JPH0141976B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to photographic materials. In particular, it relates to photographic materials containing photographically useful compounds. In photographic light-sensitive materials, blocking the photographically useful compounds used therein and incorporating them into the photographic light-sensitive materials as having a function different from their original function has various usefulness. When the photographically useful compound is a dye, if the dye is contained in the photographic light-sensitive material as it is, the following disadvantages arise. That is, systems that contain a dye during exposure include, for example, silver dye bleaching photography and dye diffusion transfer photography, but the dye-providing substance may be in the same layer as a silver halide emulsion having a corresponding photosensitive spectral region or in a silver halide emulsion. When located in the adjacent layer on the exposed side of the silver halide emulsion layer, the dye moiety acts as an undesirable filter, absorbing some of the light that would otherwise reach the silver halide emulsion layer, thereby causing a reduction in sensitivity (see below). , called the filter effect) occurs. In such cases, such a filtering effect by the dye can be eliminated by blocking the dye with a blocking group that is removed by an alkali during development and shifting its spectral absorption to the short wavelength side or to the long wavelength side. Therefore, there is an advantage that the silver halide emulsion and the dye donor can be contained in the same layer without impairing sensitivity. Furthermore, if the photographically useful substance is a developer, if the developer is blocked with a blocking group that is removed by an alkali during development and placed in the photographic light-sensitive material, development can basically be carried out using only an aqueous alkaline solution. This has the advantage of making it easier to prepare the developer and lowering the BOD of waste fluid. Further, there is an advantage that if the fogging agent is blocked and placed directly into the positive photosensitive material, fogging will be prevented and development can be carried out stably. Furthermore, if a material that releases a development inhibitor or antifogging agent after a certain period of time is added to the photographic light-sensitive material, there is an advantage that development can be carried out stably without excessive development. There are already several known techniques for blocking photographically useful compounds that have the above-mentioned advantages. For example, an acyl group (e.g.
CF ₃ CO- group (e.g., JP-A-52-34731 and JP-A-52-155530)

[Formula] Group (for example, JP-A-51 −42536),

[Formula] group (e.g., U.S. Pat. No. 4,060,418), PhSO ₂ CH ₂ CH ₂ - group (e.g., JP-A-55-138745), amide group (e.g., JP-A-55-53329), etc. There are techniques to protect useful compounds. Some of these blocking groups are hydrolyzed by normal hydrolysis under alkaline conditions, some are cleaved by intramolecular nucleophilic substitution reactions (for example, JP-A-55-53330), and some are cleaved by electron transfer into quinone- Those that form a methide structure and cleave (for example, US Pat. No. 3,674,478) are already known. Although these prior art techniques are effective and useful as blocking techniques for general photographically useful compounds, they are insufficient as protecting groups for amino groups (particularly basic amino groups) because of their slow cleavage rates. Therefore, an object of the present invention is to provide a photographic light-sensitive material containing a photographically useful compound whose amino groups are blocked and which is rapidly cleaved by an alkali. The object of the present invention has been achieved by a photographic light-sensitive material containing a photographically useful compound in which the amino group of the photographically useful compound is blocked by a blocking group represented by the following general formula. general formula [In the formula, R is a halogen atom, an alkyl group, an alkoxyl group, a nitro group, a cyano group, a sulfo group, a carboxy group, an acylamido group, a sulfonamide group,
represents a sulfamoyl group, a carbamoyl group, or an amino group (these acylamido groups, sulfonamide groups, sulfamoyl groups, carbamoyl groups, and amino groups may be substituted with an alkyl group or an aryl group), and n is 0 to 2. Represents an integer. ] In the general formula R, the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, etc., and the alkoxyl group is represented by -OR ₁ and R ₁ represents an alkyl group. In the present invention, R is preferably a halogen atom, a nitro group, a cyano group, an acylamido group, a sulfonamide group, a sulfamoyl group, or a dialkylamino group, and n is preferably 0 or 1. Photographically useful compounds used in the present invention include:
Anthraquinone dyes (e.g. described in JP-A No. 53-123128), azo dyes (e.g. described in JP-A-53-4544), azomethine dyes, dyes capable of forming metal complexes (e.g. described in JP-A-53-35533) ), developers (e.g. aminophenols, phenidones, P-phenylenediamines), fogging agents (e.g. hydrazines, JP-A-53-3326), development accelerators, electron donors, etc. Compounds that exhibit antifogging and development inhibitory effects (e.g. benzimidazoles,
benztriazoles), etc. The N-methylol phthalimide group, which is the blocking group of the present invention, has been described by GHL Nefkens et al.
Chim, 82941 (1963)) as a protecting group for carboxylic acids. In contrast, the blocking group of the present invention is used as a protecting group for photographically useful substances. The photographically useful compound blocked with the blocking group of the present invention is stable for a long period of time even when included in a photographic light-sensitive material, and is quickly cleaved in an alkali to return to the original photographically useful compound. I found out. In particular, it was effective as a protecting group for photographically useful compounds having a basic NH group in view of storage stability. Furthermore, the blocking group of the present invention was effective when the photographically useful compound was a developer. The preferred content of the compound of the present invention varies depending on the photographically useful group, but when the photographically useful group is a developer, it is 0.1 to 10 mol per mol of silver;
Preferably it is 0.3 to 3 mol. Next, specific examples of the blocked photographically useful compound of the present invention (hereinafter referred to as the compound of the present invention) will be shown, but the compound of the present invention is not limited thereto. It is well known that the N-methylol phthalimide derivative, which is an intermediate for the blocking group used in these compounds, is synthesized from the corresponding phthalimide and formalin. The compound of the present invention is
It can be obtained by reacting this methylol form with the corresponding isocyanate of a photographically useful group, or by forming a chloroformic acid derivative from this methylol form and phosgene, and condensing this derivative with an amino group of a photographically useful compound. . A synthesis example will be shown below. Synthesis mainly involves obtaining N-methylol derivatives from various phthalimide derivatives and formalin, reacting this with phosgene to produce chloroformic acid derivatives, and reacting with amines, and reacting N-methylol derivatives with various isocyanates. achieved by. (1) Synthesis of compound 12 (1-1) Synthesis of intermediate N-methylol phthalimide 29.4 g (0.2 mol) of phthalimide was dissolved in 120 g of water.
ml of 20 ml of formalin aqueous solution (37
%) and heated to form a homogeneous solution. After cooling, filter the precipitated crystals and wash with water.mp141
31.2 g of white crystals of ~142°C were obtained. Yield 95% (1-2) Intermediate Synthesis of chloroformic acid N-methylol phthalimide ester 1.63 g of the above N-methylol phthalimide
(0.01 mol) was dissolved in 20 ml of THF, 20 ml of a toluene solution of phosgene (containing 10%) was added, and the mixture was left at room temperature overnight. The solvent was then distilled off under reduced pressure at a temperature below 40°C. (1-3) Synthesis of compound 12 2.73g (0.01 mol) of 4-amino-3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)aniline was mixed with 100% ethyl acetate.
ml and added 8 ml of pyridine. To this was added the above chloroformic acid N-methylol phthalimide ester dissolved in a small amount of ethyl acetate with stirring under ice cooling. After further stirring at room temperature for 3 hours, the reaction solution was mixed with dilute acetic acid (10 ml of glacial acetic acid).
Washed twice with 100 ml of water, then washed with water, and then washed with saline. The solution was then concentrated, separated by column chromatography, and crystallized from ethanol. 0.60 g of white crystals with mp 144.5-145.5°C were obtained. Yield 13% (2) Synthesis of compound 14 (2-1) Synthesis of intermediate 4-nitrophthalimide 40 g of phthalimide was added to a mixed solution of 210 ml of concentrated sulfuric acid and 35 ml of concentrated nitric acid while cooling to below 10°C. After being left at room temperature for 2 days, it was poured into ice water, and the resulting precipitate was filtered and washed with water to obtain a crude product. This product was recrystallized from 300 ml of ethanol to obtain 23.65 g of 4-nitrophthalamide with a mp of 194 to 196°C. Yield 45.3% (2-2) Synthesis of intermediate 4-nitro-N-methylol phthalimide 1.92 g of the above 4-nitrophthalimide
(0.010 mol) was dissolved in 10 ml of dimethylformamide, 1 ml of formalin aqueous solution (37%) was added, and the mixture was heated under reflux for 10 minutes. After cooling, add 50ml of water, filter the precipitate, and wash with water.
1.70 g of white crystals with a mp of 148-153°C were obtained. Yield 80% (2-3) Intermediate Synthesis of chloroformic acid-4-nitro-N-methylol phthalimide ester Dissolve 2.2 g (0.105 mol) of the above 4-nitro-N-methylol phthalimide in 20 ml of THF, and prepare a toluene solution of phosgene. (Contains 10%) 20
ml and left overnight at room temperature. Then 40℃
The solvent was distilled off under reduced pressure. (2-4) Synthesis of compound 14 2.73 g (0.01 mol) of 4-amino-3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)aniline was mixed with ethyl acetate 100
ml, added 8 ml of pyridine, and cooled.
This is added to the above chloroformic acid-4-nitro-N-
Methylolphthalimide ester dissolved in a small amount of ethyl acetate was added, and the mixture was further stirred for 3 hours at room temperature. Dilute the reaction solution with dilute acetic acid (glacial acetic acid 10ml water)
After washing with 100 ml of water twice, washing with water, washing with brine, and concentrating the solvent, it was separated by column chromatography and crystallized from ethanol.
0.65 g of red crystals with a mp of 169-170°C were obtained.
Yield: 12.5% When using the compound of the present invention, known photography-related techniques can be used as they are, although this varies depending on the photographically useful compound to be blocked. For example, when used as a dye-providing substance in dye diffusion transfer photography, it is dispersed in a hydrophilic colloid and incorporated into a photographic light-sensitive material in the same layer as silver halide or in an adjacent layer. When the photographically useful compound is a development inhibitor, it can be included in any layer in the light-sensitive material, but when used in dye diffusion transfer photography, it is coated on a separate support in addition to the above and processed. Sometimes they can be superimposed to exert their effects on photographic materials. When the photographically useful compound has a reducing power (for example, aminophenols) that can reduce the oxidized form of other developers (for example, phenidones), a ballast group is added to at least one of the protecting group or the reagent. Additionally, a scavenger precursor for diffusion transfer photography (for example, Japanese Patent Application Laid-open No. 118831/1983)
It can also be used as When the photographically useful compound to be blocked is an auxiliary developer, a black-and-white developer, a color developer, a fogging agent, a development accelerator, etc., it is dispersed in a hydrophilic colloid and used for ordinary color and black-and-white photographic materials and diffusion transfer photographs. It can be contained in any layer of the photosensitive material. As the hydrophilic colloid, those known as photographic binders such as gelatin can be used. Furthermore, latex may be added. The method for incorporating the compound of the present invention into a hydrophilic colloid aqueous solution is as follows. That is, if the compound itself is water-soluble, the aqueous solvent can be added to the hydrophilic colloid; if the compound is poorly soluble in water (hydrophobic), latex dispersion methods (e.g., U.S. Pat. No. 4199363, Japanese Patent Application Publication No. 1973-
74538) and oil droplet dispersion in water are effective. As the oil-in-water emulsion dispersion method, methods conventionally used for dispersing hydrophobic additives such as couplers can be used. The oils include tricresyl phosphate, trihexyl phosphate, dioctyl butyl phosphate, dibutyl phthalate, lauryl amide, etc. To disperse the oil in the aqueous phase, activating agents well known in the art are used. , such as carboxylic acid, phosphoric acid, sulfuric acid ester,
anionic activators containing acidic groups such as phosphate esters,
Nonionic activators and cationic activators can be used. Other methods for dispersing the compound of the present invention include dissolving it in a water-miscible solvent (e.g., acetone, dimethylformamide, methanol, etc.) in the presence of an activator, pouring it into water, and finely dispersing it (e.g., There are direct dispersion methods using a colloid mill, etc.). When the photographically useful compound is a reducing agent such as a black and white developer, a color developer, or a fogging agent, the coating solution containing the compound of the present invention may contain known photographic antioxidants or stabilizers, such as hydroquinone derivatives, ascorbic acid, etc. Reductones, hydroxyamines, active methylene compounds, etc. can be added. When the photographically useful compound is a color developer (p-phenylenediamines), color photographic materials containing the compound of the present invention can in principle be color-developed using only an alkaline aqueous solution (activator solution).
The pH of the activator bath is preferably in the range of approximately 10 to 14, which is slightly higher than that of conventional developers. Since the activator solution is a conventional color developer except for the color developing agent, known additives for color developers can be used as they are.
For example, as alkaline agents and buffering agents, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium or potassium phosphate, potassium metaborate, borax, etc. are used. In addition, inorganic salts for adjusting ionic strength, inorganic halide compounds (e.g., sodium bromide, ammonium bromide, potassium iodide, etc.) and organic antifoggants (e.g., 6-nitrobenzimitazole, diamino phenazine, mercaptobenzimidazole, 5-methylbenztriazole,
thiouracil, etc.) may be added. Furthermore, various organic solvents such as benzyl alcohol, ethylene glycol, hexylene glycol, dimethylformamide, ethanol, methanol, methylcellosolve, etc. are used to promote the dissolution and reaction of the dispersed compound of the present invention in the activator liquid. May be added. Additionally, a phase transfer catalyst (for example, crown ethers, quaternary amines such as cecyltrimethylammonium salt, trimethylbenzylammonium salt, etc.) may be added, although this is particularly effective when dispersed in oil droplets. This may be included in the photographic material. Further, a black and white developer such as phenidone may be added to the activator solution to speed up the development, and may be included in the photographic light-sensitive material. Since the activator treatment replaces the conventional color development process, conventionally known techniques can be used for the subsequent bleaching and fixing processes. Example 1 The following experiment shows that the compound of the present invention is effective as a protecting group for amino groups in photographically useful substances. PH12 buffer solution (0.02M-NaOH-NaHCO ₃ ) 25ml Methanol solution of sample (1 x 10 ^-5 mol) 10ml Methanol solution of cyan coupler (2-carboethoxy-1-naphthol) (2 x 10 ^-5 mol) 10 ml were mixed and stirred at room temperature for 1 minute. Next, 5 ml of an aqueous solution of red blood salt (4 x 10 ^-5 mol) was added, and 1
Stir for a minute. Add to this 30 ml of ethyl acetate and 30 ml of water.
ml was added, stirred for 30 seconds, and then allowed to stand still. 5 ml of the ethyl acetate layer was taken, diluted 10 times with methanol, and the absorption of the cyan portion was measured using a spectrophotometer. By creating a calibration curve for a dye produced with a phenylenediamine compound in advance and comparing it with that,
The rate at which the protecting groups were removed (decomposition rate) could be measured.

【table】

Comparison with similar compounds 1 and 2 shows that the compound of the present invention is rapidly decomposed under alkali. Example 2 A compound of the present invention was incorporated into a practical photographic system and evaluated. A green-sensitive silver halide emulsion layer containing a magenta coupler (a) was provided on a polyethylene-laminated paper support, and a gelatin protective layer was provided thereon.
The coating amounts of coupler, silver halide, gelatin and other major additives are as follows. Reference sample (green sensitive layer) Silver chloride 0.3g/m ³ Tricresyl phosphate 0.4g/m ³ Magenta coupler (a) 0.4g/m ³ Ossein gelatin 2.5g/m ³ Phenidone derivative (b) 0.05g/m ³ Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont) 0.006 g/m ³ Hardener (c) 0.04 g/m ³ (gelatin protective layer) Ossein gelatin 1.1 g/m ³ Alkanol B 0.004 g/m ³ Hardener (c) 0.02g/m ³ magenta coupler (a) Phenidone derivative (b) Hardener (C) Sample A 0.50 g/m ³ of the following compound (comparative compound 2) dissolved in a small amount of dimethylformamide was added to an emulsion coating solution having the same composition as the reference sample. Comparative compound 2 The same gelatin protective layer as the reference sample was used. Sample B (Green Sensitive Layer) To an emulsion coating solution having the same composition as the reference sample, 0.45 g/m ³ of the following compound (comparative compound 3) was dissolved in a small amount of dimethylformamide and added. Comparative compound 3 The same gelatin protective layer as the reference sample was used. Sample C (green-sensitive layer) To an emulsion coating solution having the same composition as the reference sample, 0.50 g/m ³ of the following compound (compound 12 of the present invention) dissolved in a small amount of dimethylformamide was added. compound 12 The same gelatin protective layer as the reference sample was used. The above sample ABC was exposed using a step wedge and a sensitometer (500 CMS, 0.5 seconds).
After giving , the following process was performed. Activator bath 45°C 2 minutes Bleach-fix bath 40°C 1 minute Water washing 20°C 4 minutes Here, the composition of each treatment solution is as follows. <Activator solution> Benzyl alcohol 12ml Potassium carbonate 20g Potassium bromide 0.1g Ethanol 100ml Add water to make 1 pH 11.8 <Bleach-fix solution> Iron ammonium ethylenediaminetetraacetate 61g Diammonium ethylenediaminetetraacetate 5g Ammonium thiosulfate 13.3g Anhydrous Sodium sulfite 2.7g Add ammonia water and water to make 1 PH7.0 The results of the obtained sample ABC immediately after application and the results of the forced deterioration storage test (Note) are shown in Table 1 below.

[Table] * Significant staining.
Note: A forced aging storage test is a test in which the sample is exposed to temperature immediately after application.
After being left in an atmosphere of 50°C and 80% humidity for 48 hours, it was exposed and developed. As is clear from Table 1, using the comparative compounds
It can be seen that compared to AB, photographic material C using the compound of the present invention has better color development, less fog, and less staining due to storage, and is therefore superior. An example of using the compound of the present invention as a protecting group for a dye will be described below. The experimental method is JP-A-54-34731.
The method described in Japanese Patent Application No. 2003-100001 (Shifted dye developer) was followed. Example 3 Photosensitive element 1 was prepared by sequentially applying each of the following layers onto a transparent gelatin-subbed cellulose triacetate film.
was created. (1) Yellow dye developer layer 1 part of Exemplified Compound (1) was dissolved in 1 part of N,N-diethyl laurylamide and 3 parts of ethyl acetate, and this was added to an aqueous gelatin solution containing dispersant Alkanol B to emulsify and disperse. and applied. The amount of coating is shown below. Exemplary compound (1) 1.4 g/m ³ N,N-diethyl laurylamide 1.4 g/m ³ Gelatin 2.5 g/m ³ (2) Blue-sensitive emulsion layer Silver iodobromide emulsion 2.5 g/m ³ in terms of silver Gelatin 2.8 g/m ³ (3) Protective layer P-Tolylhydroquinone 0.22 g/m ³ Dibutyl phthalate 0.22 g/m ³ Gelatin 0.5 g/m ³ The image-receiving element was prepared by sequentially coating the following layers on baryta paper. (1) Neutralization layer A 5% acetone solution of half-butyl ester of copolymer of maleic anhydride and ethylene was applied. The dry film thickness was 20μ. (2) Isolation layer An aqueous solution of hydroxypropyl cellulose was applied. The dry film thickness was 8μ. (3) Image-receiving layer Poly-4-vinylipyridine, polyvinyl alcohol, and 1-phenyl-5-mercaptotetrazole were dissolved in water and applied with a small amount of glacial acetic acid. Poly-4-vinylpyridine 3.0g/m ³ Polyvinyl alcohol 6.0g/m ³ 1-phenyl-5-mercaptotetrazole
0.15 g/m ³ Similarly, in place of the exemplified compound (1) in the yellow dye developer layer of the photosensitive element, the following comparative compound (A) was used.
A photosensitive element was prepared using Comparative Compound (B). The light-sensitive element and the image-receiving element are wedge-exposed with blue light from the emulsion layer side and from the base side, and then overlapped with the image-receiving element, and the following alkaline processing liquid is spread between the light-sensitive element and the image-receiving element to a thickness of 20 μm. did. Alkaline treatment liquid composition Water 100ml Potassium hydroxide 11.2g Carboxymethylcellulose sodium salt 3.5g Benzotriazole 2.0g 1-phenethyl-2-picolinium bromide
2.0 g After 1 minute, the image receiving element was peeled off from the photosensitive element, and the maximum density (Dmax) and minimum density (Dmin) of the yellow image obtained on the image receiving element were measured using a blue filter.

【table】

[Table] Regarding the light-sensitive elements, the minimum density was significantly increased when exposed from the support side compared to when exposed from the emulsion layer side, indicating that comparative compound (A) caused significant desensitization. I understand. or,
It can be seen that the maximum density of the photosensitive element is low, that is, it takes too long to recover the color. On the other hand, photosensitive elements using the compounds of the present invention exhibit less desensitization and rapid color recovery.

Claims (1)

[Scope of Claims] 1. A photographic light-sensitive material, characterized in that it contains a photographically useful compound in which the amino group of the photographically useful compound having an amino group is blocked by a blocking group represented by the following general formula. general formula [In the formula, R is a halogen atom, an alkyl group, an alkoxyl group, a nitro group, a cyano group, a sulfo group, a carboxy group, an acylamido group, a sulfonamide group,
It represents a sulfamoyl group, an amino group or a carbamoyl group, and n represents an integer of 0 to 2. ]