent irradiation and blemish prevention and filter effects with a small amount of use, without causing any adverse effects on photographic properties.

In addition, since the dye is completely and quickly eluted from the photosensitive material after the development process, not only the dye contained for the above purpose remains in the finished photographic image, but also the re-dying caused by the coloring of the development solution. I can't recognize it. 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

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

dye 1 dye 2 Minority fee 3 dye 7 dye 4 dye 8 dye 5 Surprise fee 9 Next, examples of alternative methods for dye synthesis will be specifically described.

Synthesis of dye 1 = 5-sulfo-2,3,3-)limethylindolenine triethylammonium 6.8f to 1.3-
4.9 t of propane sultone was added and heated at 120°C for 2 hours. After returning to room temperature, wash with ether and methanol 15
Dissolved in 01Rt, triethylamine 5.6d and N, N
'-diphenylformamidine 1.96F and acetic anhydride 2
- and stirred at room temperature for 19 hours. A 100 m ethanol solution of potassium acetate 7 and O2 was added to the reaction solution, and the mixture was heated under reflux for 10 minutes. After cooling, the precipitated crystals were collected, washed with ethanol, and then recrystallized with aqueous ethanol to obtain 2.5 tons of reddish-brown crystals.

Melting point 300℃ or higher, λmax 548 nm dye 6
Synthesis of: 2'-methyl-5'-sulfospiro[cyclohexane-1,3'-(3'H)-indolecotriethylammonium 5.71PK1.3-7''Add 3.69f of lopansultone and heat at 120°C for 2 hours After that, the temperature was returned to room temperature and washed with ether. 2.1-liters of triethylamine, 1.47 grams of N,N'-diphenylformamidine and 1.5 grams of acetic anhydride were dissolved in 90 grams of methanol, and the mixture was stirred at room temperature for one day. A solution of potassium acetate 6 and Of in ethanol 70 was added to the solution and heated under reflux for 10 minutes.After cooling, the precipitated crystals were collected, washed well with EtOH, and then recrystallized with Yoshimizu ethanol to give reddish brown crystals of 1.45P. Melting point: 30
0° C. or higher, λmax 556 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 represented by the above-mentioned formula into a silver halide photographic emulsion or protective colloid solution, an aqueous solution or methanol, ethanol, Selonlubes, glycols,
Emulsion layers, backing layers, subbing layers, interlayers, protective layers,
It can be added and present in the ultraviolet absorbing layer.

The amount of these dyes to be used varies depending on the photographic layer to which they are applied, but is generally applied in an amount of 5 to ZooOvK 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. Furthermore, by a known method, a basic mordant such as a polymer containing an amino group or an ammonium group,
Additives such as stabilizers and their precursors, surfactants, hardeners, ultraviolet edge absorbers, optical brighteners, developing agents and their precursors, etc. 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 emulsions include gelatin tetraconductors such as pentatal gelatin and mateternated gelatin, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and colloids for dimensional stability. Degradable agents, latex polymers, etc. can be added. Further, the silver halide photographic emulsion using the dye of the present invention can be coated on a support such as baryta paper, resin coated paper, synthetic paper, natural or synthetic polymer film such as cellulose triacetate or polyester.

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

Example 1 After adding 1.55 F of gelatin to 25 F of water and swelling it,
The gelatin was dissolved by heating to 0°C. To this gelatin solution, an aqueous solution (1, OX 1
0-' mol/2.0 mg of water), a hardening agent, and a surfactant were added, and then water was added to make the total amount 401Rt. Next, this colored solution was applied onto the undercoated polyester film base so that the coating amount was 80 f/100 ml.
It was heated at ℃ for 24 hours and cut into a rectangle of 8.0 x 11.51:lf to prepare a sample. The sample was heated to D-7 at 30°0°C.
After immersing in 2 developer for 5 seconds and 15 seconds, 1 in running water.
The sample was rinsed with water for 0 seconds, and the remaining water droplets were sucked up with a mouthpiece and dried to obtain a treated sample. The optical density and density change in λmax at 500 to 800 nm of the sample and the treated sample were measured using a Shimadzu dual wavelength/double beam self-recording spectrophotometer (UV-3000).

The results obtained are shown in Table IK.

Comparative Dye A Specific Acid B Comparative Dye C 3Ux5S U s K As is clear from Table 1, the dye of the present invention is Comparative Dye A
It can be seen that the optical strength before treatment and the residual color rate after treatment are superior to that of -C.

Example 2: Add a 1% aqueous solution of dye to a 10% aqueous gelatin solution and add 80
I! 14! An optical density film of 1.0 was hardened in the same manner as in Example 1 using a colored gelatin aqueous solution obtained by adding 1,5-l, 10% saponin aqueous solution to a gelatin aqueous solution of 150 dK and 10% formalin. to obtain a coating layer. 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 a degree of each sample containing the dye of the present invention after processing was all 0.01. (However, the base concentration is 0.01) Composition of developer: Metol 3, sodium sulfite, 452 hydroquinone, 12F, sodium carbonate (monohydrate), 80f, and water to make a total volume of 1 t.

Further, the samples containing the dye of the present invention are aqueous solutions i, I! ! 1
M medium, emulsion v4 manufactured during storage, does not cause changes over time such as discoloration or fading, and has no adverse effects on photographic properties such as fogging or leaky feeling.
It was a photosensitive material that had an extremely excellent anti-fouling 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. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 may be the same or different and represent a sulfoalkyl group;
_3 represents a methine group, X^■ is a cation, and Z_
1 and Z_2 independently represent a group of nonmetallic atoms necessary to form an indole or benzindole nucleus, m and n are the numbers of sulfo groups possessed by the indole nucleus and benzindole nucleus, and integers 0 to 3 (however, m and n is never 0 at the same time). ]