JPH0340371B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material containing a dye, and more particularly to a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye. It is well known that dyes are included in silver halide photographic materials for the purpose of absorbing light of a specific wavelength for filters, anti-halation, anti-irradiation, or sensitivity adjustment. The hydrophilic colloid layer is colored with these dyes. The filter layer is usually located above the photosensitive emulsion layer or between the emulsion layers, and serves to convert the incident light that reaches the emulsion layer into a light having a preferable spectral composition. In addition, in order to improve the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back side of the support to prevent harmful effects at the interface between the emulsion layer and the support, or on the back side of the support. It is common practice to prevent halation by absorbing reflected light, or to prevent irradiation by coloring the emulsion layer to absorb harmful reflected light and scattered light from silver halide grains, etc. . Dyes used for this purpose must have good absorption spectrum characteristics depending on the purpose of use, be completely decolorized during photographic processing, be easily eluted from silver halide photographic materials, and be free after processing. There is no residual color staining caused by dyes, there is no negative effect on the photographic emulsion such as fogging or desensitization, there is no diffusion from the colored layer to other layers,
Furthermore, it must satisfy conditions such as excellent stability over time in solutions or silver halide photographic materials, and no discoloration or fading. To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, U.S. Pat.
No. 3247127, Special Publication No. 39-22069, No. 50-
91627, JP-A-52-34716, etc., styryl dyes as typified by U.S. Patent No. 1845404, merocyanine dyes typified by U.S. Patent No. 2493747, and merocyanine dyes typified by U.S. Patent No. 2843486. cyanine dyes, etc. However, the reality is that there are very few good dyes that satisfy all of the above conditions and can be used in silver halide photographic materials. The object of the present invention is to fully satisfy the above-mentioned conditions as a dye and have particularly good spectral absorption characteristics.
It is an object of the present invention to provide a silver halide photographic light-sensitive material containing a dye which is completely decolorized during photographic development processing, leaves very little residual color dye after processing, and is inert to photographic emulsions. This object of the present invention was achieved by incorporating a novel oxole dye represented by the following general formula [] into a silver halide photographic light-sensitive material. General formula [] In the formula, Q represents an aliphatic group or an aromatic group,
R represents a hydrogen atom, an aliphatic group or an aromatic group,
M represents a cation, L represents a methine group,
n is 0, 1 or 2, and p is 1 or 2. Specific examples of each substituent Q, R, M and L in the above general formula [] are shown below. Specifically, the aliphatic group represented by Q is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, etc.), and the aromatic group is: Aryl groups (e.g.
phenyl group, naphthyl group, etc.), and these aliphatic groups and aromatic groups further include halogen atoms (e.g., fluorine atom, chlorine atom, etc.),
Alkyl groups (e.g. methyl group, ethyl group, etc.),
It may have a substituent other than the sulfo group, such as a hydroxy group or an alkoxy group (for example, a methoxy group). The aliphatic group represented by R has 1 to 1 carbon atoms.
4 alkyl groups (e.g. methyl group, ethyl group,
(propyl group, etc.), aromatic groups include aryl groups (e.g., phenyl group, naphthyl group, etc.); , bromine atom, etc.), alkyl group (e.g., methyl group, ethyl group, etc.), aryl group (e.g., phenyl group, etc.), carboxyl group, sulfo group, hydroxy group, alkoxy group (e.g., methoxy group, etc.), aryloxy group ( For example, it may have a substituent such as a phenoxy group. Specifically, the cation represented by M includes a hydrogen atom, an alkali metal (e.g., sodium, potassium, etc.), an alkaline earth metal (e.g., calcium, etc.), ammonia, or an organic base (e.g., triethylamine, pyridine, piperidine, morpholine, etc.). etc.). The methine group represented by L may be substituted with an alkyl group, an aryl group or a halogen atom,
Examples of the alkyl group include a methyl group and an ethyl group, examples of the aryl group include a phenyl group, and examples of the halogen atom include a chlorine atom and a bromine atom. Next, typical examples of the oxonol dye represented by the above general formula [] will be shown, but the oxonol dye according to the present invention is not limited thereto. The dye used in the silver halide photographic material of the present invention can be synthesized by the following method. That is, 3- represented by the following general formula []
Carboxy-5-pyrazolones and general formula []
A compound represented by the following general formula [] and an organic base (e.g. pyridine, triethylamine, tri-n-propylamine, N,N-
(dimethylaniline, etc.), a pyrazolone compound represented by the following general formula [] is obtained. General formula [] General formula [] General _formula [] (MO ₃ S) - _P Q-NH ₂ General formula [] R ₁ SO ₂ R ₁ represents an alkyl group (e.g., methyl group, ethyl group, etc.) or an aryl group (e.g., phenyl group, 4-methylphenyl group, 2-chlorophenyl group, etc.),
X ₁ represents a halogen atom (eg, fluorine atom, base atom, bromine atom, etc.). A pyrazolone compound represented by the general formula [] obtained by the above method and the following general formulas [a], [
b], [c] or [d] with a basic condensing agent (e.g. pyridine, α-picoline, β-picoline, γ-picoline, 2,4,
6-collidine, triethylamine, N-ethylpiperidine, etc.),
Mono-, tri-, and pentamethine oxonol represented by the general formula [] can be synthesized. General formula [a] HC (OR ₂ ) ₃ General formula [b] General formula [c] General formula [d] In the above general formula, L and n represent the same meanings as described in the above general formula [], and _X2 represents an anion (for example, chloride, bromide, iodide, perchlorate, methyl sulfate, 4-
methyl phenyl sulfonate, etc.),
R ₂ represents an alkyl group (eg, methyl group, ethyl group, etc.). Next, methods for producing typical compounds among these dyes will be described below. Synthesis Example 1 Synthesis of 1-phenyl-3-(p-sulfophenylcarbamoyl)-5-pyrazolone. Disperse 6.4 g of 3-carboxy-1-phenyl-5-pyrazolone in 40 ml of acetonitrile.
7.2g of benzenesulfonyl chloride and 4g of pyridine
ml of sulfanilic acid and stirred at room temperature for 30 minutes.
5.4g and 10ml of pyridine were added and reacted at 70°C for 7 hours. The obtained homogeneous reaction solution was treated with dilute hydrochloric acid,
The precipitated crystals were collected. The melting point was 184-189°C. Synthesis Example 2 (Synthesis of Dye 3) 0.9 g of 1-phenyl-3-(p-sulfophenylcarbamoyl)-5-pyrazolone and 0.26 g of diphenylformamidine were placed in 15 ml of methanol, and 0.76 g of triethylamine was added. The mixture was heated under reflux for 3 hours. Next, 0.37 g of potassium acetate was added and the mixture was heated under reflux for 10 minutes. The precipitated dye was collected, thoroughly washed with methanol, and dried to obtain 0.2 g of the desired product.
The λmax of the aqueous solution of this dye was 470 nm. Synthesis Example 3 (Synthesis of Dye 2) 1.8 g of 1-phenyl-3-(p-sulfophenylcarbamoyl)-5-pyrazolone and 0.56 g of peropendianil were placed in 15 ml of methanol, and 1.5 g of triethylamine was added and heated for 90 minutes. It refluxed.
Next, 0.74 g of potassium acetate was added and the mixture was heated under reflux for 15 minutes. The precipitated dye was collected, thoroughly washed with methanol, and dried to obtain 1.6 g of the desired product. The λmax of the aqueous solution of this dye was 551 nm. Synthesis Example 4 (Synthesis of Dye 12) 2.1 g of 1-phenyl-3-(p-sulfophenylcarbamoyl)-5-pyrazolone and 0.81 g of 1,3-pentadienedianyl hydrochloride were dissolved in methanol 20
1.73 g of triethylamine was slowly added dropwise under water cooling, and the mixture was allowed to react at room temperature for 6 hours. Next, potassium acetate dissolved in 5 ml of methanol
0.84 g was added and reacted for 80 minutes at room temperature. Remove the precipitated dye, wash thoroughly with ethanol, and dry.
1.6g of the target product was obtained. λmax of the aqueous solution of this dye
was 642nm. In the silver halide photographic material of the present invention,
The dye represented by the general formula [] can be used as an anti-irradiation dye by being incorporated into a silver halide photographic emulsion, or can be used as a filter dye or halation by being incorporated into a non-photosensitive hydrophilic colloid layer. It can also be used as a protective dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. The dye according to the present invention can be easily incorporated into a silver halide photographic emulsion layer or other hydrophilic colloid layer by a conventional method. In general,
The dye can be incorporated into the silver halide photographic light-sensitive material by adding an aqueous solution of the dye or an organic or inorganic alkali salt of the dye to the coating solution.
The content of these dyes varies depending on the purpose of use, but generally per 1 m ² of area on the photosensitive material.
Apply and use at a concentration of 1.0 to 1000 mg. Supports in the silver halide photographic material of the present invention include cellulose acetate, cellulose nitrate, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene,
Polystyrene, Paraita paper, paper coated with polyolefin, glass, metal, etc. are used. Hydrophilic colloids in the silver halide photographic material of the present invention include gelatin, gelatin derivatives such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid, polyvinyl alcohol, and Examples include synthetic resins such as polyvinylpyrrolidone, cellulose derivatives such as carboxymethyl cellulose, and these can be used alone or in combination. As the silver halide emulsion in the silver halide photographic light-sensitive material of the present invention, emulsions of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. are used, These emulsions may be sensitized using known methods such as sulfur compounds, noble metal sensitizers, or polyalkylene oxide derivatives. These emulsions may further contain spectral sensitizers such as cyanine dyes, hemicyanine dyes, merocyanine dyes, oxonol dyes, and styryl dyes. In the silver halide photographic material of the present invention,
It may contain a polymer having an amino group or an ammonium group, a polymer having a nitrogen-containing heterocycle, etc. as a mordant, and may also contain a hardening agent, a coating aid, a stabilizer, an ultraviolet absorber, a fluorescent whitening agent, and an antistatic agent. It may also contain additives commonly used in photographic materials such as additives. It may also contain color couplers, dispersants thereof, development inhibiting compounds, and the like. Furthermore, the silver halide photographic light-sensitive material of the present invention can have any laminated structure normally provided to light-sensitive materials. The oxonol dye according to the present invention is distinguished from known oxonol dyes by having a -CONH-Q-(SO ₃ M) _p group at the 3-position of the pyrazolone, and can be incorporated into a silver halide photographic emulsion layer. It has good absorption spectral characteristics when photographed, is decolored during photographic processing, and is eluted from the photographic material.
It is characterized by extremely little residual color staining after processing and no adverse effect on the emulsion. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. Example 1 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
The exemplary dye (18) according to the present invention was added to this at 2.0×10 ^-4
5 ml of water containing mole was added, and further 1.25 ml of 10% saponin aqueous solution and 0.75 ml of 1% formalin solution were added, and water was added to make the total volume 50 ml. This dye solution was applied onto an acetyl cellulose support and dried to obtain a sample [1]. In addition, instead of the dye according to the present invention, using the following known dye A, sample [2]
It was created. Samples [1] and [2] were immersed in an aqueous sodium hydroxide solution (PH=10) at 30°C for 2 minutes with stirring, washed with water for 30 seconds, and dried. The visible spectrum of each sample was measured before and after immersion, and the elution rate was determined from the absorbance at the maximum absorption wavelength. Elution rate=E ₁ −E ₂ /E ₁ ×100 (%) E ₁ is the absorbance before immersion in the sodium hydroxide aqueous solution, and E ₂ is the absorbance after immersion.

[Table] As is clear from Table 1, the exemplary dyes according to the present invention were found to be easily eluted from the gelatin layer. Example 2 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
In addition, exemplary dyes (2), (5), (12), (14) according to the present invention,
Add an aqueous solution containing 2.0 x 10 ^-4 mol each of (16), (13) and (18), and further add 1.25 ml of a 10% saponin aqueous solution and 0.75 ml of a 1% formalin solution,
Water was added to bring the total volume to 50 ml. This dye solution was applied onto an acetylcellulose support, dried, and
Samples [3], [4], [5], [6], [101], [102]
] and [103]. In addition, instead of the dye according to the present invention, the following known samples B, C, D, E, G, H
Comparative samples [7],
[8],

[9], [10], [104], [105] and [10]
6〕
It was created. Each of these samples was immersed in the alkaline solution used in Example 1 at 30°C for 30 seconds, and washed with water for 20 seconds.
Dry. The visible spectrum of each sample before and after immersion was measured, and the decolorization rate was determined from the absorbance at the absorption maximum wavelength. The results and the maximum absorption wavelength in gelatin are shown in Table 2. Decolorization rate=E ₃ −E ₄ /E ₃ ×100 (%) E ₃ is the absorbance before immersion, and E ₄ is the absorbance after immersion.

【table】

[Processing process (31℃)]

Processing time 1 Color development 3 minutes 2 Bleach-fixing 1 minute 3 Washing 2 minutes 4 Stabilization 1 minute 5 Washing 2 minutes The composition of the processing solution used in each processing step is as follows. [Composition of color developer] 4-amino-3-methyl-N-ethyl-N-(β
-hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 4.0g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 28.0g Potassium bromide 1.5g Potassium hydroxide 1.0g Add water to make 1. [Composition of bleach-fix solution] Ethylenediaminetetraacetic acid iron salt 65.0g Ethylenediaminetetraacetic acid disodium salt
3.0g Anhydrous sodium sulfite 9.5g Ammonium thiosulfate 77.5g Anhydrous sodium carbonate 4.0g Add water to make 1. [Composition of stable solution] Glacial acetic acid 9ml Sodium acetate 3g Add water to make 1. Table 3 shows the density of the unexposed area of each sample after treatment.

[Table] In addition, the sensitivity of each sample is shown in Table 4, assuming that the blue sensitivity, green sensitivity, and red sensitivity of sample [11] that does not contain dye are each 100.

[Table] As is clear from Tables 3 and 4, in the samples containing the dye according to the present invention, color staining due to the residual color of the dye was not observed as in the samples containing the known dye. It was also found that there was very little adverse effect on the emulsion.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material characterized by having a hydrophilic colloid layer containing an oxonol dye represented by the following general formula. general formula (In the formula, Q represents an aliphatic group or an aromatic group, R represents a hydrogen atom, an aliphatic group, or an aromatic group, M represents a cation, L represents a methine group, n is 0, 1 or 2, and p is 1 or 2.)