JPS6015263B2 - Silver halide photographic material - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic light-sensitive material containing a curable developing agent, and more specifically, contains nordihydroguaiaretic acid as a curable developing agent and an alkyl gallate as an auxiliary developing agent. This invention relates to a silver halide photographic light-sensitive material. In general, catechol, hydroquinone, pyrogallol, etc. act as a strong developer for photosensitive silver halide, and their oxidation products react with a hydrophilic protective colloid layer, such as gelatin, to strongly harden it. It has been known for a long time as a developing agent. These curable developing agents are described, for example, in U.S. Pat.
As described in side number 3, a method of adding it to a photographic emulsion or a processing solution is also widely known. Compared to when a curable developer is added to a light-sensitive material, when it is added to a processing solution, the curable developer is more likely to diffuse and move through the emulsion layer of the light-sensitive material during processing. Not only is it difficult to obtain an image with a high iron content, but the developing agent is also difficult to work with, resulting in insufficient hardening of the image area, and as a result, some of the hardened image area dissolves during the post-development process. This may result in insufficient image density. Therefore, when obtaining a so-called wash-off relief image, it is generally preferable to incorporate the curable developer into the photosensitive material rather than adding it to the processing solution. However, if a readily water-soluble curable developer such as pyrogallol or hydroquinone is added in advance to the silver halide emulsion or to an adjacent layer, fogging may occur during long-term storage.
This often results in undesirable photographic properties such as a decrease in image density during development and insufficient curing due to a decrease in development activity. In addition, when such a developing agent is added to a silver halide photographic emulsion in advance and coated on a support and then treated with an alkaline solution after exposure, the developing agent is far removed from the alkaline solution and a sufficient silver concentration is not obtained. and a cured image may not be obtained. Further, many of the curable developing agents diffuse into the coated gelatin and therefore harden exposed areas, which can have an adverse effect on photographic properties. Therefore, in order to obtain a wash-off relief image that is favorable from the viewpoint of photographic characteristics,
There is a need for a developing agent which has strong development activity, whose oxidation product has appropriate curability, and which is stable for a long time even when added to an emulsion. What is more important is to suppress diffusion in the gelatin film or gelatin silver halide emulsion film so as not to harden the unexposed areas. One of the objects of the present invention is to provide a photosensitive material containing a developing agent which has strong development activity when treated with an alkaline activator and whose oxidation product has appropriate hardening properties against hydrophilic protective colloids. That's true. A second object of the present invention is to provide a photographic material containing a curable developing agent that can be stably incorporated into a photographic emulsion layer or a layer adjacent thereto for a long period of time. A third object of the present invention is to provide a photosensitive material that can significantly suppress the curability of unexposed areas and produce cured images with excellent photographic properties.
The above objects are achieved by containing nordihydroguaiaretic acid [1] and the general formula

This was achieved using a silver halide photographic material containing an alkyl gallic acid ester represented by [0]. [In the formula, R represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms] The compound of the present invention, nordihydroguaiaretic acid [1], naturally exists in creosote bush, so it can be obtained from It can be obtained by extraction and purification, or by synthesis using the method described in Patent Publication No. 1972-24018. The compound [b] of the present invention is widely used as an antioxidant by being added to fats and oils and butter. Then the compound

Although some preferred specific examples of [0] will be described, the compounds of the present invention are not particularly limited to these. The nordihydroguaiaretic acid of the present invention has excellent diffusion resistance and can be incorporated extremely stably into photographic materials or processing solutions, and can extremely limit gelatin surrounding exposed silver halide. This developer is noteworthy in that it hardens within the range where it is applied. Furthermore, films of photosensitive materials such as gelatin hardened using the developing agent of the present invention have extremely high dissolution resistance to alkaline solutions. Furthermore, since the developing agent of the present invention does not interact with other coexisting photographic additives, such as antifoggants, it may reduce the effects of other photographic additives or reduce the developing activity and curing activity of the present developing agent. is never lost. In order to disperse the developer of the present invention in the silver halide emulsion layer or its adjacent layer, in addition to the method of neutralizing an alkaline solution of the compound as described in U.S. Pat. No. 344,004y, cyclohexanone, A method of dissolving and dispersing in a water-soluble organic solvent such as acetone, methoxyethanol, ethoxyethanol, ethylene glycol, dioxane, dimethylformamide, or butyl phthalate,
Dinonyl phthalate, butyl benzoate, jetylhexyl zebacate, butyl stearate, dinonyl maleate, tributyl citrate, tricresyl phosphate, dioctyl butyl phosphate, trihexyl phosphate, triotadecyl phosphate, etc. US Pat. No. 3,676,137 A method of dissolving and dispersing the coupler in a high-boiling organic solvent for dispersing the coupler, jetyl succinate, dioctyl adipate, 3-ethyl biphenyl, etc., as described in 2006, can be used. Furthermore, saponin, sodium alkylsulfosuccinate, and sodium alkylbenzenesulfonate can be used as surfactants when dispersing the solution of the curable developer used in the present invention in the above-mentioned solvent in the hydrophilic protective colloid solution. etc. can also be used. Nordihydroguaiaretin used in the present invention is preferably added to the light-sensitive material in an amount of 0.01 to 1 mol/mol Ag, particularly preferably 0.03 to 0.3 mol/mol Ag. The gallic acid alkyl ester is preferably present in the light-sensitive material in an amount of 0.005 to 0.1 mol/mol, particularly 0.005 to 0.1 mol/mol.
Preferably, the amount is 0.01 and 0.03 mol/mol A. Further, gallic acid or gallic acid alkyl ester may be added to the treatment solution, and the amount added at this time is 10-5
None, 10-2 mol/s. However, it is more preferable to add the compound to the photosensitive material rather than to the processing solution. Nordihydroguaiaretic acid is used as a tanning developer in U.S. Pat. No. 2,751,295.
listed in the number. However, the patent specification merely states that when the compound is used alone, it does not exhibit as favorable properties as the catechol derivatives. That is, although the patent specification does not suggest that the compound and the gallic acid alkyl ester of the present invention are used together, the object of the present invention can be achieved by using the nordihydroguaiaretic acid of the present invention and the gallic acid alkyl ester in combination. There is no suggestion that such an effect can be obtained. Also, U.S. Patent No. 3440
No. 049 describes that the polyhydroxy-spiro bis-indane compound and the compound belonging to the gallic acid ester of the present invention can be used in combination, but the polyhydroxy-spiro bis-indane compound can be used in combination with the nordihydroguay compound of the present invention. Since it is different from aretic acid, it is obvious that the structure described in the patent specification is different from the structure of the present invention.
The present invention is based on a technical concept discovered in order to overcome the drawbacks of conventional compounds such as polyhydroxy-spiro bis-indane compounds and catechol. Furthermore, U.S. Pat. No. 3,453,10 describes that a 4-substituted-3-pyrazolidone compound and gallic acid similar to the alkyl gallate of the present invention can be used as a developer to obtain a relief image. ing. However, the patent specification does not disclose that it is used in combination with nordihydroguaiaretic acid of the present invention, and furthermore, it does not disclose at all that gallic acid alkyl ester, which is essential in the present invention, is used. On the other hand, the present invention does not intend to use a 4-substituted-3-pyrazolidone compound and an alkyl gallic acid ester together without using nordihydroguaiaretic acid. Therefore, it is clear that the technical contents of this patent and the present invention are different. The present invention was made based on the discovery that when nordihydroguaiaretic acid and a gallic acid alkyl ester were used in combination, excellent effects that could not have been expected based on conventional knowledge were discovered. A typical example of the hydrophilic protective colloid used in the photosensitive material of the present invention is gelatin. Other ingredients include casein, carboxymethyl cellulose, polyvinyl alcohol, and polyvinyl alcohol. Examples include lydone, styrene-mono-hydro-maleic acid copolymer, condensate of styrene-mono-hydro-maleic acid copolymer and polyvinyl alcohol, polyacrylate, ethyl cellulose, etc., but the present invention is not limited to these. do not have. The gelatin to be applied to the photosensitive material of the present invention may be so-called alkali-treated (lime-treated) gelatin that is soaked in an alkaline bath before gelatin extraction, acid-treated gelatin that is soaked in an acid bath, or "Bull SM Sci" Photo Japan”
No. 16, p. 30 (1966) may be used. Furthermore, low molecular weight gelatin which is partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme can also be used in the light-sensitive material of the present invention. The gelatin used in the photosensitive material of the present invention may be partially composed of colloidal albumin, casein, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, agar, sodium alginate, starch conductor, etc. Conductors, synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or their derivatives/partial hydrolysates can be substituted, and so-called gelatin conductors, i.e., in molecules, can be used. The amino groups, imino groups, hydroxyl groups, and carboxyl groups contained as functional groups are treated and modified with a reagent that has one group that can react with them, or the molecular chains of other polymeric substances are bonded to them. Alternatively, a graft polymer may be used instead. Reagents for making the above-mentioned derivatives include, for example, isocyanates, acid chlorides, and acid anhydrides described in U.S. Pat. No. 2,614,928;
Acid anhydrides listed in the Japanese Patent Publication No. 391-5514
phenylglycidyl ethers described in Japanese Patent Publication No. 42-26845, vinyl sulfone compounds described in U.S. Pat. No. 3,132,945, and compounds described in British Patent No. 861,414. N-allyl vinyl sulfonamides, US Pat. No. 31
Maleimide compounds as described in US Pat. No. 86846, acrylonitriles as shown in US Pat. No. 2,594,293, polyalkylene oxides as described in US Pat. No. 3,312,553, Samurai Kosho 42-26
845, acid esters as shown in US Pat. No. 2,763,639, and alkanesultones as described in British Patent No. 103,318'. In addition, the branched polymer grafted onto gelatin has been patented in US Patent No. 2.
No. 763625, No. 2831767, No. 2956 Total 4
Or Polymer Bottle Wax 5 595 (1
967), Ph. tSciEng 9 148 (1965), J. Pol
ymerSci A-1 9 3199 (1971), etc., acrylic acid, methacrylic acid or their esters, amides, derivatives such as nitrile, or styrene are generally called vinyl monomers. A wide variety of polymers, copolymers, etc. can be used. However, hydrophilic pinyl polymers having some degree of compatibility with gelatin are particularly desirable, such as polymers or copolymers of acrylic acid acrylamide, methacrylamide, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, and the like. The photographic emulsion layer and other layers of the photographic light-sensitive material of the present invention may also contain synthetic polymer compounds, such as latex-like water-dispersed vinyl compound polymers, especially compounds that increase the dimensional stability of the photographic material. They may be included as a mixture (of different polymers) or in combination with hydrophilic water-permeable colloids. There are many types of polymers, such as U.S. Pat.
No. 6005, No. 2739137, No. 2853457, No. 3062674, No. 3411911, No. 348
No. 8708, No. 3525620, No. 3 No. 5715,
It is described in British Patent No. 3607290, British Patent No. 3645740, British Patent No. 1186699, British Patent No. 1307373, etc. Among these descriptions are alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, alcohol Copolymers and homopolymers selected from oxyalkyl acrylates, alkoxymethacrylates, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and itaconic anhydride are commonly used.
In some cases, when these vinyl compounds are subjected to emulsion polymerization, a so-called graft-type emulsion polymerization latex, which is carried out in the coexistence of a hydrophilic protective colloid polymeric substance, may be used. When the /dihydroguaiaretic acid and alkyl gallic acid of the present invention are used in a photographic material, they can be used together with a matting agent. The matting agent is preferably a water-proof fine particle of an organic or inorganic compound with an average particle diameter of 0.2 mm to 10 mm, particularly preferably 0.3 mm to 5 mm. Examples of organic compounds include water-dispersible vinyl polymers such as polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-Q-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, and polypinyl acetate. , polyethylene carbonate, polytetrafluoroethylene, etc. Examples of cellulose derivatives include methylcellulose, ethylcellulose, cellulose acetate, cellulose acetate propionate, etc. Examples of starch derivatives include carpoxynitrophenyl starch, urea-formaldehyde Gelatin hardened with a known hardening agent such as a starch reactant, and hardened gelatin formed into microcapsule hollow particles by coacervate hardening can be preferably used. As examples of inorganic compounds, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, etc. can be preferably used. The above-mentioned matting agents can be used by mixing different types of substances as necessary. The photographic emulsion of the photographic light-sensitive material of the present invention includes well-known hardening agents, such as aldehyde compounds such as formaldehyde and glutaraldehyde, and reactive halogen-containing compounds described in U.S. Pat. No. 3,288,775 and others. Compounds having reactive ethylenically unsaturated bonds described in U.S. Pat. No. 3,635,718 and others, U.S. Pat. No. 3,017
Aziridine compounds described in No. 28, etc., epoxy compounds described in U.S. Pat. No. 3,091,537, etc., halogenated carboxyaldehydes such as mucochloric acid, dihydroxydioxane, dichlorodioxane, etc. dioxane-based compounds, divinyl sulfone-based compounds, or chromium alum, zirconium sulfate, etc., which are also known as inorganic hardening agents, are added to dry gelatin for 2 to 2 hours.
can be used at concentrations below the percent cloud cover of
Depending on the purpose, it may not be necessary to use it at all. The silver halide emulsion used in the photographic light-sensitive material of the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver chlorobromide, silver chlorobromide, etc. can be used. These silver halide grains may have any shape such as cubic system, octahedron, mixed crystal form, etc. The particle size and average particle size distribution do not need to be particularly limited, and may be of any value. These silver halide grains are produced according to known and commonly used methods. Of course, it is also useful to use the so-called single or double jet method, controlled double jet method, or the like. Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of the halogenated radiation particle is uniform inside, there are cases where the inside and outside have a different layered structure, British Patent No. 635841, U.S. Patent No. 36223, etc.
It may be of a so-called conversion type as described in No. 18. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions were produced by Mees station “The Theoryo”.
fPhotogaph, Processes (The Theory of Photographic Process), MacMma
Published by n company: P. “ChimjePho’s Gnephique” by Grafikides, published by PauIMontel (
It can be prepared by various methods such as the ammonia method, the neutral method, and the acid method, which are also described in books such as 1957) and are widely accepted. After forming such halogenated radiation particles,
wealth. Water washing is performed to remove the resulting water-soluble salts (e.g., potassium nitrate when silver bromide is made using silver nitrate and potassium bromide) from the system, followed by heat treatment with chemical sensitizers such as sodium thiosulfate, N - Sensitivity is increased without coarsening the particles by performing in the presence of N.N'-trimethylthiourea, monovalent gold thiocyanate salt, thiosulfate, stannous chloride, hexamethylenetetramine, etc.
These general laws are set out above. The above silver halide emulsion can also be chemically sensitized by conventional methods. Chemical sensitizers include, for example, U.S. Patent No. 23990,
No. 2540085, No. 2597856, No. 2597
Gold compounds such as chlorauric acid salts and gold trichloride as shown in US Pat. No. 915, US Pat.
No. 86, No. 2566245, No. 25662, No. 2
Salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium as shown in 5 Moth No. 079;
U.S. Patent No. 1574 Group No. 4, U.S. Patent No. 241068, U.S. Patent No. 3
Sulfur compounds that react with silver salts to form silver sulfide, such as those described in U.S. Patent Nos. 248785 and 25186,
No. 2521925, No. 2521926, No. 2694
Examples include stannous salts, amines, and other reducing substances as described in No. 637, No. 298361, and No. 3201254. The photographic emulsion used in the light-sensitive material of the present invention may be subjected to spectral sensitization or superchromatic sensitization, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. It can be carried out. These color sensitization techniques have been known for a long time, and are disclosed in, for example, U.S. Pat. No. 2,493,748, U.S. Pat.
No. 97, No. 3703377, No. 2688545, No. 2912329, No. 339706, No. 36156
No. 35, No. 3628964, British Patent No. 119530
No. 2, No. 1242 Technical Abbreviation No. 129, No. 62, West German Patent Publication No. 2030326, No. 212178, Hakama Kosho No. 43-4936, No. 44-14030, No. 43-10773, U.S. Patent No. 35116 mouse number, 35 secret number 052, 3527641, 361561
No. 3, No. 3615632, No. 3617295, No. 3
No. 635721, 36 Group No. 217, British Patent No. 113
There are also descriptions in No. 758 and No. 1216203.
The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material. Various compounds can be added to the above-mentioned photographic emulsions in order to prevent deterioration of ocular sensitivity and occurrence of sharpness during the manufacturing process, storage or processing of the light-sensitive material. Those compounds are 4-hydroxy-6-methyl-1,3
・An extremely large number of compounds have been known for a long time, including 7-tetrazaindene, 3-methyl-penzothiazole, 1-phenyl-5-mercaptotetrazole, many millet ring compounds, mercury-containing compounds, mercapto compounds, and metal salts. It is being An example of a compound that can be used is K. Mee
Written by “Themeo of the Photogap
hic PrMess” (3rd edition, 1966) 344
-In addition to being listed on page 9 of the original text, it is also listed in the following patents. US Patent No. 1758576, US Patent No. 2110178, US Patent No. 21310, US Patent No. 2173628, US Patent No. 269704
No. 0, No. 2304962, No. 2324123, No. 2
3941 spot number, 2444605-8, 25662
No. 45, No. 2694716, No. 2697099, No. 2708162, No. 2728663-5, No. 247
No. 6536, No. 2824001, No. 2843491, No. 2886437, No. 3052544, No. 313
No. 7577, No. 3220 Spot No. 9, No. 3226231,
No. 3236652, No. 3251691, No. 3252
No. 799, No. 3287135, No. 3326 Road No. 1, No. 34206, No. 3622339, British Patent No. 89
No. 3428, No. 40378, No. 1173609,
Same number 12001. A surfactant may be added alone or in combination to the photographic emulsion of the photographic light-sensitive material of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsifying and dispersing, sensitizing, improving photographic properties, antistatic, antiadhesive, etc.
These surfactants include natural surfactants such as saponins,
Nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines,
Quaternary ammonium salts, pyridine and other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfate ester groups, phosphate ester groups, amino acids, aminosulfonic acids, sulfuric acid or amine/alcohols. It is divided into amphoteric active agents such as phosphate esters. Some examples of surfactant compounds that can be used include U.S. Pat.
4 bag number, 32012 ball number, 3210191, 3
No. 294540, No. 3415 No. 9, No. 3441413
No. 3442654, No. 3475174, No. 35
No. 45974, West German Patent Publication No. 1942665,
British Patent No. 1077317, British Patent No. 11 No. 45, "Synthesis of Surfactants and Their Applications" by Ryohei Oda et al. (Yoko Shoten 19th Mouse Edition), and AW. Surf S by Berry
"Active Agents" (Interscience Publications Inc. 19$ Edition), J
．． P. It is described in books such as ``Encyclopedia of Surface Active Agents Volume 2'' (Chemical Babb IJ Shosh Company 1964 edition) written by Sisley. The photographic emulsions described so far are planar materials that do not undergo significant dimensional changes during processing, such as coatings on rigid or flexible supports such as glass, metal, or ceramic, depending on the purpose. do. Typical flexible supports include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, which are usually used in photographic materials. Polycarbonate films, other laminates thereof, thin glass films, paper coated with baryta, Q-olefin polymers, especially polyethylene, polypropylene, ethylene butene copolymers, etc. with 2 to 2 carbon atoms
Paper coated or laminated with Q-olefin polymer of No. 10, described in Hakama Koryo 47-190 Iso, by making the surface grainy, it improves adhesion with other polymeric substances and prints. There are plastic films with improved suitability. These supports may be transparent or transparent depending on the purpose of the photosensitive material.
Make choices that are opaque. In addition, when it is transparent, it is not only colorless and transparent, but also dyes and pigments can be added to make it colored and transparent. This has been done since the beginning with X-ray films, and J. SMPTE 67 2
He is also known for hitting 96 (19 balls). Opaque supports include those that are inherently opaque such as paper, transparent films with pigments such as dyes and titanium oxide added, or
It also includes plastic films that have been surface-treated by the method shown in No. 7-190, as well as paper and plastic films that have been made completely light-shielding by adding carbon black dye or the like. When the adhesive strength between the support and the photographic emulsion layer is insufficient, a layer having adhesive properties to both is provided as an undercoat layer. Further, in order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc. Each layer of the photographic material of the present invention may be coated by dip coating, air knife coating, curtain coating, spray coating, or as disclosed in US Pat. No. 2,681,294.
It can be coated by a variety of coating methods including extrusion coating using a hopper as described in No. U.S. Pat. No. 2,761,791 and U.S. Pat. No. 35, as necessary.
08 base No. 7 and same No. 2941898, same No. 35265
It is also possible to apply two or more layers at the same time by the method described in, for example, No. 28. The development process used in the present invention is characterized in that the development bath is an alkaline activator bath, but the other steps can be used as they are. The activator solution ranges from about 7 to 14, with a range of about 8 to 13 being particularly preferred. The temperature of the activator liquid is selected in the range of 20 pm to 7 pm, preferably 3 pm to 6000 pm. The activator used in the present invention is basically a general black and white developer from which the developing agent has been removed. Examples of activator buffers include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Tertiary sodium or potassium phosphate, potassium metaphoate, borax, etc. are used alone or in combination. In addition, hydrogen phosphate 2
Various salts can be used, such as sodium or potassium, sodium or potassium dihydrogen phosphate, sodium or potassium bicarbonate, formic acid, alkali nitrate, alkali sulfate, and the like. Further, an appropriate amount of a fog suppressant can also be included. These include inorganic halide compounds and known organic antifoggants. Representative examples of this inorganic halide compound are bromides such as sodium bromide, potassium bromide or ammonium bromide, and iodides such as potassium iodide or sodium iodide. On the other hand, examples of organic antifoggants include:
6-nitrobenzindazole described in U.S. Pat. Diaminophenazine, o-phenylene diamine, mercaptobenzimidazole, methylbenzothiazole, mercaptobenzoxazole, thiouracil, and 5-methylbenzotriazole, a compound described in Washikosho No. 46-41675, etc. Examples include ring compounds. In addition, antifoggants described in "Science Photography Handbook" Volume 2, page 119 (Maruzen, 195g, hand-published) can also be used. For controlling surface layer development,
Development inhibitors known from Japanese Patent No. 46-19039, No. 45-614, US Pat. No. 3,295,976, etc. can also be used. In addition, ammonium chloride, potassium chloride, sodium chloride, etc. can be added as necessary. Further, if necessary, any development accelerator can be added in combination. Among these are U.S. Patent No. 2,648,604,
Various pyridinium compounds and other cationic compounds represented by No. 4-9503 and U.S. Patent No. 3,671,247, cationic dyes such as phenosaffron, neutral salts such as thallium nitrate and potassium nitrate, Samurai Kosho 44-95
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, described in U.S. Pat. organic solvents and organic amines,
Includes ethanolamine, ethylenediamine, jetanolamine, etc. In addition, L. F. A. Maso
Author: Photographic Processing Chemistry-1
misthi) pages 40-43 (FMaIPress-Yama n
Also included are accelerators as detailed in King Donl968). Additionally, sodium sulfite, potassium sulfite, potassium fluoride sulfite, and sodium bisulfite can be added. Furthermore, polyphosphoric acid compounds represented by sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, or potassium salts of the above polyphosphoric acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-(hydroxy Aminopolycarboxylic acids such as methyl)ethylenediaminetriacetic acid and diethylenetriaminebentachain acid can be used as water softeners. The amount added varies depending on the hardness of the water, but is usually 0.5
It can be used for about 10 to 10 evenings. Other calcium and magnesium foods and preparations can also be used. These are J. Written by Wmems “Techniques 1 gisches Chemic”
21, P325 (1956) and 23, PII05 (19 spots). Next, preferred examples of embodiments of the present invention will be listed. 1 Nordihydroguaiaretic acid from 0.01 to 1
molar Ag and gallic acid alkyl ester 0.0
The photosensitive material according to the claims, characterized in that it contains 0.05 to 0.1 mol Ag. 2 0.01 to 0.0 gallic acid alkyl ester
The photosensitive material described in Claims and Embodiment 1, characterized in that it contains 3 mol Ag. 3. The photosensitive material described in Claims and Embodiments 1 to 2, wherein the gallic acid alkyl ester has 1 to 5 carbon atoms in the alkyl group. 4. The photosensitive material described in Claims and Embodiments Items 1 and 2, wherein the gallic acid alkyl ester is propyl gallate or butyl gallate. 5. A relief image forming method, characterized in that the photosensitive material described in Claims and Embodiments 1 to 4 is treated with an alkaline aqueous solution having a pH of 9 or more. EXAMPLE A wash-off type silver halide photographic film was prepared by the following method. Sample A An emulsion containing 175 grams of gelatin and 1.5 moles of silver chlorobromide (30 mole % silver bromide) in 2000 grams of water was prepared. The average grain size of the silver chlorobromide was 0.4 microns.
After removing soluble salts from this emulsion in a conventional manner, sodium thiosulfate was added to chemically sensitize it. The following substances were added to this raw emulsion. Saponin 6% aqueous solution
20 grams benzotriazole 1% methanol solution 4 grams tartrazine 10% aqueous solution 25
0 grams Solution 'a' with the following composition 316
3 grams of solution 'a' was then coated on a triacetate film base so that the amount of silver coated was 3 grams per pillow. This photographic film will be referred to as sample A. Sample B 175 grams of gelatin and 1 silver chloride in 2000 grams of water
．． An emulsion was prepared containing 5 mol. The average grain size of the silver chloride was 0.4 microns. After removing soluble salts from this emulsion in a conventional manner, it was chemically sensitized by adding sodium thiosulfate. The following substances were added to this raw emulsion. This emulsion was then coated in the same manner as Sample A. This photographic film will be referred to as Sample B. saponin 6
% aqueous solution 75 grams gelatin 10%
Aqueous solution 420 grams 2-mercapto-
Penzothiazole 1% methanol solution
4 grams tartrazine 10% aqueous solution
150 grams of dispersion made by the following method
1201 grams Part (b-
1) and part (b-2) were mixed and then vigorously mixed to form a dispersion. Sample C In sample A, N. D. G. In place of the solution 'a} with the exemplified compound {3'}, N. D. C. Sample A except that 287.3 grams of lysate 'c- containing only A was added.
Photographic film was made using exactly the same method. This photographic film is designated as Sample C. Dissolved solution 'c - Comparative sample ○ In sample C, the N. D. G. In place of A, 21 grams of catechol was added. A photographic film was prepared in exactly the same manner as Sample A except that the dissolving solution {d' was added. This photographic film is referred to as Comparative Sample D. Comparative sample E In sample C, the N. D. C. A. Photographic film was prepared in exactly the same manner as Sample C, except that a solution 'e} containing 35 grams of 3,3,3,3-tetramethyl-5,6,5,6-tetrahydroxy-spiro-bis-indane was added instead. I made it. This photographic film is referred to as Comparative Sample E. Sample Results 1 The above samples A to E were exposed for 5 seconds under a light sliding door, and then developed using an activator treatment solution with the following composition at 20°C, and then the unmonitored membrane portion was exposed in 40q0 of water. It was wiped off with a sponge and then dried. Table 1 shows the photographic properties of the activator treatment solution. Table 1 Sample A and Sample B prepared according to the present invention are Sample C using dihydroguaiaretic acid alone, Sample D using catechol, and Sample E using polyhydroxy-spiro bis-indane. It can be seen that the sensitivity, y, and maximum density are all higher than that of the previous one. Test Results 2 Preservability tests were conducted on samples A to E. Samples at 50 oo and 70% relative humidity for forced aging
I left it for 3 days. Thereafter, the melting point of the emulsion film and the degree of stain generation after processing were investigated. The results are shown in Table 2. Table 2 As can be seen from Table 2, Sample A and Sample B prepared according to the present invention have a small increase in melting point over time, and no staining is observed, so they have excellent storage stability.

Claims (1)

[Scope of Claims] 1. Nordihydroguaiaretic acid and gallic acid alkyl ester are contained in at least one of the light-sensitive silver halide photographic emulsion layers or other hydrophilic colloid layers coated on the support. A silver halide photographic material characterized by: Here, the alkyl group of the gallic acid alkyl ester is an optionally substituted alkyl group having 1 to 10 carbon atoms.