JPS6053302B2 - 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.

In the present invention, the 3-position of the 4,5-dihydronaphtho[2,11d]isoxazole ring and the 4-position of the 2-pyrazolin-5-one ring are bonded via a methine chain, and at least This can be achieved by coloring at least one layer of a component of a silver halide photographic light-sensitive material with at least one merocyanine-type dye having two acidic groups.

The merocyanine 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.), a substituted alkyl group (
For example, hydroxyalkyl groups such as β-hydroxyethyl and γ-hydroxypropyl, β-acetoxyethyl,
Acyloxyalkyl groups such as γ-acetoxypropyl, β-benzoyloxyethyl, β-methoxyethyl, β
monoethoxyethyl, β-isopropoxyethyl, β-(
Alkoxyalkyl groups such as β-methoxyethoxy)ethyl, carboxyalkyl groups such as carboxymethyl, β-carboxyethyl, γ-carboxypropyl, alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl, β-sulfoethyl, γ-sulfopropyl, δ-
sulfoalkyl group such as sulfobutyl, aralkyl group such as benzyl, phenethyl, sulfoaralkyl group such as p-sulfobenzyl, p-sulfophenethyl, etc.), alkenyl group (e.g. allyl), and R2 is a lower alkyl group as described for R1. group, substituted alkyl group, aryl group (e.g. phenyl), substituted aryl group (e.g. 2-carboxy7enyl, 3-sulfophenyl, 3-carboxyphenyl, 4-sulfophenyl, 4-carboxyphenyl, 2
, 5-disulfophenyl, 3,5-disulfophenyl,
3,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxy5-sulfophenyl, 3,
It represents an aryl group substituted with a carboxyl group or a sulfo group such as 6-disulfonactyl and 5,7-disulfo-2-naphthyl, and these aryl groups may further include halogen atoms such as chlorine and bromine, and alkyl groups such as methyl and ethyl. , an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, or an aryloxy group such as phenoxy.

) R3 represents an aryl group or a carboxy group which may be substituted with a lower alkyl group, an alkoxy group, an aluoxy group, a nitro group, a cyano group, a carboxy group, a sulfo group, etc. as described in R1. Further, in the above general formula, the 4,5-dihydronaphtho[2,1-d]isoxazole ring may be substituted with a lower alkyl group or a lower alkoxy group. Further, in the above general formula, R1 to R,
contains a total of at least two acidic groups (carboxy group, sulfo group), and the acidic group contains an alkali metal salt (
For example, the silver halide photographic light-sensitive material colored with the dye represented by the above general formula used in the present invention may form a "salt" such as sodium, potassium, etc.) or ammonium salt. Although the dyes have a wide absorption band in the wavelength range, there is almost no unnecessary absorption in other wavelength ranges, and all of the dyes used in the present invention have extremely high absorbance. Excellent anti-irradiation, anti-halation, and filter effects can be fully exhibited with a small amount of use, without causing any adverse effects on photographic properties such as fog, desensitization, etc.

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 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 photosensitive 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, and the 3-position of the 4,5-dihydronaphtho[2,1-d]isoxazole ring and the 4-position of the 2-pyrazolin-5-one ring are methine chains. Any merocyanine type dye that is bonded with can be used, and if necessary, two or more types of dyes can be used in combination.

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

Dye (V): 4,5-dihydro-3-methylnaphtho[2
, 1-d] Isoxazole (Pharmaceutical Journal Vol. 95, 815-
Mix 7.40y and 4.88f of 1,3-propane sultone (described in p. 821, page 197, details) and bath temperature 130-140.
Heated at ℃ for 3 hours. After cooling, crush the solidified material and
0 Tnt was added and the contents were stirred well and collected by filtration. After washing with ether 1011Lt, this product was used in the next reaction without further purification. To the quaternary salt (sulfobetaine) obtained above, ethyl orthoformate 7.72f and aniline 9
．． 68f was added and heated at a bath temperature of 90 to 100C for 2 hours.

After cooling to room temperature, 40 ml of ethanol was added, the contents were thoroughly stirred, and the precipitated crystals were collected by filtration. After washing with ethanol and drying, 9.02 fI of a yellow-brown crystalline powder with a melting point of 247.0 C (decomposed) was obtained. Next, 5.37 fI of the anilide vinyl derivative obtained above was added to a mixed solution of 20 ml of acetic anhydride and 10 ml of pyridine, and the mixture was heated under reflux for 15 minutes.

After distilling off the solvent, 2.82 f1 of 3-phenyl-1-(3-sulfopropyl)-2-pyrazolin-5-one and 50 ml of ethanol were added to the residue, and a small amount of 3.03 f of triethylamine was added dropwise to the mixture under heating under reflux. 3. After heating and refluxing the powder, an ethanol solution of potassium acetate (3.
0f1/50m1) was added.

After cooling to room temperature, the precipitated crystals were collected by filtration. Recrystallization was performed twice from aqueous ethanol, and upon drying, 1.70f of brown crystalline powder with a melting point of 300°C or higher was obtained. 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,
In the form of a solution of dimethylformamide, dimethyl sulfoxide, pyridine, etc., or a mixture of these organic solvents and water, an aqueous solution of an organic or inorganic alkali salt of a dye, or a solution of an organic solvent, it can be used as an emulsion layer, a backing layer, or a subbing layer. layer, intermediate layer, protective layer,
It can be added and present in the 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 1,00 Dm per area of the photosensitive material.
It is applied so that it becomes g. 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 heptide emulsion used in the present invention may be added with a noble metal sensitizer, a sulfur sensitizer, or a polyalkylene oxide type compound.

Further, the silver halide heptide 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 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 plasticity and latex for dimensional stability. Polymers etc. can be added.

The photographic emulsion used in the present invention can be coated on a support such as baryta paper, resin-coated paper, synthetic paper, or a natural or synthetic polymer film such as cellulose triacetate 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 1.55y of gelatin was added to 15Tn1 of water to swell it, and then heated to 4σC 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 colored solution was applied to a subbed polyester film base at a weight of 85 g/d, heated in 5C)C for 2 hours, and cut into a rectangle of &0x11.5ci to be used as a sample. . The sample was immersed in 3 (generation) D-n developer for 5 seconds and 1 hour, then rinsed in running water for 1 hour, and the adhering water droplets were sucked off with filter paper and dried to obtain a treated sample.

Macbeth transmission density measurement-504 for samples and processed samples
(Latte gelatin No. 94 was used as a filter) to measure 5 points, and the average value was taken as each concentration. The results obtained are shown in Table (1).

In the table, the concentration after treatment is 5 seconds, and 158 indicates that the time of immersion in D-72 is 5 seconds and 1 second, respectively. Table (1)
As is clearer, 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 A blue-sensitive silver iodobromide emulsion containing a yellow color former, an intermediate layer, a green-sensitive silver chlorobromide emulsion containing a magenta color former, and an intermediate layer were placed on a photographic support laminated with polyethylene. ,
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 for adding 30 mL of a 1% aqueous solution of . 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. 1. After exposing these samples,
It was 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 4.8f water to make 1e.

*Color developing agent 5 manufactured by Eastman Kodatsu
Product name: Bleach-fix solution (abbreviated as BF) EDTA*Iron salt 62.0yED
TA disodium salt 3.0f ammonium thiosulfate 75.0yθ sodium sulfite 10.0y sodium carbonate 1
Water salt 5.09 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 J effect on blue sensitivity, and coloration due to residual dye, as shown in samples containing dyes other than the present invention, was observed. I couldn't help it. Furthermore, the anti-irradiation effect was excellent, and sharp yellow images were obtained. Example 3 1.0' of each of dye numbers (■), (■), and (XI) was added as an aqueous solution to a 10% gelatin solution 1e, and a 2% chromium alum aqueous solution was added as a hardening agent. 2
5ml, 20ml of 5% saponin aqueous solution as surfactant
was added, coated on the opposite side of the emulsion-coated side of a transparent cellulose triacetate photographic film, and dried.

Claims (1)

[Scope of Claims] 1 The 3rd position of the 4,5-dihydronaphtho[2,1-d]isoxazole ring and the 4th position of the 2-pyrazolin-5-one ring are bonded by a dimethine chain, and the molecule 1. A silver halide photographic material, characterized in that at least one layer of its constituent elements is colored with at least one merocyanine-type dye having at least two acidic groups therein.