JPS6365139B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material containing a 3-pyrazolidone compound precursor. Generally, silver halide photographic materials are exposed to light and then subjected to a development process to form an image. At that time, it is well known that 3-pyrazolidones are added to the processing solution for the purpose of promoting development. It has been difficult to incorporate and use 3-pyrazolidones in photographic light-sensitive materials because 3-pyrazolidones are easily diffused and 3-pyrazolidones are susceptible to air oxidation. That is, during storage of photographic light-sensitive materials, 3-pyrazolidones may increase fog due to diffusion to the silver halide surface, may themselves be oxidized and lose their effectiveness, or oxidized products may act on silver halide and desensitize it. This is because In order to solve these problems, a precursor that can be decomposed by an alkali has been considered. The advantage of this compound is that it does not act on silver halide and does not undergo air oxidation before the development process, and also that the release timing of the necessary compound during development can be adjusted. Generally, an alkaline processing solution is used, so the difference in hydroxyl ion concentration during storage of raw film and during processing can be utilized to determine the release speed required during processing of 3-pyrazolidones and storage of raw film. The idea was to achieve both stability over time. The difference in hydroxyl ion concentration between the storage of a photographic material and the time of development is not so large in the case of commonly used processing solutions (PH8-12). Since 3-pyrazolidone used as a development accelerator is most effective when released immediately after the start of the development process, it is desirable that the release speed be as high as possible. In such cases, the basic problem is to balance the release speed during development processing with the stability during storage of the photographic material. Known compounds for this problem, e.g.
The compounds described in No. 4209580, No. 3241967, and No. 4310612 did not necessarily have satisfactory performance, and there was a need for further improvement. With these known compounds, the pH of the developing solution is 13.
Although the above-mentioned light-sensitive materials processed at a fairly high pH exhibit a certain degree of photographic performance, it is necessary to sacrifice the release speed of 3-pyrazolidones during development processing in order to ensure storage stability. The present inventors have made various studies for the purpose of improving the above-mentioned drawbacks, and have found that the compound of the present invention represented by the following general formula [] exhibits excellent photographic performance. General formula [] In the formula, A represents an aliphatic group or an aromatic group,
R ₁ and R ₂ each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms (the substituent is selected from an alkoxy group, a halogen atom, an acyloxy group, an alkoxyacyloxy group, and a carbamoyloxy group). where R ₃ represents a hydrogen atom or an aromatic group, and R ₄ represents an aromatic group. When A represents an aliphatic group, it preferably has 1 to 22 carbon atoms, is substituted or unsubstituted, and is linear or cyclic. It may be either saturated or unsaturated. Preferred substituents are an alkoxy group, a halogen atom, an aryloxy group, an aryl group, and the alkyl group or aryl group may further have a substituent. Specific examples of useful aliphatic groups include: methyl, ethyl, propyl, methoxyethyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, Octyl group, 2-
Ethylhexyl group, benzyl group, dodecyloxypropyl group, dodecyl group, 2-(2,4-di-
tert-amylphenoxy)ethoxy group, 2-chloroethyl group, phenoxyethyl group, 4-acetoxyphenoxyethyl group, and the like. When A or R ₃ represents an aromatic group, and
The aromatic groups represented by R ₄ each preferably represent a phenyl group, and each may be independently substituted or unsubstituted. Substituents include alkoxy groups, halogen atoms, alkyl groups, hydroxyl groups,
It is selected from aliphatic amide groups, aromatic amide groups, sulfonamide groups, amino groups, alkanoyloxy groups, alkoxycarbonyl groups, sulfamoyl groups, and the like. These alkyl group portions or aryl group portions may further have a substituent. Specific examples of useful aromatic groups include: phenyl, 4-methoxyphenyl, 2-
Hydroxyphenyl group, 4-chlorophenyl group,
4-methylphenyl group, 3-methylphenyl group,
4-dodecylphenyl group, 3-butoxyphenyl group, 3-pentadecylphenyl group, 2,4-dichlorophenyl group, 3-methoxyphenyl group, naphthyl group, acetamidophenyl group, methanesulfonamidophenyl group etc. Specific examples of useful R ₁ and R ₂ include: hydrogen atom, methyl group, ethyl group,
These include methoxymethyl group, acetoxymethyl group, chloromethyl group, ethoxymethyl group, pentyl group, tetradecanoyloxymethyl group, phenylcarbamoyloxymethyl group, phenoxycarbonyloxymethyl group, and ethoxycarbonyloxymethyl group. Next, specific examples of the precursor compound of the present invention will be described below. Compound example Next, typical synthesis examples of the precursor compound of the present invention are shown below. Synthesis example (1) Synthesis step of exemplified compound (1) Synthesis of 1,5-diphenyl-3-pyrazolidone 10.1g of sodium methoxide was dissolved in butanol.
Dissolved in 150ml. Heat to 100℃ and add 0.7 g of tert-butylhydroxynone and phenylhydrazine.
Then, 31.1 g of cinnamic acid ethyl ester was added dropwise. The mixture was allowed to react at this temperature for 2 hours, cooled to room temperature, and 16 ml of concentrated hydrochloric acid was added. The reaction mixture was poured into 1 water and extracted with 500 ml of ethyl acetate. The oil layer was washed with water, separated, and the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 17.2 g of 1,5-diphenyl-3-pyrazolidone. The melting point was 161-164°C. Step Synthesis of Exemplified Compound (1) 1,5-diphenyl-3 in 150 ml of chloroform
- 15g pyrazolidone and 10ml triethylamine
were mixed. In this, ethyl chlorocarbonate
7.9g was dropped. After reacting for 1 hour, the mixture was transferred to a separatory funnel and washed with water. After drying the oil layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solution of toluene and hexane to obtain exemplified compound (1).
I got 13g. The melting point was 126-127°C. Synthesis Example (2) Synthesis of Exemplified Compound (18) Exemplified Compound (18) was prepared in the same manner as in Synthesis Example (1) using an equimolar amount of phenyl chlorocarbonate instead of the ethyl chlorocarbonate used in the step. Synthesized. Recrystallization was performed from a mixed solvent of ethyl acetate and hexane, and the melting point was 119-121°C. Synthesis example (3) Synthesis step of exemplified compound (3) Synthesis of 1-(4-chlorophenyl)-5-phenyl-3-pyrazolidone In place of the cinnamic acid ethyl ester used in the step of synthesis example (1), etc. 1-(4-chlorophenyl)-2-propenoid acid ethyl ester was prepared in a similar manner using mol of 3-(4-chlorophenyl)-2-propenoid acid ethyl ester.
-chlorophenyl)-5-phenyl-3-pyrazolidone was synthesized. Recrystallization was performed from a mixed solvent of ethyl acetate and hexane, and the melting point was 164-166°C. Step Synthesis of exemplified compound (3) 1,5-
Equimolar 1-(4-chlorophenyl)-5-phenyl-3- instead of diphenyl-3-pyrazolidone
Synthesis was carried out using pyrazolidone and equimolar amount of methoxyethyl chlorocarbonate in place of ethyl chlorocarbonate. Recrystallization was performed from a mixed solvent of ethyl acetate and hexane, and the melting point was 91-92°C. Synthesis Example (4) Synthesis of Exemplified Compound (8) This was carried out in the same manner as in Synthesis Example (3). However, equimolar amount of isopropyl chlorocarbonate was used instead of methoxyethyl chlorocarbonate used in the step of Synthesis Example (3). Recrystallization was performed from methanol and acetonitrile, and the melting point was 138-140°C. Synthesis Example (5) Synthesis of Exemplified Compound (10) 16.2 g of 1-phenyl-3-pyrazolidone (phenidone) and 11.1 g of toluethylamine were dissolved in 250 ml of chloroform. Add to this a toluene solution containing 30% benzylchlorocarbonate at room temperature.
56.8g was dropped. After stirring at that temperature for 30 minutes,
The mixture was heated to 50°C and reacted for 1 hour. After cooling to room temperature, water was added and the mixture was transferred to a separatory funnel for washing. After drying the oil layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was recrystallized from acetyl to obtain 18.4 g of Exemplified Compound (10). The melting point was 131-135°C. Synthesis example (6) Synthesis step of exemplified compound (14) Synthesis of 1-(4-methylphenyl)-5-phenyl-3-pyrazolidone 10.9 g of 4-methylphenylhydrazine, tert-
A mixed solution of 0.5 g of butylhydroquinone, 26.7 ml of methanol containing 28% sodium methoxide, and 250 ml of butanol was heated and stirred under a nitrogen stream, and methanol was distilled off. 15.2 g of cinnamon acid ethyl ester was added dropwise. Further, the mixture was heated and stirred for 2 hours while distilling off the butanol at normal pressure. The reaction solution was allowed to cool to room temperature, neutralized with an aqueous hydrochloric acid solution, and extracted with ethyl acetate. The oil layer was washed with water and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, it was recrystallized from ethyl acetate to obtain 13.2 g of 1-(4-methylphenyl)-5-phenyl-3-pyrazolidone.
I got it. The melting point was 152.5-153°C. Step Synthesis of Exemplified Compound (14) This was carried out in the same manner as in the step of Synthesis Example (1). However, instead of 1,5-diphenyl-3-pyrazolidone used in Synthesis Example (1), equimolar amount of 1-(4-
methylphenyl)-5-phenyl-3-pyrazolidone was used, and equimolar hexylchlorocarbonate was used instead of ethylchlorocarbonate.
Recrystallization was performed using a mixed solvent of ethyl acetate and hexane, and the melting point was 61-62°C. Synthesis example (7) Synthesis step of exemplified compound (20) Synthesis of 4-methyl-4-tetradecanoyloxymethyl-1-phenyl-3-pyrazolinone 31 g of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolinone , 37 g of myristoyl chloride was mixed with 150 ml of acetonitrile.
After heating under reflux for 8 hours under a nitrogen stream, the mixture was left at room temperature overnight. The resulting crystals were collected and recrystallized with ethanol to obtain 30 g of the desired product. The melting point was 74-74.5°C. Step Synthesis of Exemplified Compound (20) A method similar to the step of Synthesis Example (1) using 4-methyl-4-tetradecanoyloxymethyl-1-phenyl-3-pyrazolinone and butyl chlorocarbonate obtained in step The reaction was carried out by post-treatment. An oily Exemplified Compound (20) was obtained. The compounds of the present invention can be used, for example, in coupler type color photographic materials. A common method for forming color images from color photographic materials is to convert silver halide materials into aromatic primary amines in the presence of color couplers that have the ability to form dyes by reacting with oxidized developing agents. This is a method for obtaining azomethine or indoaniline dyes by developing with a developing agent. This color development method was basically developed by LD Mannes in 1935.
It was invented by & L. Godowsky,
Various improvements have been made since then, and it is currently used in the industry worldwide. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indazolone coupler is mainly used. phenolic couplers, such as phenols and naphthols, are used primarily to form cyan images. Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter, the dye image-forming coupler is added to the silver halide emulsion. Couplers added to the emulsion must be non-diffusible (diffusion resistant) in the emulsion binder matrix. In the internal mold method, the processing process for color photographic materials basically consists of the following three steps. (1) Color development step (2) Bleaching step (3) Fixing step The bleaching step and the fixing step can be performed simultaneously. That is, it is a bleach-fixing process (so-called brix), in which developed silver and undeveloped silver halide are desilvered. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process also includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the shelf life of the image. It accompanies me. For example, a hardening bath is used to prevent excessive softening of the photosensitive film during processing, a stop bath is used to effectively stop the development reaction, an image stabilization bath is used to stabilize the image, and a desorption bath is used to remove the backing layer of the support. Examples include processes such as a membrane bath. In the above-mentioned color photographic light-sensitive materials, the compound of the present invention is generally preferably added to the emulsion as an auxiliary developer for the purpose of accelerating development, together with an internal type color coupler; May be added. The compounds of the invention can also be used in various types of instant photography. For example, U.S. Patent Nos. 3134764, 3173929, 3929848,
A method using a dye developer disclosed in US Pat. No. 3706557, etc., for example, US Pat.
4013635, etc., which releases a diffusible dye. Compounds of the invention may be used, for example, in The Theory, Of
the Photographic Process, Chapter 12,
Principles and Chemistry of Color
Photography. Silver Dye Bleach Process,
4th ed., THJames ed., Macmillan, New
York, 1977, pp. 363-366. The compounds of the present invention can also be used in black-and-white photosensitive materials. The amount of the compound of the present invention to be added is 1×10 ^-7 to 5×10 ^-1 mol, particularly 1×10 ^-4 to 1×10 ^-1 per mol of silver.
Preferably it is in moles. Regarding the timing and method of addition, it is preferable to emulsify and disperse it in the same manner as color couplers and then add it to the coating liquid. Next, examples of the present invention will be specifically illustrated. However, it is not limited to this. This will help understand how to apply the technique according to the invention. Example 1 On a cellulose triacetate film support provided with an undercoat layer, an emulsion layer containing auxiliary developers shown in Table 1 and their precursors dissolved and emulsified in a high-boiling organic solvent was coated. Samples 1 to 10 were prepared by doing the following. The amount of each substance applied was expressed numerically in the box as g/m ² or mol/m ² . In addition to the substances listed below, gelatin hardeners and coating aids were added by conventional methods. (1) Emulsion layer Negative silver iodobromide emulsion (grain size 1.5μ) (Silver 1.7×10 ^-2 mol/m ² ) Magenta coupler (cp-1) (1.30×10 ^-3 mol/m ² ) Auxiliary development Drug or its precursor (1.30×10 ^-3 mol/m ² ) Gelatin (2.50 g/m ² ) (2) Protective layer Gelatin (1.30 g/m ² ) These films were heated at a temperature of 45°C and a relative humidity of 80%. After being left under these conditions, imagewise exposure for sensitometry was applied and the next color development process was carried out. Color development process Time Temperature 1 Color development 3′15″ 38℃ 2 Bleaching 6′30″ 〃 3 Water washing 2′ 〃 4 Fixing 4′ 〃 5 Water washing 4′ 〃 6 Stability 1′ 〃 Color here The composition of each processing solution in the development processing step is as follows. Color developer water 800ml 4-(N-ethyl-N-hydroxyethyl)amino-2-methylaniline sulfate 5g Sodium sulfite 5g Hydroxylamine sulfate 2g Potassium carbonate 30g Potassium bicarbonate 1.2g Potassium bromide 1.2g Sodium chloride 0.2g Trisodium nitrilotriacetate 1.2g Add water 1 (PH10.1) Bleach solution Water 800ml Ferric ammonium salt of ethylenediaminetetraacetic acid 100g Disodium ethylenediaminetetraacetate 10g Potassium bromide 150g Acetic acid 10g Add water 1 (PH6 .0) Fixing solution Water 800ml Ammonium thiosulfate 150g Sodium sulfite 10g Sodium hydrogen sulfite 2.5g Add water 1 (PH6.0) Stabilizer Water 800ml Formalin (37%) 5ml Dry well 3ml Add water to 1. Photograph obtained Table 1 shows the gender.

[Table] It is clear from Table 1 that in the samples containing the auxiliary developer precursor according to the present invention, gamma, sensitivity, and color density increased with almost no increase in fog. The magenta coupler and auxiliary developer used here are as described above. Comparative compound (D-1) Comparative compound (D-2) Comparative compound (D-3) Comparative compound (D-4) (Compound described in U.S. Pat. No. 4,209,580) Example 2 Cellulose triacetate film provided with a subbing layer to evaluate the effectiveness of the auxiliary developer precursor in the present invention and their control compounds. Samples 11 to 17 were prepared by coating on a support an emulsion layer in which the auxiliary developer and its precursor shown in Table 2 below were added by dissolving and emulsifying the auxiliary developer and its precursor together with the coupler in a coupler solvent. did. The amount of each substance applied is shown in the box in g/m ² or mol/m ² . In addition to the following substances, a gelatin hardener and a coating aid were also added by a conventional method. (1) Emulsion layer Negative 1.5μ silver iodobromide emulsion (silver 1.60×10 ^-2 mol/m ² ) Cyan coupler (CP-2) 1.40×10 ^-3 mol/m ² Auxiliary developer or precursor 1.40×10 ^-3 mol/m ² Gelatin (2.50×10gm ² ) (2) Protective layer Gelatin (1.30g/m ² ) Sensitometry was performed after these films were left for 24 hours at a temperature of 45% and a relative humidity of 80%. The same color development process as in Example 1 was carried out. The photographic properties obtained are shown in Table 2.

【table】

[Table] It is clear from Table 2 that in the samples containing the 3-pyrazolidone precursor of the present invention, gamma, sensitivity, and color density increased without any increase in fog. The cyan coupler and 3-pyrazolidone auxiliary developer used here are as follows. Note that (D-1) and (D-2) are the same as in Example (1). Example 3 To evaluate the effectiveness of the auxiliary developer precursor in the present invention, the compounds of the present invention and their control compounds were prepared as in Example 1 on a paper support double-sided laminated with polyethylene. Samples 18 to 24 were prepared by applying the auxiliary developer and its precursor shown in . (1) Emulsion layer Negative 0.7μ silver chlorobromide emulsion (Silver 5.12×10 ^-3 mol/m ² ) Yellow coupler (CP-3) (8.53×10 ^- 4 mol/m ² ) Auxiliary developer or precursor (5.12 ×10 ^-4 mol/m ² ) Gelatin (1.35 g/m ² ) (2) Protective layer Gelatin (1.30 g/m ² ) These films were subjected to imagewise exposure for sensitometry and then subjected to the next color development process. I did it. Color development processing Time Temperature 1. Color development 12' 33°C 2. Bleach-fixing 1'30" 33°C 3. Water washing 2'30" 25-30°C Here, the composition of each processing solution in the color development processing step is as follows. Color developer Benzyl alcohol 15ml Diethylene glycol 8ml Ethylenediaminetetraacetic acid 5g Sodium sulfite 2g Anhydrous potassium carbonate 30g Hydroxylamine sulfate 3g Potassium bromide 0.6g 4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-m -Toluidine 5g Add 3/2 sulfate/monohydrate and adjust to PH10.20 Bleach-fix solution Ethylenediaminetetraacetic acid 2g Ethylenediaminetetraacetic acid ferric salt 40g Sodium sulfite 5g Ammonium thiosulfate 70g Add water 1 Obtained The results of photographic properties are shown in Table 3.

【table】

[Table] From Table 3, when an auxiliary developer is added, the precursor compound of the present invention sensitizes but causes fog, or does not increase fog but desensitizes. It can be seen that sensitization is achieved without an increase in . The yellow coupler and auxiliary developer used here are as follows. (D-1) and (D-3) are the same compounds as in Example 1. Example 4 The following photosensitive sheet and image receiving sheet were prepared. Photosensitive sheet A photosensitive sheet was prepared by coating the following emulsion layer and protective layer on a polyethylene laminate paper support. Compounds of the invention and comparative compounds were dissolved in methyl alcohol and added to the emulsion. (1) Emulsion layer Silver iodobromide emulsion containing 4% silver iodide (silver 9.2×10 ^-3 mol/m ² ) Compounds of the present invention and comparative compounds (1.0×10 ^-6 mol/m ² ) Gelatin ( 1.50g/m ² ) (2) Protective layer Ceratin (1.0g/m ² ) Image-receiving sheet A polyethylene laminate paper with a 6 μm cellulose triacetate layer was immersed in an alkaline hydrolysis solution containing silver deposition nuclei for 1 minute, and the common diffusion An image receiving sheet for transfer was prepared. The alkaline hydrolyzate was prepared as follows. Dissolve 0.1 g of nickel nitrate in 2 ml of water, add to 100 ml of glycerin, and stir vigorously.
1 g of sodium sulfide dissolved in 2 ml of water was further added to prepare a dispersion of silver deposition nuclei of nickel sulfide.
20 ml of this dispersion was added to 1000 ml of a water-methyl alcohol (1/1) solution in which 80 g of sodium hydroxide was dissolved to prepare an alkaline hydrolysis solution containing silver deposition nuclei. Forced deterioration conditions for the photosensitive sheets 25 to 31 (60°C,
The samples that were kept for 3 days and those that were not kept were subjected to imagewise exposure for sensitometry. Diffusion transfer development was carried out by spreading the following processing solution to a thickness of 0.1 mm between these photosensitive sheets and the image receiving sheet. Treatment liquid Potassium hydroxide (40% aqueous solution) 323ml Titanium dioxide 3g Hydroxyethylcellulose 79g Zinc oxide 9.75g N,N-bismethoxyethylhydroxylamine 75g Triethanolamine 45% aqueous solution 17.14g Tetrahydropyrimidinethione 0.4g 2,4-dimercapto Pyrimidine 0.35g Uracil 90g Water 1193ml The optical density of the obtained transferred silver image was measured, and the reciprocal of the exposure amount to obtain an optical density of 0.7 was defined as the sensitivity. The sensitivities are shown in Table 4 as relative values, with the sensitivity of the additive-free sample (photosensitive sheet No. 1), which was not subjected to forced deterioration conditions, taken as 100.

[Table] (This invention)
As shown in Table 4, samples 26 to 31 were all highly sensitive to No. 25, which was not added. However, in all comparative samples 26 to 28, the maximum color density decreased significantly under forced deterioration conditions. On the other hand, in the sample to which the precursor compound of the present invention was added, the color density decreased only slightly while maintaining high sensitivity. As for the comparative compounds used here, D-2 and D-3 are the same as in Example 1, and D-7 is the following. Example 5 A multilayer color photosensitive material was prepared using a cellulose triacetate film as a support and each layer had the composition shown below. 1st layer: Antihalation layer (AHL) Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer (ML) Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone 3rd layer: 1st layer Red-sensitive emulsion layer (RL ₁ ) Silver iodobromide emulsion (Silver iodide: 5 mol%)...Silver coating amount 1.79 g/ ^m2 Sensitizing dye...6 x 10 ^-5 mol increase per 1 mol of silver Sensitive dye: 1.5×10 ^-5 mol per mol of silver Coupler A: 0.04 mol per mol of silver Coupler C: 0.003 mol per mol of silver Coupler P: per mol of silver 0.0006 mol 4th layer: 2nd red-sensitive emulsion layer (RL ₂ ) Silver iodobromide emulsion (silver iodide: 4 mol%)...Silver coating amount 1.4 g/ ^m2 Sensitizing dye...for 1 mol of silver Sensitizing dye... 1.2 x ^{10 -5} mol per mol of silver Coupler A... 0.005 mol per mol of silver Coupler C... 0.0016 mol per mol of silver This invention Compound (17)...0.0025 mol per mol of silver 5th layer: Intermediate layer (ML) 6th layer, same as the 2nd layer: 1st green-sensitive emulsion layer (GL ₁ ) Silver iodobromide emulsion (IL) Silver oxide: 4 mol%) ... Coated silver amount 1.5 g/m ² Sensitizing dye... 3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye... 1 x 10 ^-5 per 1 mol of silver Mol Coupler B... 0.05 mol per mol of silver Coupler M... 0.008 mol per mol of silver Coupler Q... 0.0015 mol per mol of silver 7th layer: Second green-sensitive emulsion layer (GL ₂ ) Silver iodobromide emulsion (Silver iodide: 5 mol %) Coated silver amount 1.6 g/m ² Sensitizing dye...2.5 x 10 ^-5 mol per 1 mol of silver Sensitizing dye... per 1 mol of silver 0.8×10 ^-5 mol Coupler B...0.02 mol per mol of silver Coupler M...0.003 mol per mol of silver Compound (17) of the present invention...0.002 mol per mol of silver No. 8 Layer: Yellow Filter Layer (YFL) A gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2.5-di-t-octylhydroquinone in an aqueous gelatin solution. 9th layer: 1st blue-sensitive emulsion layer (BL ₁ ) Silver iodobromide emulsion (silver iodide: 6 mol%) ...Amount of coated silver 1.5 g/ ^m2 Coupler Y...0.25 mol per 1 mol of silver 10th layer: 2nd emulsion layer (BL ₂ ) Silver iodobromide (silver iodide: 6 mol %) ... Coated silver amount 1.1 g/m ² Coupler Y ... 0.06 mol per 1 mol of silver 11th layer: Protective layer (PL) Polymethylmethanoacrylate particles (diameter approx.
Apply a gelatin layer containing 1.5μ). In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. Compound used to prepare the sample Sensitizing dye: Anhydro 5,5'-dichloro3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt Sensitizing dye: Anhydro 9-ethyl-3・3′-
G(γ-sulfopropyl)-4,5,4'-
5′-dibenzothiacarbocyanine hydroxide/toluethylamine salt sensitizing dye: anhydro-9-ethyl-5・5′-
Dichloro-3,3'-di-(γsulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
{β-[β-(γ-sulfopropoxy)ethoxy]
Ethylimidazolocarbocyanine hydroxide sodium salt The obtained sample was processed into a 35 mm size film and subjected to imagewise exposure. Perform the development process shown below in 2
This was done in a developer tank. 1 Color development...3 minutes 15 seconds 2 Bleaching...6 minutes 30 seconds 3 Washing...3 minutes 15 seconds 4 Fixing...6 minutes 30 seconds 5 Washing... …3 minutes 15 seconds 6 Stable ………3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite (70%) 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water In addition, as a result of 1 or more, clear color negative images were obtained. The compounds of the present invention can be prepared by conventional methods of adding couplers to emulsions or dispersing them, and adding them to gelatin/silver halide emulsions or hydrophilic colloids. For example, high boiling organic solvents - dibutyl phthalate, tricresyl phosphate,
A method of mixing and dispersing wax, higher fatty acids and their esters with a coupler, for example, US Patent No.
The method described in No. 2304939, No. 2322027, etc. Another method is to mix and disperse the coupler with a low boiling point organic solvent or a water-soluble organic solvent. A method of dispersing couplers in combination with a high boiling point organic solvent. For example, U.S. Patent Nos. 2801170, 2801171,
The method described in issue 2949360 etc. A method of dispersing the coupler alone or in combination with other couplers, such as colored couplers or uncolored couplers, when the coupler itself has a sufficiently low melting point (for example, 75°C or lower). For example, the description in German Patent No. 1143707 is applicable. Dispersion aids include commonly used anionic surfactants (e.g., sodium alkylbenzene sulfonate, sodium dioctylsulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc.), amphoteric interfaces, etc. Active agents (for example, N-tetradecyl/N.N dipolyethylene α betaine, etc.) and nonionic surfactants (for example, sorbitan, monolaurate, etc.) are used. Couplers that can be used in combination with the compound of the present invention include, for example, the following known couplers. A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1971, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
-60233, No. 51-26541, No. 53-55122, etc. Specific examples of yellow couplers are U.S. Pat. No. 2,875,057, U.S. Pat.
No. 3408194, No. 3551155, No. 3582322, No. 3582322, No. 3551155, No. 3582322, No.
No. 3725072, No. 3891445, West German Patent No. 1547868,
West German Application No. 2219917, West German Application No. 2261361, West German Publication No.
No. 2414006, British Patent No. 1425020, Special Publication No. 1977-
No. 10783, JP-A-47-26133, JP-A No. 48-73147,
No. 51-102636, No. 50-6341, No. 50-123342
No. 50-130442, No. 51-21827, No. 50-
It is described in No. 87650, No. 52-82424, No. 52-115219, etc. Specific examples of cyan couplers are listed in No. 2369929 and
No. 2434272, No. 2474293, No. 2521908, No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
No. 3591383, No. 3767411, No. 4004929, West German patent application (OLS) No. 2414830, No. 2454329, Japanese Patent Application Publication No. 48-59838, No. 51-26034, No. 48-5055,
These are those described in No. 51-146828, No. 52-69624, and No. 52-90932. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, JP-A No. 51-26034, No. 52-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, Japanese Patent Application Publication No. 1983-69624, No. 49-122335
Those described in Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and JP-A-53-9116 can be used. High boiling point organic solvents include, for example, US Pat. No. 2,322,027;
No. 2533514, No. 2835579, Special Publication No. 1972-23233,
US Patent No. 3287134, British Patent No. 958441, JP-A-Sho
No. 47-1031, UK Patent No. 1222753, US Patent
No. 3936303, JP-A-51-26037, JP-A-50-
82078, U.S. Patent No. 2353262, U.S. Patent No. 2852383, U.S. Pat.
No. 3554755, No. 3676137, No. 3676142, No. 3676142, No. 3676137, No. 3676142, No.
No. 3700454, No. 3748141, No. 3837863,
OLS2538889, JP-A-51-27921, JP-A No. 51-
No. 27922, No. 51-26035, No. 51-26036, No. 50
-62632, Special Publication No. 49-29461, US Patent
It is described in No. 3936303, No. 3748141, and Japanese Patent Application Laid-open No. 1521/1983. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. Examples include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as alginate and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin as described in Bull.Soc.Sci.Phot.Japan.No.30 (1966)).
may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The product obtained by the reaction is used. In the photographic emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. The average grain size of silver halide grains in photographic emulsions (spherical or near-spherical grains, regular grains such as cubes and octahedrons, tabular grains, etc.) is based on the volume average equivalent to a sphere. The particle size (particle size) is preferably 5μ or less, particularly preferably 3μ or less. The particle size distribution may be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubes and octahedrons, or may have irregular crystal shapes such as spherical and plate shapes. It may also have a composite crystalline form. It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press (1966), Making by VLZelikman et al.
and Coating Photographic Emulsion (The
Focal Press, 1964). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a sulfite salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a nude water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. Silver halide emulsions are usually chemically sensitized. For chemical sensitization, see for example H.Frieser ed.
Die Grundlagen der Photographischen
Prozesse mit Silberhalogeniden (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, Reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; noble metal compounds (e.g., gold complex salts, Pt,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Ir and Pd can be used alone or in combination. Specific examples of these include U.S. Patent No. 1574944, U.S. Pat.
No. 2728668, No. 3656955, etc., and U.S. Patent Nos. 2983609 and 2419974 for reduction sensitization methods.
The precious metal sensitization method is described in US Pat. No. 2,399,083, US Pat. No. 2,448,060, British Patent No. 618,061, etc. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. i.e. azoles such as benzothiazolium salts, nitroindazole salts, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenz Imidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,
7) Many compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; etc. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsion dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast Various surfactants may be included for various purposes such as sensitization, sensitization), etc. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic compounds such as alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), aliphatic esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosucci Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as acid esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium, imizolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion layer of the photographic light-sensitive material prepared using the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, and thiomorpholins. , quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US patent
No. 2400532, No. 2423549, No. 2716062, No.
Those described in No. 3617280, No. 3772021, No. 3808003, British Patent No. 1488991, etc. can be used. Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure No. 176, pages 28-30 (RD
-17643), any of the known methods and known treatment liquids can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 18℃ to 50℃
Selected between 18℃ or lower temperature than 50℃
The temperature may exceed ℃. The developer used in black-and-white photographic processing can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. are used alone or in combination. be able to. The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" processing is used for photographic reproduction of line images or halftone dots.
This refers to a development process that uses dihydroxybenzenes as a developing agent and allows the development process to be carried out in a contagious manner under a low sulfite ion concentration (for details, see "Photographic Processing Chemistry" by Mason (1966)) It is described on pages 163 to 165. A special form of development processing uses a method in which a developing agent is contained in a light-sensitive material, such as an emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution to perform development. Hydrophobic developing agents are available from Research Disclosure No. 169 (RD-16928).
They can be incorporated into the emulsion layer by various methods such as those described in US Pat. No. 2,739,890, British Patent No. 813,263, or West German Patent No. 1,547,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied.
For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Volume 61 (1953), pp. 667-701); developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other A color reversal method in which a dye-positive image is obtained by performing appropriate fog treatment and subsequent color development; a silver image in which a photographic emulsion layer containing a dye is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dye. A basic bleaching method is used.The color developer generally consists of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. The color developer may also contain a PH buffer, a development inhibitor or an antifoggant. In addition, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, and antioxidants are added as necessary. It may also include. Specific examples of these additives include Research Disclosure (RD-17643) and U.S. Patent No. 4083723.
No., OLS No. 2622950, etc. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanides; dichromates, organic complexes of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. The photosensitive material made using the present invention is
No. 84636, JP-A-52-119934, JP-A-53-46732
No. 1986-9626, 1974-19741, 1973-37731, Japanese Patent Application No. 1976-76158, Japanese Patent Application No. 54-1976
-76159 and Japanese Patent Application No. 54-102962, the developer may be replenished or maintained. The bleach-fixing solution used in the photosensitive material produced using the present invention is disclosed in Japanese Patent Application Laid-open Nos. 46-781 and 48-49437.
No. 48-18191, No. 50-145231, No. 51-
It may be recycled by the method described in No. 18541, No. 51-19535, No. 51-144620, and Japanese Patent Publication No. 51-23198. The photographic light-sensitive material produced using the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. . For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. For example, US Patent No. 2376005,
Same No. 2739137, No. 2853457, No. 3062674, Same No.
No. 3411911, No. 3488708, No. 3525620, No.
Those described in British Patent No. 3607290, British Patent No. 3635715, British Patent No. 3645740, British Patent No. 1186699, British Patent No. 1307373 can be used. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. Useful sensitizing dyes include, for example, German Patent No. 929080;
U.S. Patent No. 2493748, U.S. Patent No. 2503776, U.S. Patent No. 2519001,
Same No. 2912329, No. 3656959, No. 3672897, Same No.
No. 4025349, British Patent No. 1242588, Special Publication No. 1977-
It is described in No. 14030. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are US Patent No. 2688545, US Patent No. 2977229, US Patent No.
No. 3397060, No. 3522052, No. 3527641, No. 3527641, No. 3522052, No. 3527641, No.
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3814609, No. 3672898, No. 3679428, No. 3814609, No.
No. 4026707, British Patent No. 1344281, Special Publication No. 43-4936
No. 53-12375, JP-A-52-110618, No. 52
-Described in No. 109925. In the photographic light-sensitive material produced using the present invention, the photographic emulsion layer and other layers are made of a flexible support such as plastic film, paper, or cloth, which is commonly used in photographic light-sensitive materials, or a rigid support such as glass, ceramic, or metal. applied to the support. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers ( For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer, etc. is used. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. In the photographic light-sensitive material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. U.S. Patent No. 2681294,
The methods described in No. 2761791 and No. 3526528 are advantageous methods. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of the various known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, and the like. Exposure times include not only exposure times of 1/1000 seconds to 1 second that are normally used with cameras, but also exposures shorter than 1/1000 seconds, such as exposures of 1/10 ⁴ to 1/10 ⁶ seconds using xenon flash lamps and cathode ray tubes. or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed with light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. In the photosensitive material produced using the present invention,
The photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. The photographic light-sensitive material produced using the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl hydatoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) etc.), activated vinyl compounds (1,3,
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.),
Mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.) can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. For example, UK patent
685475, U.S. Patent No. 2675316, U.S. Patent No. 2839401, U.S. Pat.
No. 2882156, No. 3048487, No. 3184309, No.
No. 3445231, West German Patent Application (OLS) No. 1914362,
Polymers described in JP-A-50-47624, JP-A-50-71332, etc. can be used. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, P-alkoxyphenols, P-oxyphenol derivatives, and bisphenols. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula in a photographic constituent layer on a support. general formula In the formula, A represents an aliphatic group or an aromatic group, and R ₁ and R ₂ are each independently a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms (as a substituent, an alkoxy group, a halogen atom, ,
(selected from acyloxy group, alkoxyacyloxy group, carbamoyloxy group),
R ₃ represents a hydrogen atom or an aromatic group, and R ₄ represents an aromatic group.