JPS6053303B2 - Colored silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to colored silver halide photographic materials.

More specifically, the present invention relates to a silver halide photographic material provided with irradiation prevention and antihalation means, and a silver halide photographic material provided with a filter layer. Silver halide photographic light-sensitive materials absorb harmful reflections, scattering, diffused light, etc. in the light-sensitive emulsion layer, or undesirable reflected light from the interface between the emulsion layer and the support base and the back surface of the support base. It is well known to prevent irradiation and halation and improve the sharpness of finished photographic images by including dyes that absorb .

In addition, by providing a colored layer (filter layer) above the emulsion layer or between them when there are multiple photographic emulsion layers such as in a multilayer color photographic light-sensitive material, the spectral composition that should be incident on the photographic emulsion layer can be controlled. It is also well known that

In order 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 must be used during solution preparation or during the production of the light-sensitive emulsion. changes during storage and storage,
Naturally, it must not cause changes over time such as fading, but it must also not adversely affect photographic properties such as fogging or dimming.

Furthermore, during the development process, it must be completely and quickly decolored or must be eluted and removed from the photographic material.

Above all, it must have spectral absorption characteristics that meet the respective purposes, and must have the effects of preventing irradiation, preventing halation, and acting as a spectral filter.
However, although quite a large number of dyes have been proposed until this month, the reality is that only a few of them satisfy the above-mentioned conditions, such as decolorization properties, dissolution properties, and photographic properties.

Accordingly, an object of the present invention is to provide a silver halide photographic material that satisfies the above conditions and has excellent eradication, anti-halation and filter effects.

The present invention relates to the 3-position of the 415,6,7-tetrahydrobenziisoxazole ring and the 4-position of the 2-pyrazolin-5-one ring.
Achieved by coloring at least one layer of a silver halide photographic light-sensitive material component with at least one merocyanine-type dye in which the two positions are bonded to each other by a methine chain and which has at least two acidic groups in the molecule. We were able to.

The meloncyanine type dye used in the present invention is particularly preferably one represented by the following general formula. General Formula In the above general formula, R1 is an alkyl group, preferably a lower alkyl group having up to 5 carbon atoms (for example, methyl, ethyl, propyl,
butyl, pentyl, etc.), substituted alkyl groups (e.g. β-
Hydroxyalkyl groups such as hydroxyethyl and γ-hydroxypropyl, acyloxyalkyl groups such as β-acetoxyethyl, γ-acetoxypropyl, and β-benzoyloxyethyl, β-methoxyethyl, β-monoethoxyethyl, β-isopropoxyethyl, Alkoxyalkyl groups such as β-(β-methoxyethoxy)ethyl, carboxyalkyl groups such as carboxymethyl, β-carboxyethyl, γ-carboxypropyl, alkoxycarbonyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl, etc. Alkyl group, β-
sulfoalkyl groups such as sulfoethyl, γ-sulfopropyl, δ-sulfobutyl, aralkyl groups such as benzyl and phenethyl, sulfoaralukyl groups such as p-sulfobenzyl and p-sulfophenethyl), alkenyl groups (e.g. allyl); , R2 is a lower alkyl group, substituted alkyl group, or aryl group (e.g. phenyl) as described for R1.
, substituted aryl groups (e.g. 2-carboxyphenyl,
3-sulfophenyl, 3-carboxyphenyl, 4-
Sulfophenyl, 4-carboxyphenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 3,4-
Aryl groups substituted with carboxy or sulfo groups such as dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxy5-sulfophenyl, 3,6-disulfonaphthyl, 5,7-disulfo-2-naphthyl These aryl groups further include halogen atoms such as chlorine and bromine, alkyl groups such as methyl and ethyl, methoxy,
It may be substituted with an alkoxy group such as ethoxy, propoxy, butoxy, or an aryloxy group such as phenoxy.

) R3 may be substituted with a lower alkyl group as described for R1, an alexyl group, an alkoxy group, an alluroxy group, a nitro group, a cyano group, a carboxy group, a sulfo group, etc. as described for R2. Represents an aryl group or a carboxy group. Furthermore, in the above general formula, the 4,5,6,7-tetrahydrobenziisoxazole ring may be substituted with a lower alkyl group or a lower alkoxy group. Further, in the above general formula, R1 to R3 contain at least two acidic groups (carboxy group, sulfo group) in total, and the acidic groups are alkali metal salts (e.g., sodium, potassium, etc.) or ammonium salts. The silver halide photographic material colored with the dye represented by the above general formula used in the present invention has a broad absorption band in the target wavelength region. Despite this, there is almost no unnecessary absorption in other wavelength regions,
In addition, all of the dyes used in the present invention have extremely high absorbance, and have excellent anti-irradiation and anti-halation effects even when used in small amounts without causing any negative effects on photographic properties such as fog or desensitization. And the filter effect can be fully exhibited.

Further, after the development process, the dye is completely and quickly decolorized from the photosensitive material, and no color staining due to the residual dye contained for the above purpose is observed in the finished photographic image. Furthermore, the dye used in the present invention does not undergo any changes such as discoloration or fading during the preparation of the dye solution, and is not affected by external conditions such as moist heat during the production of the light-sensitive emulsion or during subsequent storage. It has the advantage of being stable.

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

The dye used in the present invention is not limited to the above-mentioned exemplified dyes. Any merocyanine-type dye that is bonded with can be used, and if necessary, two or more dyes can be used in combination.

l Next, typical examples of dye synthesis methods will be specifically described.

Synthesis of dye (■) Mix 4.12f of 3-methyl-4,5,6,7-tetrahydrobenziisoxazole and 3.66f of 1,3-propane sultone,
The mixture was heated at C for 25 hours.

After cooling, the mixture was washed repeatedly with ethyl ether to obtain a hygroscopic white powder, which was used as is in the next reaction without further purification. To the sulfobetaine quaternary salt obtained above, 5.79 f of orthoethyl ethyl and 7.
26f was added and heated on a boiling water bath for 2 hours. After cooling, the mixture was washed repeatedly with ethyl ether, and then ethanol was added and stirred to obtain a solid. Re-crystallization with ethanol and drying gave 4.24' of a pale F5 color crystalline solid with a melting point of 294.0C (decomposition). Next, 0.72 f of the anilinovinyl compound obtained above was mixed with 4 ml of acetic anhydride and 2 ml of pyridine and heated under reflux.

Once the solvent is distilled off, the residue is 3-phenyl-1-(3-
Sulfopropyl)-2-pyrazolin-05-one 0.5
After adding 10 ml of 8f ethanol and heating to reflux, 1.00f of triethylamine was added and heating and refluxing was continued. A solution of 0.60 g of potassium acetate dissolved in 101 t of ethanol was added to the reaction solution, and the precipitated crystals were collected by filtration. After washing with ethanol, recrystallize from aqueous ethanol and dry to obtain an orange crystalline powder with a melting point of 300C or higher.
I got 8fI. Other dyes used in the present invention can also be easily synthesized according to the above synthesis examples.

The absorption maximum value (Nnl) of the methanol solution of the representative example of the dye used in the present invention is as follows.

To add the dye represented by the above general formula into a silver halide photographic emulsion or protective colloid solution, an aqueous solution or methanol, ethanol, cellosolves, glycols,
Emulsion layers, backing layers, subbing layers, in the form of solutions of dimethylformamide, dimethyl sulfoxide, pyridine, etc., mixtures of these organic solvents and water, aqueous solutions of organic and inorganic alkaline salts of dyes, and solutions of organic solvents. , an intermediate layer, a protective layer, and an ultraviolet absorbing layer.

The amount of these dyes used varies depending on the photographic layer to which they are applied, but is generally 5 to 1,000 per 1 Wt of area of the light-sensitive material.
It is applied so that it becomes m9.

Examples of the silver halide emulsion used in the present invention include emulsions of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Further, the silver halide emulsion used in the present invention may be added with a noble metal stimulant, a sulfur sensitizer, or a polyalkylene oxide compound.

Further, the silver halide emulsion used in the present invention is spectrally sensitized with commonly used cyanine and merocyanine dyes.

Furthermore, by a known method, the photographic material of the present invention has an amino group,
Alternatively, additives such as basic mordants, stabilizers, surfactants, hardeners, ultraviolet absorbers, and fluorescent brighteners, such as polymers containing ammonium groups and nitrogen-containing heterocycles, may be contained. can. When used in the silver halide photographic emulsion color light-sensitive material used in the present invention, a color coupler or a dispersant thereof can be contained. In addition, as a protective colloid for silver halide emulsions,
In addition to gelatin, 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.

The photographic emulsion used in the present invention can be coated on a support such as Paraita paper, resin coated paper, synthetic paper, natural or synthetic polymeric film such as cellulose triacetate or polyester. Representative examples will now be described in which dyes according to the invention are used to form anti-irradiation, anti-halation and filter layers.

Example 1 1.55 f of gelatin was added to 15 ml of water to swell it, and then heated to 40C to dissolve the gelatin.

Add to this gelatin solution an aqueous solution of the dye used in the present invention (
1.84×10 −4 mol/2.0 ml of water), a hardening agent, and a surfactant were added, and water was further added to make the total volume 20 ml. Next, this coloring solution was applied onto the undercoated polyester film base at a rate of 85m9/i, and 5CfC
The sample was heated for 2 hours and cut into a rectangle of &0×11.5 cI1 to prepare a sample. The sample was immersed in a 30'Cf) D-n developer for 5 seconds and 2 seconds, then rinsed in running water for 1 time, and the adhering water droplets were blotted with a piece of paper and dried to obtain a treated sample. .

Samples and processed samples are Macbeth transmission densitometer sum-504
(Ratsuten No. 94 was used as a gelatin filter) to measure the concentration at 5 points, and the average value was used as each concentration. The results obtained are shown in Table (1).

In the table, the concentration after treatment of 5 seconds and 1 alcohol indicate that the time of immersion in D-72 is 5 seconds and specific seconds, respectively. As is clear from Table (1), the dye used in the present invention has a large difference between the initial density and the density after treatment, indicating that the dye has excellent shedding.

Example 2 On a photographic support laminated with polyethylene, a back-sensitive silver iodobromide emulsion containing a yellow color former, an intermediate layer, a green-sensitive silver chlorobromide emulsion containing a magenta color former, an intermediate layer,
A color photographic paper was prepared which carried a red-sensitive silver chlorobromide emulsion containing a cyan color former and a protective layer.

Next, 1 kg of blue-sensitive silver iodobromide emulsion was added with the dye number of the present invention (■
) A sample was prepared exactly the same as the above sample except that 0 ml of a 1% aqueous solution of 1% was added. Further, as a comparative sample, a color photographic paper was prepared in which a dye (4) having the following structure outside the present invention was added in the same manner as above. After these samples were exposed, they were treated with the following treatment solution.

Color developer (abbreviated as CD) Benzyl alcohol 15.0ml Potassium bromide 0.3f Sodium hexametaphosphate 0.5f Sodium sulfite monohydrate 2&0f CD-3*
Add 4.8 fI water to make 1'.

*Product name of color developing agent manufactured by Eastman Kodatsu Co., Ltd. Bleach-fix solution (abbreviated as BF') EDTA *Iron salt
62.0f EDTA disodium salt
3.0f ammonium thiosulfate
75.0f Sodium sulfite
10.0f Sodium carbonate monohydrate 5.0
f Add water to make 1e.

*Substantially stable solution of ethylenediaminetetraacetic acid (abbreviated as SB) 45% acetic acid 19.0ml 1 Sodium acetate 3.0f Add water to make 1e.

The treatment temperature and time were as shown in Table (2).

Table 3 shows the sensitivity obtained.

However, the blue, green, and red sensitivities of the sample to which no anti-irradiation dye was added are each expressed as 100. The density of the unexposed part of each sample after processing is shown in the table (4
).

Next, in order to compare the decolorization properties in rapid processing, a processing solution was prepared by removing only CD-3 from the above color developing solution (CD
Table (6) shows the results of measuring each concentration of the base after processing under the treatment conditions shown in Table (5).
As is clear from the above results, the sample containing the dye used in the present invention has little effect on blue sensitivity;
No coloration due to residual dye was observed, as was the case with samples containing dyes other than those of the present invention. Furthermore, the anti-irradiation effect was excellent, and sharp yellow images were obtained. Example 3 1.0f1 each of dyes with dye numbers (■), (■), and (XI)
were added as an aqueous solution to 1' of 10% gelatin solution, and 25 ml of 2% chromium alum aqueous solution as a hardening agent and 20 t of 5% saponin aqueous solution as a surfactant were added to make a transparent cellulose triacetate photographic material. It was coated on the opposite side of the film to the emulsion coated side and dried.

Claims (1)

[Claims] 1 The 3rd position of the 4,5,6,7-tetrahydrobenziisoxazole ring and the 4th position of the 2-pyrazolin-5-one ring are bonded via a dimethine chain, and at least 2
At least one merocyanine-type dye having acidic groups
A silver halide photographic material characterized in that at least one layer of constituent elements is colored with seeds.