JPH0363060B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photosensitive material which prevents damage caused by scattering of incident light by various constituent photographic element layers of the silver halide photosensitive material, so-called halation and irradiation. The present invention relates to a silver halide photosensitive material which prevents such damage by using a preventive dye. The image light beam incident on a silver halide photosensitive material (hereinafter abbreviated as a photosensitive material) is transmitted through a photosensitive silver halide emulsion layer (hereinafter abbreviated as an emulsion layer) and a non-photosensitive intermediate layer constituting the photosensitive material. It is scattered in various photographic constituent layers (hereinafter referred to as constituent layers) such as the support layer, giving a sensitive area with unclear boundaries outside the image luminous flux range, and significantly reducing the sharpness of the image. One type of light scattering is irradiation, which is reflection on the surface of silver halide grains included in the constituent layers and other particles that have a different refractive index from the binder of the constituent layers, or refraction of the particles and redirection of the incident direction. This is light scattering due to light that changes direction and exits into the binder, and it is difficult to take measures against the refractive index, so we decided to add an anti-light scattering dye (hereinafter abbreviated as an anti-scattering dye) to the constituent layer. Therefore, efforts are being made to eliminate obstacles caused by radiation. Another type of light scattering is halation. This is caused by refraction and reflection at the interfaces of various constituent layers with different refractive indexes. The various constituent layers generally have different optical densities and therefore different refractive indices depending on the degree of hardness or the substance contained in the constituent layers, but the most important factors are the binder and support of the constituent layers, and the relationship between the binder and air. Since the image light flux is at the interface between The focus is on prevention. That is, a constituent layer containing an anti-dispersion dye is provided between the emulsion layer and the support layer, or the support itself is colored, or a backing containing carbon black, an anti-dispersion dye, etc. is provided on the opposite side of the support layer from the emulsion layer. Measures to prevent halation, such as providing layers, have been taken. Note that the support coloring method and the backing layer method may not be applicable depending on the light-sensitive material. Anti-scattering dyes play an extremely important role in eliminating disturbances caused by light scattering. Ideally, anti-scattering dyes should have a light absorption rate and absorption wavelength range that do not impair the sensitivity and sensitivity spectrum of the photosensitive material. It must not impair the properties of the various constituent layers of the material. In particular, it is rare that it is inert to the emulsion layer. Furthermore, it is unnecessary after light scattering is eliminated during exposure, and on the contrary, it interferes with the intended use of the photosensitive material, so it has excellent decolorizing properties that either disappears from the photosensitive material or becomes completely colorless at the same time as the photosensitive material is processed. Must be. Many efforts have been made by those skilled in the art to find dyes that meet these conditions. For example, oxonol dyes having a pyrazolone nucleus, typified by the dyes described in British Patent No. 506385;
Oxonol dyes having barbituric acid nuclei represented by the dyes described in U.S. Pat. No. 3,247,127, and others such as those described in U.S. Pat. No. 2,533,472, U.S. Pat. oxonol dyes, hemioxanol dyes represented by the dyes described in British Patent No. 584,609, styryl dyes represented by the dyes described in US Pat. No. 2,298,733, and US Pat. No. 2,493,747. Examples include merocyanine dyes, typified by the dyes described in the book, and cyanine dyes, typified by the dyes described in US Pat. No. 2,843,486. Styryl dyes such as those described in British Patent No. 733124, British Patent No.
Specification No. 1075653 (general formula), British Patent No. 1153341, British Patent No. 1284730, French Patent No.
No. 1401588 (but general formula) Merocyanine dyes as described in each specification, U.S. Patent No. 2843486, No. 3294539, British Patent No. 1075653
Examples include cyanine dyes as described in each specification (with general formula and general formula). Most of the dyes that are decolorized in the photographic processing process are decolorized by sulfites (or acidic sulfites) contained in the developing solution or by alkaline conditions with them. For example, as described in British Patent No. 506385. These dyes are usually selected to be decolorized during the photographic processing process. However, few of them are completely decolorized, and many of them leave a slight stain on the film after processing. In addition, many dyes that are completely bleached are incomplete, and decompose while stagnant as a coating solution during the coating process of photosensitive material manufacturing.
They often have the disadvantage of varying dye concentrations at the beginning and end of the application. An object of the present invention is to provide a light-sensitive material in which the problem of light scattering is eliminated without impairing the photographic properties of the light-sensitive material, and in which the anti-dispersion dye used has good decolorizing properties. The object of the present invention is to provide a silver halide photosensitive material in which at least one constituent photographic element layer of the material contains a dye represented by the following general formula (), a dye represented by the general formula (), and a dye represented by the general formula (). This can be achieved using a silver halide photosensitive material containing a dye shown in the following. In the formula, R ₁ represents a carboxyl group or an alkyl group, and R ₂ represents a phenyl group substituted with a sulfo group. Further, R ₃ , R ₄ , R ₅ and R ₆ represent an alkyl group or an alkyl group substituted with a hydroxyl group. R ₇ and R ₈ are sulfo group, sulfoalkyl group,
It represents an alkoxy group, a sulfonato group, or a sulfonatoalkyl group, and at least one of R ₇ and R ₈ is a sulfonato group or a sulfoalkyl group. These dyes are stable even when the coating solution is stagnant and are good as anti-dispersion dyes, but when used alone, they cause significant staining after treatment. However, when these three are used in combination, a constituent layer that is free from contamination after treatment and is highly effective as an anti-light scattering layer can be obtained. For the synthesis of these dyes, dyes of general formula () may be synthesized according to Japanese Patent Publication No. 31-10578, and dyes of general formula () may be synthesized according to German Patent No. 616007. do it. In addition, in the case of dyes of the general formula (), for example, JP-A-51-
It can be synthesized with reference to Japanese Patent No. 10927. The dyes of the general formulas (), () and () of the present invention may be contained in the emulsion layer or in other constituent layers containing hydrophilic colloids, but may be contained in the backing layer. The most advantageous case is that no mordant is required. Specific examples represented by the general formulas (), (), and () used in the present invention are shown below. Dyes belonging to general formula () Dyes belonging to general formula () Dyes belonging to general formula () In the photographic material of the present invention, the dye can be introduced into the hydrophilic colloid layer by a conventional method. That is, an aqueous solution of the dye at an appropriate concentration is added to the silver halide photographic emulsion solution before coating when coloring the emulsion layer, or an aqueous solution of a hydrophilic colloid when coloring non-light-sensitive constituent layers. In addition, these liquids may be coated on the support or on the layers constituting the photosensitive material by a known method. The amount of dye added to the coating solution is determined in a conventional manner based on the desired absorption density of the anti-light scattering layer, layer thickness, dye absorption, etc. Since the dye used in the present invention has high solubility in water and high compatibility with major hydrophilic colloids, the amount added is usually hardly restricted by solubility or compatibility. The dye-containing hydrophilic colloid layer of the present invention can be applied by dipping coating (including the use of an air knife), curtain coating, or extrusion coating (for example, using the hopper described in U.S. Pat. No. 2,681,294). including methods), etc.
Various application methods can be used. It is also possible to simultaneously apply two or more layers by the methods described in US Pat. No. 2,761,791 and US Pat. No. 2,941,898. In addition to the aqueous dye based on the present invention, other water-soluble dyes known so far may be used in the emulsion layer and other hydrophilic colloid layers of the light-sensitive material to the extent that the effects of the present invention are not substantially impaired. It may also contain a dye. Alkali-soluble pigments such as manganese dioxide can be included with the dyes according to the invention. The layer to be colored according to the invention can contain a polymeric mordant as well as a hydrophilic colloid. Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues, such as those described in UK Patent No. 685,475; Polymers, maleic anhydride copolymers or derivatives thereof as described in British Patent No. 906083, British Patent No.
Polymers obtained by the reaction of polyvinyl alkyl ketone and aminoguanidine as described in US Pat. Such a polymer, JP-A-1988
Addition polymers of bisacrylamide and secondary diamine or quaternary salts thereof as described in Publication No. 24733, polyvinylpyridine or polyvinyl as described in British Patent Nos. 765520 and 766202. quinoline-containing terpolymers or quaternary polymers, such as those described in DE 1914361 and DE 1914362, of various types known as mordants for acid dyes suitable for light-sensitive materials. Polymers can be used. In addition to hydrophilic colloids, dyes, pigments, and mordants, the dye-containing hydrophilic colloid layer of the present invention includes hardeners, coating aids, plasticizers, slipping agents, matting agents, formulated polymerization latex, and electrostatically charged materials. It can contain additives with various functions to improve the quality of the photosensitive material, such as inhibitors, ultraviolet absorbers, and antioxidants. In the light-sensitive material of the present invention, the emulsion layer may be single or plural, and the dye-containing emulsion layer or other hydrophilic colloid layer may be single or plural. Hydrophilic colloids constituting the photosensitive material of the present invention include not only gelatin (which may be treated with lime or acid), but also gelatin derivatives such as gelatin and aromatic colloids such as those described in U.S. Pat. No. 2,614,928. Gelatin derivatives made by reaction with sulfonyl chlorides, acid chlorides, acid anhydrides, isocyanates, 1,4-diketones, by reaction of gelatin with trimellitic anhydride as described in U.S. Pat. No. 3,118,766 Gelatin derivatives produced by the reaction of gelatin with an organic acid containing an active halogen described in Japanese Patent Publication No. 39-5514, Japanese Patent Publication No. 1972-
Gelatin derivatives obtained by the reaction of aromatic glycidyl ether and gelatin described in Publication No. 26845,
Gelatin derivatives obtained by reacting gelatin with maleimide, maleamic acid, unsaturated aliphatic diamide, etc. described in U.S. Patent No. 3186846, sulfoalkylated gelatin described in British Patent No. 1033189, U.S. patent Polyoxyalkylene derivatives of gelatin as described in Specification No. 3312553; polymer grafted products of gelatin, such as acrylic acid, methacrylic acid, their monovalent or esters with alcohols, as well as amides, acrylic (or methacrylic) ) Gelatin grafted with nitrile, styrene and other vinyl monomers alone or in combination; synthetic hydrophilic polymeric substances such as vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth)acrylate), (meth)acrylamide , homopolymers containing monomers such as N-substituted (meth)acrylamide or mutual copolymers of these, copolymers of these with (meth)acrylic acid esters, vinyl acetate, styrene, etc., and any of the above. Copolymers with maleic anhydride, maleamic acid, etc.; natural hydrophilic polymeric substances other than gelatin, such as casein, agar, alginate polysaccharides, etc., can also be used alone or in combination. Supports include soda glass, potash glass,
Glass plates made of glasses such as borosilicate glass, quartz glass, etc.; polyesters such as polyalkyl (meth)acrylate, polystyrene, polyvinyl chloride, partially formalized polyvinyl alcohol, polycarbonate or polyethylene terephthalate, nylon, etc. Films, paper, baryta-coated paper made of synthetic polymers such as polyamide, or semi-synthetic polymers such as cellulose nitrate, cellulose acetate-butyrate, etc.
Any of the transparent or opaque supports used in photographic elements can be used, such as paper coated with alpha-olefin polymers, synthetic papers such as polystyrene, ceramics, and metals. In the light-sensitive material of the present invention, the emulsion layer and other constituent layers containing hydrophilic colloids can be hardened by adding a commonly used hardening agent. Hardeners include: aldehydes, such as glyoxal as described in US Pat. No. 1,870,354, glutaraldehyde as described in British Patent No. 825,544; N-methylol compounds, such as N,N'-dimethylol; Urea, British Patent No. 676628
dimethylolhydantoin, etc.; dioxane derivatives, such as those described in U.S. Pat.
Dihydroxydioxane described in the specification of US Pat. No. 3380829, or the above derivative described in Japanese Patent Publication No. 46-38713; Compounds having an epoxy group, such as US Pat. Compounds described in publications; compounds with reactive halogens, such as those described in U.S. Pat.
2,4-dichloro-6 described in specification No. 3325287
-Hydroxy-1,3,5-triazine; mucohalogenic acids, such as mucochloric acid and mucobromic acid described in U.S. Pat. No. 2,080,019, or the same derivatives as described in Japanese Patent Publication No. 1872-1972; U.S. Pat. No. 2,726,162 Bis(methanesulfonate ester) described in the specification of US Pat. Compounds described in Publication No. 37-8790; Divinyl sulfones, such as the compounds described in US Pat. No. 2,579,871; Compounds having a reactive olefin bond, such as the compounds described in German Patent No. 872,153. divinyl ketone, such as U.S. Patent No. 3,255,000,
3635718, British Patent No. 994869, West German Patent No.
Compounds having an acryloyl group as described in US Pat. No. 1090472; alkylene bismaleimides as described in US Pat. No. 2,992,109; isocyanates as described in US Pat. No. 3,103,437; US Pat. No. 3,100,704 Carboimides described in specifications, etc.; isoxazole derivatives, such as compounds described in U.S. Pat. , such as the dialdehyde starch described in U.S. Pat. These can be used alone or in combination. In the light-sensitive material of the present invention, various known surfactants can be added to the emulsion layer and other constituent layers as coating aids, or for antistatic purposes, improving slipperiness, and other purposes. For example, saponin, polyethylene glycol, U.S. Pat.
Polyethylene glycol-polypropylene glycol condensates described in US Pat. No. 3,294,540, polyalkylene glycol ethers, polyalkylene glycol esters, polyalkylene glycol amides, etc. described in US Pat. No. 2,240,472 and US Pat. No. 2,831,766 Nonionic surfactants; e.g. alkyl carboxylates,
Alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, U.S. Patent No. 2739891
N-acylated-N-alkyltaurine described in US Pat. No. 2,359,980, US Pat.
maleopimarate described in specification No. 2447750,
or anionic surfactants such as the compounds described in US Pat. No. 2,823,123 and US Pat. No. 3,415,649;
For example, British Patent No. 1159825, Special Publication No. 48-43924
Amphoteric surfactants such as the compounds described in each of the publications and specifications of US Pat. No. 3,726,683 can be used. In the light-sensitive material of the present invention, the constituent layers include slipping agents, such as higher alcohol esters of higher fatty acids described in US Pat. No. 2,588,756 and US Pat. No. 3,121,060, casein as described in US Pat. It may also contain higher fatty acid calcium salts described in the specification of No. 1263722, silicon compounds described in the specifications of British Patent No. 1313384, US Pat. No. 3,042,522, and US Pat. No. 3,489,567. Dispersions of liquid paraffin and the like can also be used for this purpose. In the light-sensitive material of the present invention, the emulsion layer and other constituent layers contain plasticizers, such as glycerin, diols described in U.S. Pat. No. 2,960,404, and trihydric aliphatic alcohols as described in U.S. Pat. No. 3,520,694. May include. In the light-sensitive material of the present invention, the emulsion layer and other constituent layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of increasing dimensional stability. For example, alkyl (meth)acrylate, alkoxy (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, A polymer containing a combination of saturated dicarboxylic acid, sulfoalkyl acrylate, styrene sulfonic acid, etc. as monomer components can be used. As a specific example,
U.S. Patent No. 2376005, U.S. Patent No. 3607290, U.S. Patent No. 3645740
British Patent No. 1186699, British Patent No. 1307373, U.S. Patent No. 3062674, British Patent No. 2739137, British Patent No. 3411911, British Patent No.
Examples include polymers described in the specifications of No. 3488708, No. 3635715, and No. 2853457. In the light-sensitive material of the present invention, the constituent layers include matting agents such as the silica described in Swiss Patent No. 330158, the glass powder described in French Patent No. 1296995, and the matting agent described in British Patent No. 1173181. inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc; starch as described in US Pat. No. 2,322,037; starch derivatives as described in Belgian Patent No. 625,451 or British Patent No. 981,198; Polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 30158, polyacrylonitrile described in US Patent No. 3079257, US Patent No. 3022169
organic particles such as the polycarbonate described in the patent specification. In the light-sensitive material of the present invention, the emulsion layer and other constituent layers may contain an ultraviolet absorber such as a compound belonging to the benzophenone, benzotriazole, or thiazolidine family. These ultraviolet absorbers may be mordanted into specific layers in the same manner as dyes. In the light-sensitive material of the present invention, the emulsion layer and other constituent layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener, and these may be water-soluble or water-insoluble brighteners. Whitening agents may also be used in the form of dispersions. In the light-sensitive material of the present invention, the constituent layers may contain compounds having the purpose of preventing color fogging in the case of color light-sensitive materials or preventing color mixing between layers, such as alkylhydroquinones, dialkylhydroquinones, aryl-substituted hydroquinones, sulfo-substituted hydroquinones, etc. , polymer compounds having hydroquinone residues, catechol derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acids, etc., may optionally be included as a dispersion. Specific examples of compounds include British patent no.
No. 557750, No. 557802; U.S. Patent No. 2336327,
Same No. 2360290, No. 2403721, No. 2728659, Same No.
No. 2732300, No. 2735765, No. 2418613, No. 2732300, No. 2735765, No. 2418613, No.
No. 2675314, No. 2710801, No. 2816028, No.
2360290, French Patent No. 885982, US Patent No. 2336327, French Patent No. 2403721, British Patent No. 1133500
No. 3,457,079, U.S. Patent No. 2,360,290
No., No. 2384658, specifications, and Special Publication No. 13496, No. 43-1384
There is a compound described in the publication No. In order to introduce these compounds into the constituent layers, for example, a method of dispersing them in a hydrophilic colloid together with a high boiling point organic solvent such as an aliphatic ester, an aromatic carboxylic acid alkyl ester, an aromatic phosphate ester, or an aromatic ether; A method such as adding it to a hydrophilic colloid as an alkaline aqueous solution can be used. The silver halide emulsion used in the light-sensitive material of the present invention can be prepared by various conventionally known methods so as to have properties suitable for the intended use of the light-sensitive material. As the silver halide, any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, etc. may be used, and the content ratio of the halogen is not particularly limited. Protective colloids used during the formation of silver halide precipitates include commonly used gelatin, acylated gelatin such as phthalated gelatin and succinylated gelatin, and grafts such as acrylamide and hydroxyalkyl (meth)acrylate. gelatin derivatives such as gelatin; e.g., three monomers: acrylic acid (or methacrylic acid), acrylamide (or methacrylamide), and amine derivatives of any of them (e.g., N-(dialkylaminoalkyl)-acrylamide); Synthetic polymers such as copolymers consisting of the following can be used alone or in combination. A known method can be used to prepare the silver halide emulsion. For example, “The Theory of the Photographic Process” by CEKMess
3rd ed., 1966, Mac Millan Co., New
York; “Chimie” by P. Grafkides
Photographique”2nd ed., 1957, Photocinema
Paul Montel, Paric; “Die” edited by H. Frieser
Grundlagender Photographische Prozesse mit
Silberhalogeniden”1968.Akademische
Verlaggesellschaft Frankfurt-am-Main.2nd
The principles and methods described in Vol. 609-674, pages 735-743, etc. can be used. Any of the acidic method, neutral method, or ammonia method may be used, and the single-jet method or double-jet method may be used. Berichte der Bunsengesellschaft fu¨r
physikallische Chemie, Band 67 (1963),
The so-called control jet method, as described on pages 349 et seq., can also be used if necessary. Such a method is advantageous in obtaining emulsions with extremely narrow grain size distribution. The shape of the silver halide grains may be a cube, an octahedron, a dodecahedron due to the coexistence of these, various twin crystals, or a mixture thereof. Silver halide emulsions may be coarse grained or fine grained. The silver halide emulsion may or may not be physically ripened. After the emulsion is precipitated or physically ripened, soluble salts are usually removed, and even if the long-known Nudel water washing method is used, inorganic salts containing polyvalent anions (for example, ammonium sulfate) cannot be removed. ,
Coagulation methods using anionic surfactants, anionic polymers such as polystyrene sulfonic acid, or gelatin derivatives such as aliphatic or aromatic, acylated gelatin may also be used. The silver halide emulsion used in the present invention may or may not be chemically sensitized. Chemical sensitization methods are described by Mess, Grafkides, or Frieser (eds.).
The method described in et al. and various other known methods can be used. That is, sulfur-containing compounds that can react with silver ions, such as thiosulfates, or U.S. Pat.
No. 2278947, No. 2410689, No. 3189458, No.
3501313, compounds described in French Patent No. 2059245, or sulfur sensitization using activated gelatin;
stannous salts described in specification No. 2487850;
U.S. Patent No. 2518698, U.S. Patent No. 2521925, U.S. Patent No. 2521926
amines described in the specifications of No. 2419973 and No. 2419975, iminoaminomethane sulfuric acid described in U.S. Patent No. 2983610, silane compounds described in U.S. Patent No. 2594637, etc. Journal of Photographic Science
HW described in Volume 1 (1953) page 163 et seq.
Reduction sensitization method such as Wood's method; U.S. Patent No.
Gold sensitization method using gold complex salt or gold thiosulfate complex described in No. 2399083; US Patent No.
No. 2448060, No. 2540086, No. 2566245, No.
Sensitization methods using salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium, which are described in each specification of No. 2566263, can be used alone or in combination. Also, instead of or in conjunction with sulfur sensitization, U.S. Pat.
The selenium sensitization method described in No. 3297446 can also be used. The silver halide emulsion used in the light-sensitive material of the invention may be spectrally sensitized to long-wave blue light, green light, red light or infrared light using a sensitizing dye. As sensitizing dyes, cyanine dyes, merocyanine dyes,
Any of complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemincyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. The dye belonging to cyanine may have any nitrogen-containing heterocyclic ring such as pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole or pyridine as a basic nucleus. These nuclei have substituents such as alkyl groups, alkylene groups, hydroxyalkyl groups, carboxyalkyl groups, sulfoalkyl groups, aminoalkyl groups, alkoxyalkyl groups, sulfohydroxyalkyl groups, and sulfoalkoxyalkyl groups. You may. These nuclei also contain unsubstituted or halogen atoms,
Alkyl group, alkoxy group, hydroxy group, cyano group, carboxy group, alkoxycarbonyl group,
A hydrocarbon ring substituted with an alkylamino group, a dialkylamino group, an acylamino group, a phenyl group, a fluoroalkyl group, or such a heteroartic ring may be fused. Cyanine dye is
They may be symmetrical or asymmetrical, and the methyl and polymethine chains may be substituted with alkyl groups, phenyl groups, substituted phenyl groups such as carboxyphenyl groups, isophorone nuclei, or heteroartic ring nuclei. The merocyanine dye has the above-mentioned basic nucleus and acidic nucleus such as 2-thioxazolidinedione, rhodanine,
Acidic nuclei such as thiohydantoin, barbituric acid, thiobarbituric acid or

A compound having a group (A is an electron-withdrawing group) may be used.
The acidic nucleus may be substituted with an alkyl group, an alkylene group, a phenyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group, an alkoxyalkyl group, an acylamino group, a heterocyclic nucleus, or the like. These sensitizing dyes may be used singly or in combination. A large number of combinations of sensitizing dyes are known for the purpose of supersensitization. Along with sensitizing dyes, substances that exhibit supersensitizing effects without substantially absorbing visible light, such as U.S. Pat.
Compounds having a pyrimidinylamino group or triazinylamino group described in specifications such as No. 3615632 and No. 3615641, aromatic organic acid-formaldehyde condensates described in British Patent No. 1137580, azaindenes, or Cadmium salts and the like may also be included in the emulsion. In the light-sensitive material of the present invention, various compounds may be contained in the emulsion for the purpose of preventing fog during the manufacturing process, storage of the light-sensitive material, or development processing, or for stabilizing photographic performance. That is, azoles such as benztriazole,
Benzthiazolium salts as described in U.S. Pat. No. 2,131,038; aminobenzimidazole as described in U.S. Pat. No. 2,324,123; nitroazoles such as nitrobenzindazole; Nitrobenzimidazole, such as the nitroaminobenzimidazole described in U.S. Pat. No. 2,324,123; halogen-substituted azoles, such as 5-chlorobenzimidazole, 5-bromoimidazole, or 6-chlorobenzimidazole; mercaptoazoles , such as mercaptothiazole derivatives described in US Pat. No. 2,824,001, mercaptobenzthiazole, US Pat. No. 2,679,099
The derivative described in US Pat. No. 3,252,799
Mercaptoimidazole derivatives described in US Pat.
2843491, mercaptothiadiazole described in U.S. Pat. No. 1,758,576, U.S. Pat.
phenylmercaptotetrazoles, etc., as described in US Pat. No. 2,304,927; mercaptopyrimidines, as described in US Pat. No. 2,304,962;
Mercaptotriazine as described in GB 2476536; mercaptotetrazaindene as described in GB 3226231; thiosalicylic acid as described in US 2 377 375;
Thiobenzoic acid described in specification No. 3226231, Tokukosho
Sugar mercaptal and various other mercapto compounds described in Publication No. 47-8743, U.S. Patent No. 3251691
Oxazolinthione described in the specification of the Japanese Patent Publication No. 43
Triazolothiadiazole described in Japanese Patent No.-17932 and the like can be added. Also, azaindene compounds, such as tetrazaindenes, such as U.S. Pat.
Compounds described in each specification, Japanese Patent Publication No. 39-10166, and Japanese Patent Publication No. 42-10516; pentazaindenes, such as compounds described in U.S. Patent No. 2713541 and Japanese Patent Publication No. 43-13495 Alternatively, a nitrogen-containing heterocyclic compound having an antifogging effect such as urazol described in US Pat. No. 2,708,161 can be added. Also, benzenesulfinic acid and benzenethiosulfonic acid described in US Pat. No. 2,394,198, Japanese Patent Publication No. 43-4136
Benzene sulfinic acid amide described in Japanese Patent Publication No. 1987-8743, sugar mercaptal described in Japanese Patent Publication No. 47-8743, etc. can be added. In addition, US Patent No. 2691588, British Patent No. 623488, Japanese Patent Publication No. 43-4941,
Various chelating agents described in Japanese Patent No. 43-13496 can be added. In the light-sensitive material of the present invention, the emulsion layer or other constituent layers may be added for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, as described in US Pat.
Polyalkylene oxides as described in US Pat. No. 2,441,389, ethers, esters, and amides of polyalkylene oxides as described in US Pat.
No. 45-15188, No. 46-43435, No. 47-8106
Other polyalkylene oxide derivatives described in U.S. Pat. The thioether compounds described in Japanese Patent Publication No. 47-28325; pyrrolidine and the like described in Japanese Patent Publication No. 45-27037; urethane or urea derivatives described in Japanese Patent Publication No. 40-23465; The imidazole derivatives described in Japanese Patent Publication No. 45541; polymers such as those described in Japanese Patent Publication No. 45-26471; and pyrazolidones described in Japanese Patent Publication No. 45-27670 may also be included. An inorganic or organic mercury compound may be added to the emulsion in the light-sensitive material of the invention for the purpose of sensitization or fog prevention. For example, U.S. Pat.
Mercury complex salts described in US Pat. No. 2728664; US Pat.
Benzthiazole mercury salts described in US Pat. No. 2728667; for example, mercury salt compounds described in US Pat. No. 2728663 and US Pat. No. 2732302; organic compounds described in US Pat. Mercury compounds can be used. When the silver halide grain size is particularly small (less than 0.4 μm), the emulsion in the light-sensitive material of the present invention may be used as a sensitizer, for example, in British Patent No. 1316493,
No. 1317138, No. 1317139, No. 1317709, No. 1317138, No. 1317139, No. 1317709, No.
Compounds described in German Patent No. 1297901 and West German Patent Publication No. 2235031 can be added. In the light-sensitive material of the present invention, the emulsion layer may contain a commonly used non-diffusive color image forming coupler. A color image-forming coupler is a compound that reacts with an oxidation product of an aromatic primary amine developing agent to form a dye during photographic development (hereinafter abbreviated as coupler). The coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for color correction or a coupler that releases a development inhibitor. As yellow-forming couplers, ring-opening ketomethylene compounds such as acylaminoacetamide compounds are useful; as magenta-forming couplers, pyrazolone-based or cyanoacetyl-based compounds are useful; and as cyan-forming couplers, naphthol-based or phenol-based compounds are useful. The coupler can be introduced into the emulsion layer using a method commonly used for multicolor light-sensitive materials. The present invention is also applicable to multilayer, multicolor light-sensitive materials having at least two different spectral sensitivities on a support. A multilayer multicolor light-sensitive material usually has 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. The usual combination is that 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. In the light-sensitive material of the present invention, the emulsion layer and other constituent layers contain a developing agent such as aromatic diols such as hydroquinone, aminophenols, phenylenediamines, 3-pyrazolidones, ascorbic acid or its derivatives, It may be included alone or in combination. Combinations of hydroquinone and N-hydroxylalkyl-substituted para-aminophenol derivatives as described in Japanese Patent Publication No. 48-43814 are particularly useful. The developing agent can also be added as a dispersion if it is water-insoluble. The emulsion layer and other constituent layers in the light-sensitive material of the present invention can be coated by various known coating methods. Coating methods include dipping coating, air knife coating, roller coating, curtain coating, and extrusion coating. US Patent No. 2681294
The method described therein is one of the advantageous methods. Further, two or more layers may be applied simultaneously using methods such as those described in US Pat. No. 2,761,791 and US Pat. No. 3,526,528. The photosensitive material of the invention may have an antistatic layer or a conductive layer, for example a vapor-deposited or electrodeposited metal layer, or a layer consisting of an ionic polymer. Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used, and the treatment temperature can be lower than 18°C, from 18°C to 50°C, or higher than 50°C. Depending on the purpose, the light-sensitive material of the present invention can be subjected to either a development process for forming a silver image (black and white photographic process) or a color photographic process consisting of a development process for forming a dye image. When subjecting the light-sensitive material of the present invention to black-and-white photographic processing,
The developer solution used can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone,
isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3- pyrazolidone,
1-phenyl-4-ethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (e.g. o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4 -diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (such as 1-(p-hydroxyphenyl)-3-aminopyrazoline, 1
-(p-methylaminophenyl)-3-aminopyrazoline, 1-(p-aminophenyl)-3-aminopyrazoline, 1-(p-amino-m-methylphenyl)-3-aminopyrazoline, etc.), etc. can be used alone or in combination. The developer may also contain preservatives (e.g. sulfites, bisulfites, ascorbic acid, etc.), alkaline agents (hydroxides, carbonates, etc.), PH buffers (e.g. carbonates, borates, etc.), as necessary. boric acid, acetic acid, citric acid, alkanolamines, etc.), solubilizing agents (e.g. polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (e.g. nonionic surfactants including polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants,
Defoamers, antifoggants (e.g. halides such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benztriazole, benzthiazole, tetrazoles, thiazoles, etc.), chelating agents (e.g. ethylenediamine) tetraacetic acid or its alkali metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (such as U.S. Pat.
2304025 and Japanese Patent Publication No. 47-45541), a hardening agent (for example, glutaraldehyde, etc.), an antifoaming agent, etc. can be added. A so-called "lith type" development process can be applied to the photosensitive material of the present invention. "Lith-type" development processing is a development process in which dihydroxybenzenes are usually used as a developing agent and a low sulfite ion concentration is used for the photographic reproduction of line images or the halftone dot photographic reproduction of halftone images. This refers to a developing process that is carried out contagiously. In the light-sensitive material of the present invention, the dye is easily decolorized even at a low sulfite ion concentration, so its advantage is particularly emphasized in the "lith type" development process. As a special form of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution to perform development. Such development treatment is often used in combination with silver salt stabilization treatment using thiocyanate as one of the methods for rapid processing of light-sensitive materials, and such treatment is also possible. In the case of such rapid processing, the effects of the present invention are particularly large. As the fixer, one having a commonly used composition can be used. A fixer is generally an aqueous solution consisting of a fixer, a hardener, and others, and the pH is usually
It is 3.8-5.0. As a fixing agent, in addition to thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate, and thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, organic sulfur compounds that can form soluble stable silver complex salts can be used. A fixing agent known in the art can be used. It is common to add to the fixer a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum, etc., which acts as a hardening agent. When forming a dye image, conventional methods can be applied. For example, “Journal of the Society of
Motion Picture and Television Engineers”61
Vol. (1953), pp. 667-701, the negative-positive method involves giving an imagewise exposure and developing with a developer containing a black and white developing agent to produce a negative silver image, which is then subjected to at least one uniform process. Color reversal methods, in which a dye-positive image is created by exposure (or other suitable fogging treatment) followed by color development, or direct positive emulsion methods, in which a dye-positive image is created, are used. Color developers generally consist of alkaline aqueous solutions containing color developing agents. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., N,N-diethylparaphenylene diamine, N-ethyl-N-(β-hydroxyethyl)amino-2-methylaniline, −
(N-ethyl-N-β-methanesulfonamidoethyl)amino-2-methylaniline, N,N-diethylamino-2-ethoxyaniline, etc.), p
-Aminophenols (for example, 4-(aminophenol, 2,6-dichloro-4-aminophenol, 2-bromo-4-aminophenol, etc.), etc.) are used.The color developer may contain other usual additives, such as alkali. metal sulfites, carbonates,
Can include bisulfites, bromides, iodides, alkaline buffers, and the like. Furthermore, if necessary, dye-forming couplers, competitive couplers, antifoggants, hardeners, antioxidants, thickeners, and the like may be added. According to the present invention, even if any of the constituent layers of the photosensitive material contains a dye, it does not matter whether it is photographic processing (black and white processing or color processing).In addition to normal black and white processing,
It also includes so-called Lith-type photographic processing, rapid photographic processing consisting of an activation bath and/or silver salt stabilization treatment that does not contain a developing agent, and silver salt diffusion transfer processing.Color processing includes negative processing and color processing in which color is added to a color developing solution. Any type of color reversal processing with or without forming couplers, processing by silver dye bleaching method, color image forming method by diffusion transfer, etc.) may be used, especially in photographic processing where processing time is shortened. Does not leave any color residue on the material. According to the present invention, any one of the constituent layers of the photosensitive material (generally, it is often a layer containing a dye)
When a polymeric mordant is present in the layer to selectively dye that layer, the dye is well retained in that layer and diffusion to other layers is extremely small. Alternatively, it functions well as a layer for other purposes, and there is very little effect of reducing sensitivity due to a filter effect on the emulsion layer above this layer (distant from the support). In addition, even if a cationic polymer mordant is present in any of the hydrophilic colloid layers, no coloring remains on the photographic material after the photographic processing as described above. EXAMPLES The present invention will be explained in more detail with reference to Examples below. Example 1 Dye A of the present invention was added to an 8% aqueous gelatin solution 1 containing a hardener and a coating aid as shown in Table 1 below.
-1, B-1 and C-1 and dyes X-1 and X-2 outside the invention for comparison, and coated on a primed polyester base at a gelatin content of 60 mg per 100 ^cm2 . Dry. These samples were mixed with commercially available squirrel developer CDL-271.
(manufactured by Konishiroku Photo Industry Co., Ltd.) at 27℃ for 1 minute and 40 seconds,
Commercially available fixer CFL-811 (manufactured by Konishiroku Photo Industry Co., Ltd.)
The sample was treated at 27°C for 1 minute, washed with water, and dried to prepare an evaluation sample. This sample was cut into 10 pieces, stacked one on top of the other, and visually observed for the degree of contamination. The results are shown in Table-1.

【table】

[Table] As can be seen from these results, when only one of each of the three dyes of the present invention is used or when one of the three dyes of the present invention is replaced with a dye other than the present invention staining occurs, whereas only sample 6, which is a combination of dyes of the present invention, does not cause staining. Example 2 An 8% gelatin aqueous solution 1 containing a hardening agent and a coating aid contained dyes according to the present invention and dyes outside the present invention as shown in Table 2 below. Each mixed solution was divided into two parts, and one part was immediately coated and dried in the same manner as in Example 1. A portion of the remaining residue was left at 40°C for 10 hours, and then applied and dried in the same manner. These samples were visually observed to determine whether there was any color change due to long-term standing. The results are shown in Table-2.

【table】

[Table] From this result, one of the three dyes of the present invention
Dye 2, in which the seed was replaced with a dye other than the present invention, has poor dye stability and causes color fluctuations when left for a long time, but Sample 1, a combination of dyes of the present invention, does not cause color fluctuations and is stable. Recognize. Also, sample 1
As in Example 1, Sample 2 had good decolorizing properties and Sample 2 had poor decolorizing properties. Example 3 The dye solution shown in Example 1 was coated as an antihalation backing layer on the opposite side of the backing layer, and gold sensitization and sulfur sensitization were applied in a conventional manner to obtain ortho-sensitized average particles. Diameter 0.25μ
m silver chloroiodobromide emulsion (silver chloride 80 mol%, silver bromide
19.9 mol%, silver iodide 0.1 mol%), the amount of coated silver was
Samples 1 to 8 were obtained by coating at a concentration of 35 mgAg/100cm ² . Sakura Squirrel Ortho OS (product of Konishiroku Photo Industry Co., Ltd.)
The image was exposed to light using a gray contact screen (150 lines), developed with Lith developer CDL-271 (manufactured by Konishiroku Photo Industry Co., Ltd.) at 27°C for 1 minute and 40 seconds, and then subjected to the usual fixing water washing and drying process. In this way, a screen manuscript with a halftone dot area ratio of 50% was prepared. Sample 1~ where this screen manuscript was prepared above
8, and reversed the negatives and positives at various exposure doses. The exposed sample was developed with Lith developer CDL-271 at 27 DEG C. for 1 minute and 40 seconds, and then subjected to conventional fixing, water washing and drying treatments. The halftone area ratio of the obtained sample was measured and the halftone area ratio was 50.
% screen original was returned at three exposure points. The results are shown in Table 3 below.

[Table] In sample 6 provided with the anti-halation backing layer of the present invention, even if the exposure amount was changed, the halftone dot area ratio after the return process was determined from the screen original with a halftone dot area ratio of 50% at each exposure amount. There is little deviation at points, especially at large exposure points where halftone dots tend to collapse. Therefore, a good uniform halftone dot image can be obtained over the entire exposure range. This shows that the antihalation effect is working effectively, which is preferable in practical work. Example 4 Dyes of the invention A-1, B- of sample 6 of Example 1
Evaluations were conducted in the same manner as in Example 1 and Example 3 using the dyes of the present invention shown in Table 4 instead of 1 and C-1, and the results are shown in Table 4.

[Table] From Table 4, it can be seen that the sample containing the dyes of the present invention did not cause staining, and as in Example 3, a good and uniform halftone dot image was obtained over the entire exposure range. Example 5 Dyes of the invention A-1, B- of sample 1 of Example 2
Evaluations were conducted in the same manner as in Example 2 using the dyes of the present invention shown in Table 5 instead of 1 and C-1, and the results are shown in Table 5.

【table】

[Table] From Table 5, it can be seen that the samples in which the dyes of the present invention were combined did not cause color fluctuation and were stable.

Claims (1)

[Claims] 1. A dye represented by the following general formula (), a dye represented by the following general formula (), and a dye represented by the following general formula ().
A silver halide photosensitive material containing a dye represented by: [In the formula, R ₁ represents a carboxyl group or an alkyl group, and R ₂ represents a phenyl group substituted with a sulfo group. Further, R ₃ , R ₄ , R ₅ and R ₆ represent an alkyl group or an alkyl group substituted with a hydroxyl group. R ₇ and R ₈ represent a sulfo group, a sulfoalkyl group, an alkoxy group, a sulfonato group, or a sulfonatoalkyl group, and at least one of R ₇ and R ₈ is a sulfonato group or a sulfoalkyl group. ]