JPH0554654B2 - - 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. In silver halide photographic light-sensitive materials (hereinafter referred to as photographic materials), dyes are added to the photographic material for the purpose of absorbing light of a specific wavelength for the purpose of filtering, preventing halation, preventing irradiation, or adjusting the sensitivity of photographic emulsions. It is well known that the hydrophilic colloid layer is colored with a dye. A filter layer is usually located above a photosensitive emulsion layer or between two emulsion layers, and serves to convert incident light that reaches the emulsion layer into 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. ing. Dyes used for such purposes must have good absorption spectral characteristics depending on the purpose of use, be completely decolored during photographic processing, be easily eluted from the photographic material, and be free from the dye after processing. There is no residual color contamination, there is no negative effect on the photographic emulsion such as fogging or desensitization, there is no diffusion from the dyed layer to other layers, and there is no staining in the solution or photographic material. It must satisfy various conditions such as excellent stability over time 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, UK patent no.
506385 specification, US Patent No. 3247127 specification,
oxonol dyes described in Japanese Patent Publication No. 39-22069 and Japanese Patent Publication No. 43-13168, styryl dyes represented by U.S. Patent No. 1845404, merocyanine dyes represented by U.S. Patent No. 2493747,
There are cyanide dyes as typified by US Pat. No. 2,843,486. However, the reality is that there are very few good dyes that satisfy all of the above conditions and can be used in photographic materials. The object of the present invention is to have good absorption spectrum characteristics, be decolorized during photographic processing, be eluted from photographic materials, have extremely little residual color contamination after processing, and be inert to photographic emulsions. An object of the present invention is to provide a silver halide photographic material containing a dye. This object of the present invention is achieved by a silver halide photosensitive material containing a novel oxonol dye represented by the following general formula (). General formula () In the formula, R represents an aryl group or a heterocyclic group having at least one carboxy group. However, it does not have a sulfo group. L represents a methine group, and n represents 0, 1 or 2. Examples of the aryl group represented by R include 4-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxy-2-methylphenyl group, 4-carboxy-2-chlorophenyl group, 3
-Carboxy-4-chlorophenyl group, 5-carboxy-2-chlorophenyl group, 4-carboxy-2-methoxyphenyl group, 4-carboxy-2
-hydroxyphenyl group, 4-carboxy-2,
5-dichlorophenyl group, 4-carboxy-2,
6-dimethylphenyl group, 2,5-dicarboxyphenyl group, 3,5-dicarboxyphenyl group,
3-carboxy-4-phenoxyphenyl group, 4
-carboxy-2-chloro-6-methylphenyl group, 3,6-dicarboxy-α-naflu group, 3,
Examples include 6-dicarboxy-8-hydroxy-α-naphthyl group, 7-carboxy-5-hydroxy-β-naphthyl group, and 6,8-dicarboxy-β-naphthyl group. Further, the carboxy group may be bonded to an aryl group via a divalent organic group, for example, 4-
(4-carboxyphenoxy)phenyl group, 4-
Examples include (2-carboxyethyl)phenyl group, 3-(carboxymethylamino)phenyl group, and 4-(2-carboxyethoxy)phenyl group. As the heterocyclic group represented by R, for example, 2
-(6-carboxy)benzthiazolyl group, 2-
(6-carboxy)benzoxazolyl group and the like can be mentioned. The methine group represented by L is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, tert-butyl group, etc.) or
It may be substituted with an aryl group (eg, phenyl group, tolyl group, etc.). Typical specific examples of the oxonol dye represented by the general formula () are shown below, but the dye according to the present invention is not limited thereto. Exemplary dye The oxonol dye represented by the general formula () is a 3-cyano dye represented by the following general formula ().
5-pyrazolo body and the following general formula (-a), (
It can be synthesized by reacting a compound represented by -b), (-c) or (-d) in the presence of a base. General formula () General formula (-a) General formula (-b) HC(OR') ₃ General formula (-c) General formula (-d) In the formula, R, L and n represent the same meanings as in the above general formula (), and G is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom)
Alternatively, it represents a monovalent organic group, trifluoromethyl group, ethoxycarbonyl group, etc. X represents an anion (for example, chloride, bromide, iodide, perchlorate, P-toluenesulfonate, methylsulfonate, ethylsulfonate, etc.), and m represents 0 or 1.
R' represents a methyl group or an ethyl group. Further, as the base to be present, pyridine, piperidine, triethylamine, triethanolamine, morpholine, ammonia, etc. are used. Solvents for the compounds include alcohols (e.g., methanol, ethanol, etc.), ethylene glycol, ethylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl alcohol, etc.), acetonitrile, dimethyl sulfoxide, amides ( For example, dimethylformamide, dimethylacetamide, acetamide, etc.) are used. The reaction is suitably carried out at a temperature from 0°C to the boiling point of the solvent used, and the reaction reagent 3-cyano-5-pyrazolone represented by the general formula (-a ), (-b), (-
It is appropriate to use about twice the molar amount of the compound represented by c) or (-d). Also, 3-cyano-5 represented by the general formula ()
-Pyrazolone compounds can be synthesized using the production method described in British Patent No. 585,780. Synthesis of the oxonol dye of the present invention will be specifically explained below by showing synthesis examples. Synthesis Example 1 (Synthesis of Exemplary Dye (1)) 1-(4'-carboxyphenyl)-3-cyano-
3.4 g of 5-pyrazolone and 3.4 g of ethyl orthoformate were placed in 50 ml of acetic anhydride, heated, and then 3.1 g of potassium acetate was added and reacted at 100° C. for 30 minutes. After cooling, the precipitated dye was filtered out, washed with acetone, then methanol, and dried.
g dye was obtained. The λ _nax of an aqueous solution of this dye is 476n
It was m. Synthesis Example 2 (Synthesis of Exemplary Dye (6)) 1-(4'-carboxyphenyl)-3-cyano-
11.5 g of 5-pyrazolone and 5.6 g of malondialdehyde dianyl were placed in 200 ml of ethanol, and 12.6 g of triethylamine was added, and the mixture was heated under reflux.
The reaction was allowed to proceed for 1 hour. Next, 9.8 g of potassium acetate dissolved in 100 ml of methanol was added and refluxed for another 5 minutes. After cooling, the precipitated dye was collected by filtration, washed with acetone, then washed with methanol and dried.
11.2 g of dye was obtained. λ _nax of the aqueous solution of this dye
was 557 nm. Synthesis Example 3 (Synthesis of Exemplary Dye (13)) 1-(4'-carboxyphenyl)-3-cyano-
Add 9.2 g of 5-pyrazolone and 5.7 g of glutacondialdehyde dianyl hydrochloride to 100 ml of dimethyl formaldehyde, and add triethylamine.
6.1 g was added and stirred at room temperature for 4 hours. next,
5.9 g of potassium acetate dissolved in 150 ml of methanol was added and stirred. The precipitated dye crystals were collected by filtration, washed with acetone, then methanol, and dried to obtain 8.2 g of dye. The λ _nax of the aqueous solution of this dye was 644 nm. The oxonol dye according to the present invention is distinguished from known oxonol dyes by having a cyano group at the 3-position of the 5-pyrazolone ring and a carboxyl group at the 1-position substituent. Further, the oxonol dye according to the present invention has good absorption spectrum characteristics, and is characterized in that it is decolorized and completely eluted from the photographic material during photographic processing. Usually, photographic processing is carried out under alkaline conditions for a short period of time, and in order for the dye to completely dissolve from the photographic material during the photographic processing, especially from the photographic material coated in multiple layers, it is necessary to A water solubilizing group is required in the molecular structure of In addition, dyes can be easily incorporated into photographic materials by simply adding an aqueous coating solution to the coating solution. In the case of non-aqueous dyes, residual dyes that are once decolored during the development process will be slightly restored in color during the next processing step or during storage over time, resulting in staining. In addition, in order to incorporate such dyes into photographic materials,
It must be dissolved in an organic solvent such as methanol or dimethylformamide and emulsified and dispersed, which is undesirable in terms of workability and toxicity. The oxonol dyes according to the invention are therefore the non-aqueous dyes mentioned in German Patent No. 1961866 (German Patent No.
It is essentially different from Exemplified Dye 7) in the specification of No. 1961866. In the photographic material of the present invention, the oxonol dye represented by the above general formula can be incorporated into a silver halide photographic emulsion and used as an anti-irradiation dye, or can be incorporated into a non-photosensitive hydrophilic colloid layer. It can also be used as a filter dye or an antihalation 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. Generally, a dye or an organic/inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, and the solution is added to a coating solution and coated by a known method to incorporate the coating into the photographic material. I can do it. The content of these dyes varies depending on the purpose of use, but is generally applied in an amount of 1 to 800 mg per ^square meter of area on the photographic material. Supports in the photographic material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate,
For example, there are polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin coated papers, polypropylene synthetic papers, glass plates, metals, etc., and the support values for each of them depend on the intended use of the photographic material. , is selected as appropriate. Hydrophilic colloids in the photographic material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid;
Examples include synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, and cellulose derivatives such as carboxymethyl cellulose, and these may be used alone or in combination. The silver halide emulsion used in the photographic material of the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., which are commonly used in silver halide photographic emulsions. Anything is included. The silver halide emulsion used in the photographic material of the present invention can be produced by various manufacturing methods including the usual manufacturing method.
For example, the method described in Japanese Patent Publication No. 46-7772, or the method described in U.S. Pat. It can be produced by any production method, such as a so-called compound emulsion production method, in which an emulsion of grains is formed and then at least a portion of the grains is converted into silver bromide salt or silver iodobromide salt. This silver halide emulsion may contain chemical sensitizers such as sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, active or inactive selenium sensitizers, potassium chloride sensitizers, etc. Gold compounds such as aurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride, etc., palladium compounds such as ammonium chloroparadate, sodium chloropalladite, etc., potassium chloroplatinate, etc. Noble metal sensitizers such as platinium compounds, ruthenium compounds, rhodium compounds, iridium compounds, etc. or combinations of such sensitizers can be used for sensitization. In addition to chemical sensitization, this emulsion can also be reduced sensitized with a reducing agent, such as triazoles,
imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, admium compounds,
It can be stabilized with mercaptans or a mixture thereof, and can also contain a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound. The photographic emulsion used in the photographic material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary. Various sensitizing dyes can be used, such as cyanine dyes, merocyanine dyes, complex cyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, and streptocyanine dyes. One type of dye or a combination of two or more types can be used. In the photographic material of the present invention, glycerin, 1,
Dihydroxy alkanes such as 5-pentanediol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, wetting agents such as water-dispersible particulate polymer compounds obtained by emulsion polymerization, plasticity and film property improvers, etc. It can also contain active substances such as aldehyde compounds, N-methylol compounds such as N,N'-dimethylol urea, mucohalogen acids, divinyl sulfones, and 2,4-dichloro-6-hydroxy-S-triazine. Hardeners such as halogen compounds, dioxane derivatives, divinyl ketones, isocyanates, carbodiimides, etc., and interfaces with sabonin, polyalkylene glycols, polyalkylene glycol ethers, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, etc. In addition to the activator, photographic additives such as fluorescent brighteners, antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers can be included. In the photographic material of the present invention, in the photographic emulsion layer,
It may contain a color coupler, and the coupler may be either 4-equivalent or 2-equivalent,
It may be a colored coupler for masking or a coupler that releases a development inhibitor. As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based couplers, as magenta-forming couplers, pyrazolone-based compounds, and as cyan-forming couplers, phenolic or naphthol-based compounds are usually advantageously used. Further, the photographic material of the present invention can have any layer structure that can be taken by ordinary photographic materials. Next, the present invention will be specifically 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,
To this, 5 ml of water containing 2.0 x 10 ^-4 mol of exemplary dye (6) according to the present invention was added, and then a 10% sabonin aqueous solution was added.
1.25 ml and 0.75 ml of 1% formalin solution were added, and water was added to bring the total volume to 50 ml. This dye solution was applied onto an acetyl cellulose support and dried to obtain a sample [1]. Moreover, instead of the dye according to the present invention,
Sample [2] was prepared using the following known dye A. In preparing sample [2], 2.0× of known dye A was used.
5 ml of a dimethylformamide solution containing 10 ^-4 mol was used, but when added to an aqueous gelatin solution, it became an emulsion and was emulsified and dispersed. Known dye A (dye described in German patent no. 1961866) Samples [1] and [2] were immersed in an aqueous sodium hydroxide solution (PH=10) at 30°C for 5 minutes with stirring, washed with water for 30 seconds, and dried. The visible spectrum of each test after immersion was measured, 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] In addition, samples [1] and [2] were immersed in a developer having the composition shown below at 30°C for 1 minute, then immersed in a 2.5% acetic acid aqueous solution for 15 seconds, and washed with water for 20 seconds.
Dry. When each sample was left at room temperature for one month, sample [2] had pale pink staining, but sample [1] had no contamination at all. Composition of developer Sodium sulfite (anhydrous) Sodium hydroquinone carbonate (monohydrate) Potassium bromide 3.0g 45.0g 12.0g 80.0g 2.0g Add water to make 1. It was found that the dye according to the present invention is easily eluted from the gelatin layer and does not cause recolor staining during storage like the known dye A. Example 2 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
To this was added 5 ml of water containing 2.0 x 10 ^-4 mol each of exemplary dyes (1), (6) and (13) according to the present invention, and further 1.25 ml of 10% saponin aqueous solution and 0.75 ml of 1% formalin solution. was added, and water was added to bring the total volume to 50 ml. This dye solution was applied onto an acetylcellulose support and dried to obtain samples [3], [4], and [5]. Moreover, instead of the dye according to the present invention,
Comparative samples [6], [7] and [8] were prepared in the same manner using the following known dyes B, C and D. Known dyes B, C and D

[Table] Each of these samples was immersed in the developer used in Example 1 at 30° C. for 1 minute, washed with water for 20 seconds, and then dried. The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the absorbance at the maximum absorption 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 in the developer, and E ₄ is the absorbance after immersion in the developer.)

[Table] As is clear from Table 2, it was found that the dye according to the present invention has a preferable spectral absorption maximum and exhibits excellent decolorizing properties compared to known dyes. In addition, in the samples containing known dyes (B, C, and D), the treatment solution was slightly colored by the eluted dye, but with the dye according to the present invention, no such colored contamination was observed. Example 3 On a support made of polyethylene-coated paper, the following layers were sequentially placed from the support side to create a color photographic material (sample

[9]). 1st layer...yellow coupler; α-pivalyl-α-(1
-benzyl-2-phenyl-3,5-dioxotriazolidin-4-yl)-2'-chloro-
5′-[γ-(2,4-di-t-amylphenoxybutyramide acetanilide, hardener (dichlortriazine) and surfactant (saponin)
A blue-sensitive silver halide emulsion layer (silver chlorobromide emulsion containing 90 mol% silver bromide, sensitized using a sensitizing dye) containing a coating silver amount of 3.5 mg/100
cm ² . Second layer: A gelatin layer (intermediate layer) was provided. 3rd layer...magenta coupler; 1-(2,4,6-
Green containing trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone, hardener (dichlorotriazine) and surfactant (saponin) A sensitive silver halide emulsion layer (silver chlorobromide emulsion containing 80% silver bromide, sensitized using a sensitizing dye) was provided so that the amount of coated silver was 4.5 mg/100 cm ² . Fourth layer: A gelatin layer (intermediate layer) was provided. 5th layer...Cyan coupler; 2,4-dichloro-3
-Methyl-6-(2,4-di-t-aminophenoxyacetamide) A red-sensitive silver halide emulsion layer containing a phenol hardener (dichlortriazine) and a surfactant (saponin) (75
A silver chlorobromide emulsion containing mol% silver bromide, sensitized using a sensitizing dye. ) coated silver amount is 2.0
mg/100cm ² . Sixth layer: A gelatin layer (protective layer) was provided. Furthermore, a green-sensitive emulsion (third layer coating solution) was prepared by adding 200 ml of a 2% aqueous solution of the exemplary dye (9) according to the present invention or the known dye E per 1 kg of the emulsion.

Sample [10] and sample [11] were prepared in the same manner as [9]. Known dye E These samples

After exposing [9], [10] and [11], they were processed according to the following processing steps. [Processing process (31℃)] Processing time 1 Color development 3 minutes 2 Bleach-fixing 1 minute 3 Water washing 2 minutes 4 Stabilization 1 minute 5 Water washing 2 minutes The composition of the processing solution used in each step is as follows. be. [Composition of color developer] 4-amino-3-methyl-N-ethyl-N-(β
-Hydroxyethyl)aniline sulfate 4.8g Anhydrous sodium sulfite 4.0g Hydroxyalumine 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-fixing] 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. [Fixer composition] 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] As is clear from Table 3, in the samples containing the dye according to the present invention, no color contamination due to residual color of the dye was observed, as was the case with the samples containing the known samples. We also compared the sensitivity of each sample and found that
It was found that the samples according to the present invention had very little adverse effect on the emulsion. Example 4 80 ml of a 1% aqueous solution of sample (8) according to the present invention was added to 350 ml of 10% gelatin, and then a 1% formalin solution was added.
Add 10ml and 12.5ml of 10% saponin aqueous solution,
Water was added to bring the total volume to 500 ml, and a gelatin solution of the dye was prepared. Coating the dye coating solution on the back side of a cellulose acetate film support coated with an orthomatically spectrally sensitized silver chlorobromide emulsion (containing 80 moles of silver bromide) layer and a protective gelatin layer;
Sample [12] was prepared. In place of the exemplified dye (8), the dye (11) according to the present invention
Samples [13] and [14] were prepared in the same manner using known dye F. Known dye F After each of these samples [12], [13] and [14] were exposed, they were developed for 2 minutes at 27°C using a developer having the composition shown below, followed by fixing, washing with water and drying in a conventional manner. Composition of developer: Hydroquinone 15g Formaldehyde sodium bisulfite adduct
60g Sodium sulfite 2g Sodium carbonate monohydrate 85g Boric acid 9g Add water to make 1. (Add sodium hydroxide so that the pH becomes 9.90.) After treatment, the sample [14] containing the known dye exhibited a pale pink color and residual color staining due to the dye was observed, but the dye according to the present invention No dye contamination was observed in samples [12] and [13] using . Furthermore, the photographic material had an excellent antihalation effect without causing any adverse effects such as fogging or desensitization on photographic emulsions.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing an oxonol dye represented by the following general formula (). General formula () [In the formula, R represents an aryl group or a heterocyclic group having at least one carboxy group. However, it does not have a sulfo group. L represents a methine group, and n represents 0, 1 or 2. ]