Color photographic light-sensitive material

Abstract

 Multi-layer silver halide color photographic light-sensitive material suitable for miniaturized photographic images because of the image sharpness and insensitivity to formaldehyde vapor has, furthest from the support, its green-sensitive emulsion layer, covered with a protective layer functioning also as a yellow filter layer, said green-sensitive emulsion layer comprising a magenta coupler having the formula (1), (II), (III), (IV) or (V):







wherein R¹ and R² each represents alkyl, aryl, heterocyclic ring amino, acylamino, hydroxy, alkoxy, alkylthio, carboxy, or an esterified carboxy radical; R³ represents a hydrogen atom or a coupling-off radical; Cp represents a blocking coupler radical which, after the reaction thereof with the oxidation product of a color developing agent, produces a colorless or alkali-soluble reaction product.

Description

[0001] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a novel silver halide multi-layered color photographic light-sensitive material which is intended for camera-exposure use in the negative-to-positive printing process and which is improved particularly on the sharpness thereof.

[0002] In recent years, the miniaturization of photographic cameras has been still further in progress. The miniaturization of a camera is accomplished in two ways: One way is to miniaturize a camera without changing the sizes of a multi-layered color photographic light-sensitive material to be used and of the image frame thereof, and the other to miniaturize a camera with reducing in size the multi-layered color photographic light-sensitive material to be used and the image frame thereof. The former, since it is a way in which the miniaturization of a camera is accomplished by use of camera parts reduced in the dimensions thereof, is independent of the photographic characteristics of the multi-layered color photographic light-sensitive material used, but there is naturally a limit to-the miniaturization of the camera in the way. On the other hand, the latter is an effective way that enables a camera to be substantially miniaturized.

[0003] However, if the image frame of a multi-layered color photographic light-sensitive material is reduced in size, because in order to make a print of the same size a larger enlarging magnification needs to be used, the sharpness of the resulting print image quality becomes so much worse. Therefore, to further miniaturize a camera with the image frame of the multi-layered color photographic light-sensitive material used reduced in size, it is essential that the multi-layered color photographic light-sensitive material be provided with an excellent sharpness as one of the high-image-quality photographic characteristics thereof. The development of such a high-image-quality photographic characteristics-having multi-layered color photographic light-sensitive material has now been earnestly demanded.

[0004] For some important and well-known reasons, a subtractive multi-layered color photographic light-sensitive material intended for use in the actual color reproduction comprises at least three independent layers coated on such a support as a cellulose ester base or a polyester base, of which the layer closes to the support contains generally a silver haldie spectrally sensitized to the red region of the visible spectra and a cyan coupler. Generally, on this layer is present a silver halide layer spectrally sensitised to the green region of the visible spectra and containing a magenta coupler, and further on this green-sensitive layer is present the third layer substantially sensitive to the blue region only of the visible spectra and containing an yellow coupler.

[0005] Various methods have hitherto been developed for improving the sharpness of multi-layered color photographic light-sensitive materials.

[0006] Techniques for the improvement on the sharpness of photographic images are broadly classified into two: One is a method which utilizes the development effect, and the other a method which utilizes the optical effect, the latter including such techniques for improving the sharpness utilizing the optical effect as the improvement by the prevention of the scattering of light caused by the silver halide particles, etc., inside a multi-layered color photographic light-sensitive material; the improvement by the prevention of the halation phenomenon with an antihalation treatment on the support, etc.; the improvement by an appropriate arrangement of the component layers; and the like.

[0007] For example, there have been known the improvement by reducing the silver halide amount as described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 117032/1976 and 115219/1977; the improvement by positioning part of the blue-sensitive layers, with the effective sensitivity thereof re-. tained as it is, underneath the green-sensitive layer or the red-sensitive layer and minimizing the influence by the scattering light upon the green-sensitive layer as described in U.S. Patent No. 3,658,536; the improvement by positioning part of the green-sensitive layers uppermost and by the antihalation or antiiradiation treatment with mordanting an acid dye to the fine coacervate particles of a cationic nitrogen- containing activator as described in Japanese Patent Examined Publication No. 37018/1978. However, such conventionally known development effect- and optical effect-utilizing methods, although used in the most effective way, have been still unable to give any desired characteristics. Particularly, these optical effect-utilizing methods showed the disadvantages that they brought about noticeable desensitization and the deterioration of the purity of formed colors.

[0008] On the other hand, in recent years, with the increasing use in daily life of new-type building materials, furniture materials, resin-treated materials, adhesives, etc., which generate such harmful gases as of formalin and the like, there have been increasing opportunities for color photographic light-sensitive materials to come into contact with such harmful gases.

[0009] Generally speaking, it is desirable for color photographic light-sensitive materials that the photographic characteristics thereof do not change during the period including the time before and after camera exposure up to the processing thereof. However, when a coupler-in-emulsion type color photographic light-sensitive material containing couplers is placed in the atmosphere of formaldehyde gas, the couplers and other various additives contained therein react with the formaldehyde thereby to be changed to non-color-formable compounds and to cause such photographically undesirable serious deteriorations of the photographic characteristics thereof as, e.g., the deteriorations of the formed color densities and of gammas, the increase in fog, and the like. Such influences by formalin gas would be furthered if the construction of the layers of a color light-sensitive material is changed or if the material is reduced in size.

[0010] It is therefore an object of the present invention to provide a silver halide color photographic light-sensitive material which is improved on the above-described conventional disadvantages, particularly improved so as not to cause the deterioration of the purity of the formed colors and the desensitization thereof, which is capable of producing a dye image excellent in the sharpness thereof, and which is so significantly improved as to cause the formed dye image to sufficiently resist formalin gas.

[0011] And another object of the present invention will become apparent in the following desclosure of the present'invention.

[0012] As a result of our various studies it has now been found that the above object of the present invention can be accom- _Dlished hv a silver halid^p color photographic light-sensitive material which has on the transparent support thereof a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, an yellow filter layer, a blue-sensitive silver halide emulsion layer and a protective layer, wherein said protective layer is a uppermost layer functioning also as an yellow filter layer and said green-sensitive silver halide emulsion layer is positioned farthest from said support and substantially comprises a photographic coupler capable of forming a magenta dye image by the reaction thereof with the oxidized product of an aromatic primary amine color developing agent, said photographic couplers having the following formulas (I), (II), (III), (IV) and (V):



wherein _R¹ and _R² each represents an alkyl, an aryl, a heterocyclic ring, amino, an acylamino, hydroxy, an alkoxy, an alkyl- thio, carboxy, or an esterified carboxy radical; R³ represents a hydrogen atom or a coupling-off radical; Cp represents a blocking coupler radical which, after the reaction thereof with the oxidized product of a color developing agent, produces a colorless or alkali-soluble reaction product.

[0013] The Cp is preferably represented by -CHR⁴R⁵ radical wherein R⁴ represents an alkyl-O-CO-, an alkyl-CO-, an aryl-O-CO-, an aryl-CO-, -COOH, -N0₂ or -CN; and R⁵ represents the same radicals as defined in R⁴ or an aryl-NHCO- radical (wherein at least one of the R⁴ and R⁵ contains an alkyl or aryl that is substituted by not less than one carboxy, sulfo, or hydroxy radical).

[0014] The above -CHR⁴R⁵ represents a blocking radical that produces a reaction product eliminated to become mobile from the foregoing magenta dye forming coupler radical after the reaction thereof with the oxidized color developing agent.

[0015] The present invention is illustrated in further detail below:

The silver halide color photographic light-sensitive material of the present invention is characterized by being composed in such a manner that, in order to improve the sharpness of a formed dye image on the multi-layered color photographic light-sensitive material, the green-sensitive silver halide emulsion layer (the silver halide emulsion layer is hereinafter simply called "emulsion layer") which contributes visually most effectively to the sharpness of the image is positioned farthest from the support, and into the green-sensitive emulsion layer are incorporated such non-diffusion couplers as having the foregoing formulas which exert no bad influence upon the sharpness of the resulting dye image and which are suitable for improving the sensitivity and preservability of the light-sensitive material, and, besides, the protective layer is present together with an yellow filter layer on the green-sensitive emulsion layer.

[0016] Thus, those magenta couplers having the foregoing formulas, which are to be contained in the above-mentioned green-sensitive emulsion layer, are first illustrated in further detail below:

The coupling-off radical represented by R in the foregoing formulas in the present invention may be any arbitrary coupling-off radical known to those skilled in the art. Such a radical may change the equivalent of the coupler, may change the reactivity of the coupler, or otherwise may exert advantageous influences upon the coupler-coated layers or other layers contained in the element (after being released from the coupler, the radical may exert such functions as, for example, development inhibition, bleach inhibition, bleach acceleration, color supplement, and other various functions).

[0017] Typical examples of the coupling-off radical include halogen, alkoxy, aryloxy, heterocyclylocy, sulfonyloxy, acyloxy, acyl, heterocyclyl, thiacyano, alkyl-thio, aryl-thio, heterocyclyl-thio, sulfonamido, sulfonyloxy and aryl-azo radicals.

[0018] Preferred coupling-off radicals represented by R³ in the present invention include those represented by the formulas:

wherein X is an oxygen atom or a sulfur atom; R is an alkyl, a heterocyclic or an acyl radical; and Q is a group of non-metallic atoms necessary to form a 5-member or 6-member ring.

[0019] The following are preferred examples of the coupling-off radicals of the present invention having Formula (VI) and Formula (VII), but the radicals of the present invention are not limited thereto.

Exemplified compounds:

[0020] 

[0021] Particularly typical couplers according to the present invention are subsequently given below:

Exemplified couplers:

[0022] 





wherein Ph is phenyl, and R is hydrogen

wherein Me is methyl, and Bu is butyl

wherein R is hydrogen or ethyl

wherein X is hydrogen, chlorine or











wherein R is hydrogen or ethyl







wherein R is hydrogen or ethyl

wherein R is hydrogen or ethyl

wherein R is hydrogen or ethyl

[0023] As previously mentioned, in the present invention, the protective layer located on the green-sensitive emulsion layer which is positioned farthest from the support is combined with an yellow filter layer. The density of this yellow filter layer may be not more than 50% of the whole yellow filter density possessed by the silver halide color photographic light-sensitive material or otherwise may be 100%. In addition, the above-mentioned yellow filter layer may be a single layer or may also be a plurality of layers.

[0024] The layers other than the foregoing green-sensitive emulsion layers of the silver halide color photographic light-sensitive material of the present invention, that is, the blue-sensitive emulsion layer and the red-sensitive emulsion layer, may contain couplers other than the couplers having the foregoing formulas.

[0025] For example, for the blue-sensitive emulsion layer, open-chained ketomethylene compounds have been conventionally used; particularly benzoyl-acetanilide type yellow couplers and pivaloyl-acetanilide type yellow.couplers have been generally extensively used. Further, two-equivalent type yellow couplers whose carbon atom in the coupling position thereof is substituted by a substituent that can be eliminated during the coupling reaction have also been advantageously used. Examples of these yellow couplers are described in, e.g., U.S. Patent Nos. 2,875,057, 3,265,506, 3,664,841, 3,408,194, 3,447,928, 3,277,155 and 3,415,652, Japanese Patent Examined Publication No. 13576/1974, and Japanese Patent O.P.I. Publication Nos. 29432/1973, 66834/1973, 10736/1972, 122335/1974, 28834/1975 and 132926/1975.

[0026] Cyan couplers applicable to the present invention are generally phenol or naphthol derivatives, examples of which include those described in, e.g., U.S. Patent Nos. 2,423,730, 2,474,293, 2,801,171, 2,895,826, 3,476,563, 3,737,316, 3,758,308 and 3,839,044, and Japanese Patent O.P.I. Publication Nos. 37425/1972, 10135/1975, 25228/1975, 112038/1975, 117422/ 1975 and 130441/1975.

[0027] Further, as colored cyan couplers, such compounds obtained by substituting colorless cyan couplers with aryl-azo in the coupling position thereof as those described in, e.g., U.S. Patent Nos. 2,521,908 and 3,034,892, British Patent No. 1,255,111, and Japanese Patent O.P.I. Publication No. 22028/ 1973 may be generally used, and there may also be used those colored cyan couplers of the type that the reaction thereof with the oxidized product of a developing agent causes the dye thereof to be dissolved into the processing bath as described in, e.g., Japanese Patent O.P.I. Publication Nos. 10135/1975 and 123341/1975, and U.S. Patent No. 3,476,563.

[0028] The magenta couplers of the present invention having the foregoing formulas (I) and (It) are desirable to be used generally within the range of preferably from 5x10 4 mole to 8x10^-1 mole per mole of the silver contained in the emulsion layer, and most preferably from 1x10^-2 mole to 8x10^-1 mole. Alternatively, according to purposes, the couplers are desirable to be used in a quantity of at least 0.5% or preferably at least 2% of all the couplers used in the silver halide color photographic light-sensitive material of the present invention.

[0029] In the present invention, DIR (developing inhibitor releasing) compound may be preferably incorporated into the component layers of the light-sensitive material. Such DIR compounds, include those whose component capable of reacting with the oxidized product of a color developing agent has directly a development inhibiting component and those whose same component has a development inhibiting component through a timing radical. Those preferred as the latter DIR compounds have the formula:

wherein A is a component capable of reacting with the oxidized product of a color developing agent, which is allowed to be any component if capable of releasing a TIME-Z radical by the reaction thereof with the oxidized product of a color developing agent; TIME represents a timing radical; and Z represents a component that is released from the TIME radical to thereby inhibit the development.

[0030] Examples of the above TIME may be those produced by the intramolecular nucleophilic substitution reaction as described in Japanese Patent O.P.I. Publication No. 145135/1979 or otherwise may be those by the electron transfer along the conjugated chain as described in Japanese Patent Application No. 17644/ 1980; in short, they may be those compounds wherein the coupling thereof with the A-TIME is first severed to release the TIME-Z radical, and the coupling of the TIME-Z is then severed to release the Z.

[0031] The Z includes such development inhibiting components as described in Research Disclosure Vol. 176, No. 17643, Dec. 1978 (hereinafter referred to as Publication-1), preferred ones among which are mercaptotetrazole, selenotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzotriazole, benzodiazole, and derivatives of these compounds.

[0032] The preferred development inhibiting components are those represented by the following formulas:





wherein R⁷ is hydrogen, an alkyl radical having from 1 to 8 carbon atoms (such as methyl, ethyl, butyl), phenyl or a substituted phenyl; and R⁸ is hydrogen, not less than'one halogen (such as chlorine, fluorine, bromine), a lower alkyl radical. having from 1 to 4 carbon atoms, or nitro radical.

[0033] To be more concrete, the foregoing Formula (VIII) further includes those compounds having the following Formulas (IX), (XII) and (XITI):

wherein A and Z are as defined in Formula (VIII), and those excluding A and Z correspond to the TIME of Formula (VIII) wherein X is a group of atoms necessary to complete a substitutable benzene or naphthalene ring; and R⁹ and R¹⁰ each is hydrogen, an alkyl or aryl radical.

[0034] The -

radical is substituted in the ortho- or para- position on the ring to the O atom.

[0035] A compound having Formula (IX), when reacting with the oxidized product of a color developing agent, is cleaved to first produce a compound having the following Formula (X), which is subsequently cleaved again by the electron transfer along the conjugated system to produce a compound having the following Formula (XI) and concurrently produce Z.

[0036] Those compounds having Formula (XI) are the compounds called quinone-methide or naphthoquinone-methide.

wherein A and Z are as defined in Formula (VIII), and the

radical corresponds to the TIME radical in Formula (VIII).

wherein A and Z are as defined in Formula (VIII), and the Nu-X-E corresponds to the TIME radical in Formula (VIII); Nu is a nucleophilic radical having an electron-rich oxygen atom, sulfur atom or nitrogen atom; E is an electrophilic radical having an electron-insufficient carbonyl, thiocarbonyl, phosphonyl or thiophosphonyl radical, the electrophilic radical being bonded with Z; and X is a combining radical which relates Nu and E dimensionally and which, after Nu is released from A, is capable of effecting an intramolecular nucleophilic substitution reaction to thereby release Z.

[0037] These DIR compounds having a development inhibiting component through a timing radical are disclosed in Japanese Patent O.P.I. Publication No. 145135/1979 and Japanese Patent Application No. 17644/1980.

[0038] On the other hand, preferred DIR compounds whose component capable of reacting with the oxidized product of a color developing agent has directly a development inhibiting component are those having the following formula:

wherein B is a component capable of reacting with the oxidized product of a color developing agent and reacts with the oxidized product of a color developing agent to thereby release Y radical (a development inhibiting component). As the Y, the development inhibiting components defined in Formula (VIII) may be used.

[0039] The DIR compounds whose component capable of reacting with the oxidized product of a color developing agent has directly a development inhibiting component include those as described in, e.g., U.S. Patent Nos. 3,958,993, 3,961,959 and 3,938,996, Japanese Patent O.P.I. Publication Nos. 147716/1975, 152731/1975, 105819/1976, 6724/1976 and 46817/1977, U.S. Patent Nos. 3,928,041, 3,227,554, 3,773,201 and 3,632,345, British Patent No. 2,010,818, and Japanese Patent O.P.I. Publication No. 43030/1977.

[0040] The A in Fromulas (VIII) , (XII) and (XIII) and the B in Formula (XIV) include those which form a dye by the reaction thereof with the oxidized product of a color developing agent and those which do not.

[0041] The preferred DIR compounds used in the present invention are those having Formula (VIII) and those having Formula (XIV), and the Y radical thereof includes benzotriazole radicals, particularly, those radicals represented by Formula (e) and Formula (f).

[0042] The DIR compound for use in the present invention may be either one that has a timing radical or one that has no timing radial, or may also be used in combination of both.

[0043] In the case where a certain color sensitivity-having emulsion layer is comprised of a plurality of layers differing in the sensitivity, the DIR compound may be incorporared into one of the layers or into not less than two of the layers, but is desirable to be incorporated into at least a lower sensitivity-having emulsion layer.

[0044] In the color photographic light-sensitive material of the present invention, the total using amount of the DIR compound, when using either one of or both DIR compounds having a timing radical and having no timing radical, is desirable to be within the range of from 5x10^-4 to 5x10^-2 mole, and most preferably from 1x10 ^-3 to 1x10^-2 mole per mole of the silver halide contained in the emulsion. The mixing molar ratio of both DIR compounds in the case of using in combination of both may be arbitrarily selected, but the desirable ratio of the DIR compound having a timing radical to that having no timing radical is within the range of from 0.02 to 50 mole%, and most preferably from 0.1 to 5.0 mole%.

[0045] In the color photographic light-sensitive material of the present invention, both a compound having Formula (I) or Formula (V) and a DIR compound are preferably to be incorporated into at least one of the light-sensitive silver halide emulsion layers; for example, in the case of applying both compounds to an ordinary multi-layered color photographic light-sensitive material having blue-sensitive, green-sensitive and red-sensitive emulsion layers, the compounds may be incorporated into one of or not less than two of these layers.

[0046] In the case where a certain color sensitivity-having emulsion layer is composed of a plurality of layers differing in the sensitivity, the compounds may be incorporated into one of or not less than two layers.

[0047] The color light-sensitive material of this invention is desirable to have at least one layer each of blue-sensitive, green-sensitive and red-sensitive emulsion layers, and further contains nondiffusion type couplers in appropriate combination with the respective light-sensitive silver halide emulsion layers.

[0048] The nondiffusion couplers may be any of 6-equivalent, 4- equivalent and two-equivalent couplers, and are also allowed to be of low molecular weight or to be the so-called polymer couplers.

[0049] As the yellow coupler, open-chained ketomethylene couplers may be used, among which benzoyl acetanilide compounds and pivaloyl acetanilide compounds are useful.

[0050] These couplers are generally used in a quantity of from 2x10 ² to 5x10 ¹ mole, and preferably from 1x10^-2 to 5x10^-1 mole per mole of the silver contained in the emulsion.

[0051] For the incorporation of the compounds having Formula (I) and Formula (V) and the above-described couplers into color light-sensitive materials there are various methods, among which the latex dispersion method and the oil-in-water type emulsification dispersion method are particularly useful. These dispersion methods have been conventionally well-known, and particularly the latex dispersion method and the effect thereof are discribed in Japanese Patent O.P.I. Publication Nos. 74538/1974, 59943/1976 and 32552/1979, and Research Disclosure, Aug. 1976, No. 14850, pp. 77 - 79.

[0052] Appropriate latexes for use in the method are homopolymers, copolymers and terpolymers of such monomers as, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyl-trimethyl-ammonium methosulfate, 3-(methacryloyloxy)propane-l-sulfonic acid sodium salt, N-isopropyl-acrylamide, N-[2-(2-methyl-4-oxopentyl)]-acrylamide, 2-acrylamide-2-methylpropane-sulfonic acid, and the like. The oil-in-water type emulsification dispersion method and conventionally known methods for dispersing such hydrophobic additives as couplers may also be used. The DIR couplers for use in this invention and the compounds having Formula (I) and Formula (V) of this invention may be either dispersed together with other different couplers or dispersed separately and added independently.

[0053] A single scavenger layer or a plurality of scavenger layers may be placed in an appropriate position among the component layers of the color light-sensitive material, whereby the layer or a unit of layers subjected to the influence of the development inhibitor can be controlled.

[0054] As the silver halide emulsion for use in the color photographic light-sensitive material of the present invention there may be used an arbitrary silver halide emulsion used by those skilled in the art, including such normally usable silver halide emulsions as of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, and the like. The particles of the silver halide used in such silver halide emulsions may be either coarse-grained or fine-grained, and the particle size distribution may be either wider or narrower, but the distribution is desirable to be narrower.

[0055] The crystals of these silver halide particles may be either normal or twin, and the ratio of the [100] faces to the [111] faces thereof may be discretional, but the particles of normal crystal are preferred.

[0056] According to the preferred embodiment of the present invention, that the green-sensitive silver halide emulsion layer positioned farthest from the support comprises substantially regular silver halide particles means that at least 80% by weight or by the number of the silver halide particles is in the regular form, and at least 95% by weight or by the number of the silver halide particles is in the regular form.

[0057] That the silver halide particles for use in this invention has the regular structure or in the regular form means that the particles do not contain such an anisotropic growth as in twin faces but grows all isotropically; for example, they are in the tetradecahedral, regular-octahedral, or spherical form. Methods for the production of such regular silver halide particles are well-known and described in, e.g., J. Phot. Sci., 5, 332 (1961), Ber. Bunsenges, Phys. Chem. 67, 949 (1963), Intern. Congress Phot. Sci. Tokyo (1967), and the like.

[0058] Further, the crystal structure of these silver halide particles may be either uniform from the inside through the outside thereof or stratified with different stratums of the inside and of the outside thereof. And these silver halides may be either of the type of forming a latent image mainly on the surface of the particles thereof or of the type of forming a latent image inside the particles thereof. These silver halide particles may be prepared by known methods practiced by those skilled in the art.

[0059] The silver halide emulsion to be used in the present invention is desirable to be free of the water-soluble salt thereof, but may be used with the water-soluble salt not removed therefrom. In addition, not less than two different silver halide emulsions separately prepared may be mixed to be used.

[0060] As the binder material for the silver halide emulsion layers of the multi-layered color photographic light-sensitive material, those conventionally known materials may be used, e.g., such gelatin derivatives as gelatin, phenyl-carbamylated gelatin, acylated gelatin, phthalated gelatin, and the like. These binder materials may, if necessary, be used as a compatible mixture of not less than two of them.

[0061] The silver halide photographic emulsion prepared by dispersing the above-described silver halide particles into a binder liquid may be chemically sensitized by a chemical sensitizer. Chemical sensitizers advantageously usable in the present invention are broadly classified into 4: noble-metallic sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.

[0062] Noble-metallic sensitizers applicable to the invention include gold compounds and ruthenium, rhodium, palladium, iridium, platinum, and the like. In addition, gold compounds may be used together with ammonium thiocyanate or sodium thiocyanate.

[0063] Applicable sulfur sensitizers include active gelatin and sulfur compounds.

[0064] Selenium sensitizers include active and inert selenium compounds.

[0065] Reduction sensitizers include stannous salts, polyamines, bisalkylaminosulfide, silane compounds, imino-aminomethane- sulfinic acid, hydrazinium salts, hydrazine derivatives, and the like.

[0066] The multi-layered color photographic light-sensitive material of this invention may contain, in addition to the foregoing additives, various additives useful for photographic light-sensitive materials such as stabilizers, development accelerators, hardeners, surface active agents, antistain agents, lubricants, ultraviolet absorbing agents, and others.

[0067] The multi-layered silver halide color photographic light-sensitive material of the present invention may, in addition to the silver halide emulsion layers, be provided arbitrarily with such auxiliary layers as a protective layer, interlayers, filter layers, an antihalation layer, a backing layer, and the like.

[0068] For the support, those conventionally known materials such as plastic film, plastic-laminated paper, baryta paper, synthetic paper, and the like, may be used by arbitrarily selecting therefrom according to the purpose of the photographic light-sensitive material to be used.

[0069] As the support there may also be used those described in Japanese Patent Examined Publication No. 500272/1981, which are such that the support is provided on the surface thereof with a plurality of microcavities which are open toward in one direction of the surface. These support materials are generally coated thereon with a subbing layer in order to strengthen the adhesion thereof to a photographic emulsion layer.

[0070] The multi-layered color photographic light-sensitive material of the present invention, after being exposed imagewise, is processed by a normally used color developing method to thereby obtain an image. The fundamental processing steps in the negative-to-positive process include color development, bleaching, and fixing processes. In some cases, the color photographic light-sensitive material is processed in these respective fundamental processing steps separately, but, in some other cases, in lieu of being processed in not less than two processing steps, is processed at one time in a combined processing liquid retaining their respective functions, such as, for example, the processing in a monobath color processing liquid containing a color developing agent, a ferric salt bleaching component, and a thiosulfate fixing component, or in a monobath bleach-fixing liquid containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching component and a thiosulfate fixing component.

[0071] There are no special restrictions on the method for the processing of the multi-layered color photographic light-sensitive material of the present invention, and all appropriate processing methods may be applied, typical examples of which are: a processing method wherein the color light-sensitive material is color-developed, bleach-fixed, and, if necessary, washed and then stabilized; another processing method wherein the color light-sensitive material is color-developed, bleached and fixed separately, and, if necessary, washed and stabilized; a further processing method wherein the light-sensitive material is subjected to the processings in order of prehardening, neutralizing, color-developing, stop- fixing, washing, bleaching, fixing, washing, post-hardening, and washing; still another processing method wherein the light-sensitive material is subjected to the processings in order of color developing, washing, supplementary color developing, stopping, bleaching, fixing, washing, and stabilizing; a still further processing method wherein the developed silver produced by a color development is halogenation-bleached, and then color-developed again to thereby increase the quantities of the dyes to be produced; another method wherein such an amplifier as a peroxide, a cobalt complex salt, or the like, is used to process a light-sensitive material containing a small amount of silver; and other equivalent methods. Any of these methods may be used.

[0072] Aromatic primary amine color developing agents include p-phenylenediamines and p-aminophenols, but the former is typically used. Such color developing agents may be used by being incorporated into the multi-layered color photographic light-sensitive material.

[0073] As the precursor of the color developing agent to be used in the present invention there may be used such Schiff base type precursors of color developing agents as described in U.S. Patent Nos. 2,507,114, 2,695,234, and 3,342,599, and Research Disclosure vol. 151, No. 15159, Nov. 1979, and those described in Research Disclosure vol. 129, No. 12924, Oct. 1976, vol. 121, No. 12146, June 1974, and vol. 139, No. 13924, Nov. 1975.

[0074] To a color developer liquid, if necessary, may be added various additives.

[0075] The present invention enables to improve significantly the sharpness of the dye image produced in the multi-layered color photographic light-sensitive material, particularly, the sensitivity, color purity, resistance to formalin, and sharpness of the dye image formed in the green-sensitive emulsion layer which is positioned farthest from the support because the sharpness of the dye image formed in the green-sensitive silver halide emulsion layer of the multi-layered color photographic light-sensitive material affects largely the quality of the light-sensitive material for photographic printing use which is the final photographic product.

[0076] In the silver halide color photographic light-sensitive material according to the present invention, the sensitivity thereof is lower than that of the blue-sensitive silver halide emulsion layer of conventional color light-sensitive materials, but the problem of the substantial low-sensitivity of the color light-sensitive material can be nearly solved by the adjustment of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer.

[0077] The present invention is illustrated in further detail in reference to examples below, but the present invention is not limited thereto.

Example 1

Comparative Sample 1:

[0078] On an antihalation layer-coated triacetate base the following layers were coated in the order given below to thereby prepare Comparative Sample 1: lst layer (red-sensitive silver halide emulsion layer):

[0079] To 1000 g of a highly sensitive silver iodobromide. emulsion sensitized by a sensitizing dye to the red spectral resion (silver iodide content 4-mole%; containing 20 g of silver halide and 3 g of gelatin per 100 g of the emulsion) was added a cyan coupler-dispersed liquid (C-l, described hereinafter) so that the quantity thereof becomes 8 mole% per mole of the silver, and further added the following stabilizers (A) and (B) to thereby prepare an emulsion liquid, which was then coated so that the thickness thereof becomes 4.4 µ after drying.

2nd layer (interlayer):

[0080] An interlayer containing 0.5 g/m² of gelatin and 0.1 g/m² of 2,5-di-t-octyl hydroquinone was coated so that the dried thickness is 0.6 p. 3rd layer (green-sensitive silver halide emulsion layer):

[0081] To 1000 g of a highly sensitive silver iodobromide emulsion sensitized by a sensitizing dye to the green spectral region (silver iodide content 4 mole%, containing 20 g of silver halide and 3 g of gelatin per 100 g of the emulsion) was added a magenta coupler-dispersed liquid (M-l, described hereinafter) so that the quantity thereof becomes 8 mole% per mole of the silver, and further added the foregoing stabilizers (A) and (B) to thereby prepare an emulsion liquid, which was then coated so that the thickness thereof becomes 5.0 p after drying. 4th layer (yellow filter layer):

[0082] An yellow colloidal silver-dispersed yellow filter layer containing 0.07 g/m² of 2,5-di-t-octyl hydroquinone and 0.9 g/ m² of gelatin was coated so that the yellow density is 1.0 and the dried thickness thereof is 0.86 µ.

5th layer (blue-sensitive silver halide emulsion layer):

[0083] To 1000 g of a highly sensitive silver iodobromide emulsion sensitized to the blue spectral region (silver iodide content 4 mole%; containing 20 g of silver halide and 3 g of gelatin per 100 g of the emulsion) was added an yellow coupler-dispersed liquid (Y-l, described hereinafter) so that the quantity thereof becomes 10 mole% per mole of the silver, and further added the foregoing stabilizers (A) and (B) to thereby prepare an emulsion liquid, which was then coated so that the thickness thereof becomes after drying 7.0 µ.

6th layer (protective layer):

[0084] A protective layer containing 1.3 g/m² of gelatin and 1 g/ m² of 1,2-bis-vinyl-sulfonyl ethane was coated so that the thickness thereof becomes 0.6 µ after drying.

Comparative Sample 2:

[0085] On a similar support to that used in Comparative Sample 1 the following liquids were coated in the order given below: 1st layer (red-sensitive silver halide emulsion layer):

[0086] An emulsion for the 1st layer was prepared in the same manner as in the lst layer of Comparative Sample 1 and then coated also in the same manner.

2nd layer (interlayer):

[0087] A liquid for the 2nd layer was prepared in the same manner as in the 2nd layer of Comparative Sample 1 and then coated also in the same manner.

3rd layer (blue-sensitive silver halide emulsion layer):

[0088] The preparation and coating were made in the same manners as in the 5th layer of Comparative Sample 1 with the exception of using a blue-sensitive emulsion whose sensitivity is higher than (8 times as much high as) that of the blue-sensitive emulsion layer used as the 5th layer of Comparative Sample 1.

4th layer (interlayer):

[0089] A liquid for the 4th layer was prepared and coated in the same manner as in the 2nd layer of Comparative Sample 1.

5th layer (green-sensitive silver halide emulsion layer):

[0090] The preparation and coating were made in the same manners as in the 3rd layer of Comparative Sample 1 with the exception of using a green-sensitive emulsion whose sensitivity is a little less than (9/10 time as low as) that of the green-sensitive emulsion used for the 3rd layer of Comparative Sample 1.

6th layer (protective-yellow filter layer):

[0091] 1,2-bis-vinyl-sulfonyl ethane was added to the liquid prepared for the 4th layer of Comparative Sample 1 to .produce a coating liquid, which was then coated so that the thickness thereof becomes 0.86 p after drying.

Comparative Sample 3:

[0092] On a similar support to that used in Comparative Sample 1 the following liquids were coated in the order given below:

[0093] Liquids for the lst, 2nd, 3rd, 4th and 5th layers were prepared and coated in the same manners as in Comparative Sample 1.

6th layer (protective-yellow filter layer):

[0094] The liquid for the yellow filter layer as the 6th layer of Comparative Sample 1 was reprepared adjusting the quantity of silver so that the yellow filter density thereof become 1/2 and then coated so that the thickness thereof become 0.86 p after drying.

Comparative Sample 4:

[0095] On a similar support to that used in Comparative Sample 1 the following liquids were coated in the order given below:

[0096] Liquids for the lst, 2nd, 3rd and 4th layers were prepared and coated in the same manners as in Comparative Sample 2.

5th layer (green-sensitive silver halide emulsion layer):

[0097] A liquid for the 5th layer was prepared and coated in the same manners as in the 5th layer of Comparative Sample 1 with the exception that the magenta coupler-dispersed liquid (M-l, described hereinafter) was replaced by a liquid (M-2, described hereinafter).

6th layer (protective-yellow filter layer):

[0098] A liquid for the 6th layer was prepared and coated in the same manners as in the 6th layer of Comparative Sample 2.

Sample 5 for the Invention:

[0099] On a similar support to that used in Comparative Sample 1 the following liquids were coated in the order given below:

[0100] Liquids for the lst, 2nd, 3rd and 4th layers were prepared and coated in the same manners as in Comparative Sample 2.

5th layer (green-sensitive silver halide emulsion layer):

[0101] A liquid for the 5th layer was prepared and coated in the same manners as in the 5th layer of Comparative Sample 4 with the exception that the magenta coupler-dispersed liquid (M-2, described hereinafter) was replaced by a liquid (M-3, described hereinafter).

6th layer (yellow filter layer):

[0102] A liquid for the 6th layer was prepared and coated in the same manners as in the 6th layer of Sample 4.

Sample 6 for the Invention:

[0103] Liquids for the respective layers were prepared and coated in the same manners as in the respective layers of Sample 5 with the exception that the magenta color-dispersed liquid of the 5th layer (M-3, described hereinafter) was replaced by a liquid (M-4, described hereinafter).

Sample 7 for the Invention:

[0104] Liquids for the respective layers were prepared and coated in the same manners as in the respective layers of Sample 5 with the exception that the magenta coupler-dispersed liquid of the 5th layer (M-3, described hereinafter) was replaced by a liquid (M-5, described hereinafter).

Sample 8 for the Invention:

[0105] On a similar support to that used in Comparative Sample 1 the following liquids were coated in the order given below: 1st layer (blue-sensitive silver halide emulsion layer):

[0106] An emulsion for the lst layer was prepared and coated in the same manners as in the 3rd layer of Sample 2.

2nd layer (interlayer) :

[0107] A liquid for the 2nd layer was prepared and coated in the same manners as in the 2nd layer of Sample 2.

3rd layer (red-sensitive silver halide emulsion layer):

[0108] An emulsion for the 3rd layer was prepared and coated in the same manners as in the lst layer of Sample 2.

4th layer (interlayer):

[0109] A liquid for the 4th layer was prepared and coated in the same manners as in the 4th layer of Sample 2 except that a magenta dye was added thereto.

5th layer (green-sensitive silver halide emulsion layer):

[0110] A liquid for the 5th layer was prepared and coated in the same manners as in the 5th layer of Sample 6.

6th layer (protective-yellow filter layer):

[0111] A liquid for the 6th layer was prepared and coated in the same manners as in the 6th layer of Sample 2.

Dispersed Liquid (C-1):

[0112] 50 g of a nondiffusion cyan coupler (Coupler C-l, given hereinafter), 4 g of a colored cyan coupler (Coupler CC-1, given hereinafter) and 0.7 g of a DIR compound (Coupler D-l, given hereinafter) were dissolved by heating into a mixutre of 55 g of tricresyl phosphate (abbreviated hereinafter to TCp) with 110 ml of ethyl acetate (abbreviated hereinafter to EA), the resulting solution was added to 400 ml of a 7.5% aqueous gelatin solution containing 4 g of sodium triisopropyl-naphthalene-sulfonate, this mixture was then emulsified and dispersed by means of a colloid mill, and then the whole quantity was made to 1000 ml.

Dispersed Liquid (Y-1):

[0113] 300 g of a nondiffusion yellow coupler (Coupler Y-l, given hereinafter) and 3.0 g of a DIR compound (Coupler T-l, given hereinafter) were dissolved by heating into a mixture of 150 g of dibutyl phthalate (abbreviated hereinafter to DBp) with 500 ml of EA, the resulting solution was added to 1600 ml of a 7.5% aqueous gelatin solution containing 18 g of sodium triisopropyl-naphthalene-sulfonate, and this mixture was then emulsified to be dispersed by means of a colloid mill, and the whole quantity thereof was made to 2500 ml.

Dispersed Liquid (M-1):

[0114] 45 g of a nondiffusion magenta coupler (Coupler M-I, given hereinafter), 18 g of a nondiffusion magenta coupler (Coupler M-2, given hereinafter), 14 g of a nondiffusion magenta coupler (Coupler CM-1, given hereinafter), 0.4 g of a DIR compound (Coupler D-l, given hereinafter) and 0.2 g of a DIR compound (Coupler T-l, given hereinafter) were dissolved by heating into a mixture of 77 g of TCp with 280 ml of EA, the resulting solution was added to 500 ml of a 7.5% aqueous gelatin solution containing 8 g of sodium triisopropyl-naphthalene-sulfonate, and this mixture was then emulsified to be dispersed by means of a colloid mill and the whole quantity thereof was made to 1000 ml.

Dispersed Liquid (M-2):

[0115] 50 g of a nondiffusion magenta coupler (Coupler M-l, given hereinafter), 22 g of a nondiffusion magenta coupler (Coupler M-2, given hereinafter), 0.4 g of a DIR compound (Coupler D-l, given hereinafter) and 0.2 g of a DIR compound (Coupler T-l, given hereinafter) were dissolved into a mixture of 77 g of _TCp with 280 ml of EA, the resulting solution was added to 500 ml of a 7.5% aqueous gelatin solution containing 8 g of sodium triisopropyl-naphthalene-sulfonate, and this mixture was emulsified to be dispersed by means of a colloid mill, and then the whole quantity thereof was made to 1000 ml.

Dispersed Liquid (M-3):

[0116] 65 g of a nondiffusion magenta coupler (Exemplified Coupler 13), 0.1 g of a DIR compound (Coupler D-1, given hereinafter) and 0.1 g of a DIR compound (Coupler T-1, given hereinafter) were dissolved into a mixture of 65 g of TCp with 260 ml of EA, and after that this was emulsified to be dispersed in the same manner as in the foregoing Dispersed Liquid (M-2) to thereby prepare Dispersed Liquid (M-3).

Dispersed Liquid (M-4):

[0117] 83 g of a nondiffusion magenta coupler (Exemplified Coupler 8) and 0.1 g of a DIR compound (Coupler T-l, given hereinafter) were dissolved into a mixture of 83 g of TCp with 330 ml of EA, and after that this was emulsified to be dispersed in the same manner as in the foregoing Dispsersed Liquid (M-3) to thereby prepare Dispersed Liquid (M-4).

Dispersed Liquid (M-5):

[0118] 88 g of a nondiffusion magenta coupler (Exemplified Coupler 15) and 0.15 g of DIR compound (Coupler T-1, given hereinafter) were dissolved into a mixture of 88 g of TCp with 350 ml of EA, and after that this was emulsified to be dispersed in the same manner as in the foregoing Dispersed Liquid (M-3) to thereby prepare Dispersed Liquid (M-5).

Coupler C-1:

[0119] 1-hydroxy-4-(β-methoxyethylaminocarbonyl-methoxy)-N-[δ-(2,4-di-tert-amyl-phenoxy)butyl]-2-naphthamide

Coupler CC-l:

[0120] 1-hydroxy-4-[4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[δ-(2,4-di-t-amyl-phenoxy)butyl]-2-naphthamide disodium salt

Coupler M-l:

[0121] 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amyl-phenoxy- acetamido)-benzamido]-5-pyrazolone

Coupler M-2:

[0122] 4,4'-methylene-bis{1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amyl-phenoxyacetamido)benzamido]-5-pyrazolone} Coupler CM-l:

[0123] 1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenyl-succinimidoanilino)-5-pyrazolone

[0124] Each of the above-prepared samples was exposed through an optical wedge to a white light, and after that Samples 1 to 8 each was processed in accordance with the following processing steps:

[0125] The compositions of processing liquids that were used in the processing steps are as follows:

Color developer bath:

[0126] 

Bleaching bath:

[0127] 

Fixer bath:

[0128] 

Stabilizer bath:

[0129] 

[0130] Subsequently, an evaluation was made on the sharpness of the color image formed on each of the green-sensitive emulsion layers of the foregoing samples. The obtained results are as given in Table 1. In addition, the evaluation of the sharpness of each image was made in the manner that MTF (Modulation Transfer Function) is first determined for each sample, and then the magnitudes of the values of MTF of the samples at the spatial frequencies of 20/mm and 60/mm are compared.

[0131] As apparent from the comparison between Sample 1 and Sample 5 to 8, it is understood that Samples 5 to 8 are improved significantly in the sharpness of the green-sensitive emulsion layers thereof. Comparative Sample 2 shows the noticeable deterioration of the sensitivity of the blue-sensitive emulsion layer thereof partly because of the filtering effect by the colored coupler contained in the green-sensitive emulsion layer thereof. In addition, the deterioration of the actual photographic speed at the time of a camera exposure also was recognized. Comparative Sample 3 is improved to prevent the sensitivity from being deteriorated, but because the green-sensitive emulsion layer thereof is also sensitive to blue light, the color purity of the resulting image becomes deteriorated. Likewise, Comparative Sample 4 also shows the deterioration of the color purity and clearness of the image thereon due to the irregular absorption (secondary absorption) in the 400 - 500 nm region by the magenta dye contained therein: this is a serious obstacle to the color reproduction. In contrast, it is found that Samples 5, 6, 7 and 8 of the present invention are so excellent silver halide color photographic light-sensitive materials that they show the remarkable improvement in the graininess and sharpness thereof and no deterioration of the color purity of the resulting images thereof nor deterioration of the actual photographic speed in camera exposures.

Example 2

[0132] Samples 1, 2, 5, 6 and 8 of the samples used in Example 1 were exposed through an optical wedge to a white light and then subjected to the following treatment, and after that the samples were processed in the same manner as in Example 1. Treatment: The samples were allowed to stand over a period of 17 hours under the atmospheric condition retained in a closed container of a relative humidity (RH) of 75%, temperature of 40°C, and formaldehyde gas concentration of 5x10^-4 mole/liter. The obtained results are as shown in Table 2.

[0133] As apparent from the results shown in Table 2 it is understood that Samples 5 to 8 of the present invention are.hardly subject to the bad influence by formalin and excellent in the preservability thereof when stored unprocessed.

Claims

1. A silver halide color photographic light-sensitive material comprising a support having thereon a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a yellow filter layer, a blue-sensitive silver halide emulsion layer and a protective layer, characterized in that said protective layer is an uppermost layer functioning also as a yellow filter layer, and said green-sensitive silver halide emulsion layer is positioned farthest from said support and substantially comprises a photographic coupler capable of forming a magenta dye image on reaction with the oxidation product of an aromatic primary amine color developing agent, said photographic coupler having the formula (I), (II), (III), (IV) or (V):



wherein R¹ and R 2 each represents alkyl, aryl, heterocyclic ring, amino, acylamino, hydroxy, alkoxy, alkylthio, carboxy, or an esterified carboxy radical; R³ represents a hydrogen atom or a coupling-off radical; Cp represents a blocking coupler radical which, after the reaction thereof with the oxidation product of a color developing agent, produces a colorless or alkali-soluble reaction product.

2. A material according to Claim 1, characterized in that Cp is a radical having the Formula:

wherein R₅ is an alkyl-O-CO-, alkyl-CO-, aryl-O-CO-, an aryl-CO-, -COOH, -N0₂ or -CN radical; and R₆ is a radical as defined for R₅ or is aryl-NHCO-, provided that at least one of R₅ and R₆ contains an alkyl or aryl radical substituted by at least one carboxy, sulfo or hydroxy radical.

3. A material according to Claim 1 or 2 characterized in that said protective layer has a filter density of not less than 50% of the whole yellow filter density of said silver halide color photographic light-sensitive material.

4. A material according to any preceding Claim, characterized in that said green-sensitive silver halide emulsion layer comprises regular silver halide particles.

5. A material according to any preceding Claim characterized in that Cp represents halogen or an alkoxy, aryloxy, heterocyclyloxy, sulfonyloxy, acyloxy, acyl, heterocyclyl, thiacyano, alkylthio, arylthio, heterocyclylthio, sulfonamideo, sulfonyloxy or aryl-azo radical.

6. A material according to Claim 5 characterized in that Cp represents a group having the formula:

wherein X represents an oxygen or sulfur atom; R⁶ represents an alkyl, heterocyclic or acyl radical; and Q represents the non-metallic atoms necessary to form, together with the nitrogen atom, a 5-member or 6-member ring.

7. A material according to any preceding Claim characterized in that the coupler is employed in an amount from 5x10^-4 to 8x10^-1 mole per mole of silver in the emulsion layer.

8. A material according to any preceding Claim characterized in that one or more DIR compounds are incorporated into the component layers.