JPS5953532B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material containing a dye.

More specifically, the present invention relates to a silver halide photographic material provided with anti-irradiation and anti-halation means. Silver halide photographic light-sensitive materials absorb harmful reflections, scattering, and diffuse colored light in the light-sensitive emulsion layer, or absorb 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 that the inclusion of absorbing dyes improves the sharpness of finished photographic images by preventing irradiation and halation.

In order to prevent irradiation and halation, dyes contained in the light-sensitive emulsion layer, an intermediate layer between the emulsion layer and the support, or a backing layer of the support may discolor or fade during solution preparation, or during the production and storage of the light-sensitive emulsion. It goes without saying that it must not change over time, and it must not have any negative effects on photographic properties such as fog or desensitization.

Furthermore, during the photographic development process, the color must be completely and quickly erased or eluted from the photographic material.
Above all, each dye must have spectral absorption characteristics that match its purpose, and must also have anti-irradiation and anti-halation effects.However, although a considerable number of dyes have been proposed to date, The reality is that there are only a few that satisfy the above properties such as physical properties and photographic properties.

The present inventors applied a methine oxonol dye represented by the general formula below to a silver halide photographic light-sensitive material, and found that the dye satisfies the above characteristics and has excellent irradiation and antihalation effects. I found it.

In the general formula, R1 and R2 represent hydrogen, an alkyl group (for example, preferably a methyl group, an ethyl group, an n-butyl group, a cyclohexyl group, an n-hexyl group, a benzyl group, a carboxymethyl group, an ethoxycarbonylmethyl group, an n -ptoxycarbonylmethyl group, 2-[■■Hydroxypropyl group, 2-
chloroethyl group, 2-cyanoethyl group, 2-(2-hydroxyethoxy)ethyl group, 2-methylsulfonylethyl group, etc.), alkenyl group (e.g. allyl group etc.), or diaryl group (e.g. preferably phenyl group, 4 -Sulfophenyl group, 3-sulfophenyl group, 4-carboxyphenol group, 3-canoleboxyphenyl group, 2.5
-disulfophenyl group, 3,5-disnorphenyl group, 3,4-dicanoleboxyphe,nyl group, 3,5-dicarboxyphenyl group, 3-carboxy-5-sulfophenyl group, etc.), These aryl groups further contain halogen atoms (e.g. chlorine, bromine, etc.) and lower alkyl groups (
For example, methyl group, ethyl group, etc.), lower alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), substituted amino group [alkyl group as a substituent (for example, methyl group, ethyl group, etc.), Examples include acyl groups (eg, acetyl group, propionyl group, etc.), which may be either mono-substituted or di-substituted.

R3 is hydrogen, an alkyl group (for example, preferably a methyl group, an ethyl group, an n-butyl group, a benzyl group, a sulfomethyl group, a carboxymethyl group, a 2-hydroxyethyl group,
2-sulfoethyl group, 2-carboxyethyl group, 3-sulfopropyl group, 3-carboxypropyl group, 4-sulfobutyl group, 2-ethoxycarbonylethyl group, etc.), alkenyl group (e.g. allyl group etc.), or aryl group (e.g. , preferably a phenyl group, 2-carboxyphenyl group, 3-sulfophenyl group, 3-carboxyphenyl group, 4-sulfophenyl group, 4-canoleboxyphenylene group, 2,5-disnorefophenyl group, 3・5-disulfophenyl group, 3,4-dicarboxyphenol group, 3.
5-dicanoleboxyphenol group, 3-canoleboxy-5-sulfophenyl group, 3,6-disulfo-1-naphthyl group, 5,7-disulfo-2-naphthyl group, etc.), and these aryl groups include Furthermore, halogen atoms (e.g. chlorine, bromine, etc.), lower alkyl groups (e.g. methyl group, ethyl group, etc.), hydroxy groups, lower alkoxy groups (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), etc. are substituted. It's okay.

In addition, the sulfo group or carboxy group in R1, R2, and R3 is an alkali metal salt (e.g., sodium, ryorium, etc.)
, may form salts such as ammonium salts. Further, R1, R2, and R3 may be the same or different. However, at least one of R1, R2, and R3 has a sulfo- or carboxy-substituted group.
n is 0, 1, or 2, and the methine chain connecting the cyclic structures at both ends in the formula is a lower alkyl group (e.g., methyl group, ethyl group, etc.) or an aryl group (e.g., phenyl group, etc.) may be replaced by. Tautomers of the structure represented by the above general formula are also within the scope of the dye according to the present invention. Although the silver halide photographic light-sensitive material colored with the methine oxonol dye represented by the above general formula according to the present invention has a wide absorption band in the target absorption wavelength region, it has a wide absorption band in other wavelength regions. There is almost no unnecessary absorption, and all of these dyes according to the present invention have extremely high absorbance, and can be used in small amounts without causing negative effects on photographic properties such as fog or desensitization. Excellent anti-irradiation and anti-halation effects can be fully exhibited.

Further, after the development process, the dye is completely and quickly decolored from the photosensitive material, and the finished photographic image does not show any coloration due to the residual dye contained for the above purpose. Furthermore, the dye according to the present invention does not undergo any changes such as discoloration or fading during the preparation of the dye solution, and is completely unaffected 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 methine oxonol dye used in the present invention is not limited to the above-mentioned exemplified dyes, but any dye having the chemical structure of the above general formula can be used.If necessary, two or more types of methine oxonol dyes may be used. The above dyes can be used in combination.

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

Synthesis Example 1 Dye (1): 12.96 g of 5-anilinomethylene-1,3-dimethylbarbituric acid, 12.07 g of 3-(2-sulfoethyl)rhodanine, and 20.2 g of triethylamine.
4 g was dissolved in 500 ml of pyridine and 250 ml of water, and stirred on an oil bath at a melting temperature of 100±5° C. for 6 hours.

After distilling off the distillate from the post-reaction solution under reduced pressure on a water bath, 500 ml of ethanol is added to the residue, heated and then allowed to cool, and the precipitated crystals are filtered out. After washing with ethanol, further washing with hot ethyl acetate,
After drying, 14.5 g of orange powder is obtained. Maximum absorption value of aqueous solution 456 mμ. Synthesis example 2 Dye (V): 5
-2.31 g of anilinomethylenebarbitunoleic acid and 3-
1.91 g of canoleboxymethinolerhodanine and 4.1 g of triethylamine are dissolved in 200 ml of pyridine and stirred at an oil bath temperature of 100±5° C. for 6 hours.

The aqueous solution of the post-reaction solution is dried under reduced pressure, the residue is dissolved in water-containing methanol, and insoluble materials are removed. 2g of potassium acetate in the deep water
After heating, the mixture was dried under reduced pressure on a water bath, and the residue was thoroughly washed with ethanol and dried to obtain 3.3 g of orange powder. Maximum absorption value of aqueous solution 450 mμ. Synthesis Example 3 Dye (IX): 1.75 g of 1-ethyl-3-(3-sulfophenyl)barbituric acid potassium salt, 1.53 g of 5-acetanilide methylene-3-ethylrhodanine, and 1.52 g of triethylamine in 40 ml of pyridine. dissolve,
Stir for 30 minutes at a water bath temperature of 85±5°C.

The post-reaction solution was dried under reduced pressure on a water bath, and the residue was recrystallized from ethanol and dried to obtain orange crystals 1.5. Maximum absorption value of aqueous solution 456 mμ. Synthesis example 4 dyes (
XVllll): 1.64 g of 5-(γ-acetanilideprobenylidene)-1,3-dimethylbarbituric acid and 3
1.21 g of -(2-sulfoethyl)rhodanine and 2 g of triethylamine are dissolved in 100 ml of methanol and 70 ml of water, and heated under reflux on a water bath for 1 hour.

After the post-reaction, 1 g of potassium acetate was added, the mixture was dried under reduced pressure on a water bath, the residue was dissolved in water-containing methanol, and insoluble materials were removed.
The filtrate is dried and the residue is washed with hot acetone and dried to give a red powder. Maximum absorption value of aqueous solution 495 mμ.
Synthesis Example 5 Dye (X): 5-(5-acetanilide-2,4-pentadienylidene)-1,3-dimethylbarbituric acid 3
．． 53g and 3-(2-sulfoethyl)rhodanine 2.4
1g and 4.1g of triethylamine in 200ml of pyridine
and 40 ml of water and stirred for 7 hours at an oil bath temperature of 100±5°C.

After cooling to room temperature, analyze. Filter off the crystals. The extract was dried on a water bath under reduced pressure, the residue was dissolved in ethanol, and the insoluble materials were removed. 2 g of potassium acetate is added to the bottom liquid, heated, and then allowed to cool to room temperature. When the precipitate is filtered and dried, blue-purple crystals 2.4
g is obtained. Maximum absorption value of aqueous solution 540 mμ. Further, other dyes used in the present invention can be easily synthesized according to the above synthesis method. Obtained as above,
The dye represented by the above general formula can be present in the emulsion layer, intermediate layer, protective layer, undercoat layer, backing layer, and ultraviolet absorbing layer in the silver halide photographic light-sensitive material.

When applied to photosensitive materials, adding an aqueous solution of dye is a common and simple method, but depending on the purpose of use,
It is also possible to prepare and add reactants with metal ions, especially silver ions, or to add highly polar organic solvents such as methanol, ethanol, methyl cellosolve, ethylene glycol, glycerin, polyethylene glycol, acetonitrile, DMF.
, DMSO, pyridine, etc. or a mixture of these solvents and water; an aqueous solution of a salt of an organic or inorganic dye with an alkali; or a solution of an organic solvent. The amount of these dyes used varies depending on which photographic layer they are applied to, etc., but is generally applied in an amount of 5 to 1000 mg per 1 meter area of the light-sensitive material. The silver halide emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, and the crystal form, crystal habit, grain size, etc. There are no restrictions on the silver ion concentration, hydrogen ion concentration, etc.

Emulsions can be produced by various known methods. For example, forward mixing method, back mixing method, simultaneous mixing method,
J Camo V2, US Patent No. 2592250, US Patent No. 3622
318, etc., ammonia method, acidic to neutral method, ethylenediamine method as described in U.S. Pat. No. 2,448,534, JP-A-4816
Examples include the silver iodide nuclear method as described in No. 5925, and a method combining these methods. Further, the emulsion is disclosed in US Pat. No. 1,574,944, US Pat.
It may be sensitized with a sulfur compound as described in U.S. Pat. No. 0689, U.S. Pat. 25400
Gold compounds as described in US Pat. No. 85, No. 2597856, US Pat. No. 2597916, etc., US Pat.
No. 60, No. 2540086, No. 2566245, No. 2566263, No. 2598079, etc., salts of noble metals such as palladium, iridium, rhodium, ruthenium, platinum, etc.;
No. 0, No. 2518698, No. 2521925, No. 2
No. 521926, No. 2694637, No. 298361
It may be sensitized with reducing substances such as amines and stannous salts, and polyalkylene oxide compounds as described in No. 0 and No. 3201254. Binders used in the emulsion include lime-treated gelatin, acid-treated gelatin, U.S. Pat. Nos. 2,594,293 and 2,614,928.
No. 2763639, No. 3118766, No. 31
No. 32945, No. 3186846, No. 3312553
British Patent No. 861414, British Patent No. 1033189,
Gelatin derivatives, casein, colloidal albumin, cellulose derivatives such as canoleboxymethylcellulose and hydroxyethyl cellulose, agar, alginic acid and its esters as described in Japanese Patent Publication Nos. 39-5514 and 42-26845, etc. , derivatives such as amides,
Synthetic polymer binders such as sugar derivatives, polyvinyl alcohol, and poly-N-vinylpyrrolidone can be used. These binders can be hardened with various hardeners. Hardeners include aldehydes such as formaldehyde and glutaraldehyde, ketones such as diacetyl and cyclopentanedione, and US Pat. No. 328,877.
Compounds described in British Patent No. 5, British Patent No. 2732303, British Patent No. 974723, British Patent No. 1167207, etc., bis(2-chloroethyl)urea, 2-hydroxy-4,6-
Reactive halogen-containing compounds such as dichloro-1,3,5-triazine, U.S. Pat. Nos. 3,232,763 and 3,635
Compounds described in No. 718, British Patent No. 994869, etc., divinyl sulfone, 5-acetyl-1,3-
Reactive olefins such as diaryloylhexahydro-1,3,5-triazine, U.S. Pat. No. 2,732,316;
Compounds described in US Pat. No. 2,586,168, etc., N-methylol compounds such as N-hydroxymethylphthalimide, isocyanates described in US Pat. No. 3,103,437, etc., US Pat. No. 2,950,197, US Pat.
Aziridine compounds described in No. 4404, No. 2983611, No. 3017280, etc., U.S. Patent No. 27
Acid derivatives described in US Pat. No. 25294 and US Pat. No. 2,725,295, carbodiimides described in US Pat. No. 3,100,704, etc., epoxies described in US Pat. No. 3,091,537, etc., US Pat. No. 3,321,313.
Isoxazoles, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, inorganic hardeners such as tarom alum and zirconium sulfate, etc., are known. It is being

Various other organic and inorganic compounds can be added to the silver halide emulsions used in combination with the dyes of the invention. For example, US Pat. No. 1,758,576, US Pat.
No. 0178, No. 2131038, No. 2173628, No. 2697040, No. 2304962, No. 232
No. 4123, No. 2394198, No. 2444605, No. 2444606, No. 2444607, No. 244
No. 4608, No. 2476536, No. 2566245, No. 2694716, No. 2697099, No. 270
No. 8162, No. 2728663, No. 2728664, No. 2728665, No. 2824001, No. 284
No. 3491, No. 2886437, No. 3052544, No. 3137577, No. 3220839, No. 322
No. 6231, No. 3236652, No. 3251691, No. 3252799, No. 3287135, No. 332
6681, 3420668, 3622339, 3573056, British Patent No. 893428, 403789, 1173609, 120018
Antifoggants, stabilizers and crystal habit modifiers as described in US Pat. 27479
No. 96, No. 2784087, No. 3253921, No. 3352681, No. 3533794, No. 37388
No. 37, No. 3754919, No. 3769294, British Patent No. 1026142, Japanese Patent Publication No. 491-26139,
Ultraviolet absorbers such as those described in Japanese Patent No. 50-25337 and Japanese Patent No. 51-6540, U.S. Patent No. 2360
No. 290, No. 3432300, No. 3573050,
No. 3574627, No. 3698909, No. 3764
No. 337, German Published Patent No. 2146668, Special Publication No. 1973
No.-31256, No. 131625, No. 48-
No. 31626, No. 1973-20973, No. 2097-2
No. 0974, No. 49-20977, No. 30-1973
No. 462, JP-A-47-37635, JP-A-48-26
No. 133, No. 134326, No. 134326, No. 134326, No. 50-63
38, No. 50-6339, etc., other surfactants, development accelerators, desilvering accelerators, known sharpness-improving dyes other than those of the present invention, and the like. Also, JP-A-50-145124 and JP-A-51-16921.
No., No. 5265426, No. 134425, No. 32325'', No. 117123, No. 52
No. 52-128125, 25217-1973
No. 50-118724, 32635-1973
No., Special Publication No. 1972-10254, Special Publication No. 43-13498
The dye according to the present invention is used in combination with a mordant such as that described in No. 1985-85222, No. 15820-1970, No. 16051-1970, No. 1418-1971, etc. You may. The photographic material of the present invention is
Commonly used supports, such as plastituta film,
It can be applied to paper, cloth, glass, ceramics, metal, etc. Examples regarding the photographic properties of the dye according to the present invention are shown below.

Example 1 1.55 g of gelatin was added to 15 ml of water, swollen and then heated to 40°C to form a solution, into which were added 1.84 x 10 -4 mol each of the dye according to the present invention and a known dye, and a hardener. , add surfactant, and add water to bring the total volume to 20 ml.

This colored solution was coated on a subbed polyester film base at a concentration of 85 g/M2, and
The sample is heated for several days and cut into a rectangle of 8.0 x 11.5 d.

The sample is immersed in D-72 developer at 30° C. for 5 seconds and 15 seconds, washed under running water for 10 seconds, and the adhering water droplets are quickly absorbed using fuchi paper and dried to obtain a treated sample.
Samples and processed samples are measured using a Maghes transmission densitometer TD-
504 (Latte gelatin NO.94 as a filter)
), measure at 5 points, and use the average value as each concentration. As a known dye, a compound having the following structure was used. The results are shown in a table below.

A high initial concentration in this table indicates a high absorbance of the dye, and a larger difference from the concentration after treatment indicates a better decolorizing property of the dye. A concentration of 5 seconds after treatment indicates that the time of immersion in D-72 was 5 seconds. Example 2 A 1% methanol solution of the dye was added to a 10% gelatin aqueous solution, and the optical density was adjusted to 1.0 when a coating layer of 85 g/M2 was formed. A hardened coating layer having an optical density of 1.0 is obtained by the same procedure as in Example 1 using a colored aqueous gelatin solution obtained by adding 5 ml of gelatin and 10% formalin (1.5 ml of the same).

A pure silver bromide emulsion was coated on this coated layer and developed at 20° C. for 1 minute and 30 seconds using a developer having the composition shown below, followed by fixing, washing with water, and drying according to a conventional method. The optical density of the obtained treated film was measured using the method carried out in Example 1, and the results shown in Table 2 were obtained. For comparison, the known dye A. A sample using B was prepared and the results obtained by the same operation are shown. Composition of developer Metol 3g Sodium sulfite 45g Hydroquinone 12g Sodium carbonate (
monohydrate) 80g sodium bromide
Add 2g water
Let the total amount be 11.

In addition, the samples containing dye numbers (1), (IV), and (V) were photosensitive materials that had extremely excellent antihalation effects without any negative effects such as desensitization or fogging during emulsion coating or after storage. Ta.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1, R_2, R_3 represent hydrogen, an alkyl group, an aryl group, or an alkenyl group, R_1,
R_2 and R_3 may be the same or different. However, at least one of R_1, R_2, and R_3 shall have a sulfo- or carboxy-substituted group. n is 0, 1, or 2, and the methine chain connecting the two cyclic structures at both ends may be substituted with a lower alkyl group or an aryl group. 1. A silver halide photographic material, characterized in that at least one layer of the constituent elements of the silver halide photographic material contains at least one methine oxonol dye (including tautomers) represented by: