EP0286850B1

EP0286850B1 - Method for preventing an organic colored substance from fading by light, stabilized colored compositions and photographic elements and materials

Info

Publication number: EP0286850B1
Application number: EP19880104072
Authority: EP
Inventors: Yutaka Kaneko
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1987-03-18
Filing date: 1988-03-15
Publication date: 1993-05-19
Anticipated expiration: 2008-03-15
Also published as: JPH0697333B2; EP0286850A1; JPS63229454A

Description

The present invention relates to a method for preventing an organic colored substance from fading by light.
It is widely known that organic colored substances generally tend to fade by exposure to light. A number of studies to prevent such fading by light of organic colored substances have been making progress in the fields of, e.g., printing ink, pigments for fibers and color photography.
The present invention can be very advantageously used for the purpose of preventing such colored substances from fading by light.
The term 'light' used herein implies electromagnetic waves in the range of from 300 nm to 800 nm, including ultraviolet rays of less than about 400 nm, visible rays of from about 400 nm to about 700 nm, and infrared rays of from about 700 nm to about 800 nm.
Regarding those methods for improving the light resistance of organic colored substances, e.g., organic dyes or pigments, there are a number of reports; for example, U.S. Patent No. 3,432,300 describes that organic compounds such as indophenol, indoaniline, azo and azomethine dyes, etc., to be used in color photography can be improved in fastness against visible and ultraviolet rays by being mixed with phenol-type compounds having condensed heterocyclic systems.
In the field of silver halide light-sensitive color photographic materials, it is desired that dye images that have been obtained from the couplers used do not fade when exposed to light over a long period of time, or fade even when stored under a high temperature/high humidity condition.
It is known, however, that the fastness of such dye images against rays -mainly ultraviolet rays or visible rays-is not considered satisfactory; these dye images are liable to fade or discolor when exposed to these active rays. In order to overcome such shortcomings, there have been conventionally proposed methods which use various selected couplers capable of forming less-fading dye images, which use ultraviolet absorbing agents for protecting dye images from ultraviolet rays, and which introduce into couplers a group capable of providing light resistance thereto.
However, in order to make dye images satisfactorily light-resistant by using, for example, an ultraviolet absorbing agent, a relatively large amount of the agent needs to be used. In this instance, there are cases where the dye image is conspicuously stained due to the color of the ultraviolet absorbing agent itself. Also, the use of an ultraviolet absorbing agent is not effective at all in preventing the fading of dye images by visible rays, so that the improvement in light resistance by using an ultraviolet absorbing agent has its limits. Further, there are also known those methods for preventing dye images from fading which use an antifading agent having a phenolic hydroxyl agent or a group capable of producing a phenolic hydroxyl group; for example, there are proposals for the use of phenol and bisphenols in Japanese Patent Examined Publication Nos. 31256/1973, 31625/1973, 30462/1976, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 134326/1974 and 134327/1974, the use of pyrogallol, gallic acid and its esters in U.S. Patent No. 3,069,262, the use of α-tocopherols and their acyl derivatives in U.S Patent Nos. 2,360,290 and 4,015,990, the use of hydroquinone derivatives in Japanese Patent Examined Publication No. 27534/1977, Japanese Patent O.P.I. Publication No. 14751/1977 and U.S. Patent No. 2,735,765, the use of 6-hydroxy-chromans in U.S. Patent Nos. 3,432,300 and 3,574,627, and the use of 6,6ʹ-dihydroxy-2,2ʹ-spirobichromans in Japanese Patent Examined Publication No. 20977/1974. However, these compounds are effective to some extent but not adequate as antiphotofading agents or antiphotodiscoloration agents.
British Patent No. 1,451,000 proposes the improvement of the stability of an organic colored substance against light by use of an azomethine quenching compound whose absorption spectrum peak is in a longer wave length region than that of the colored substance. The proposal, however, is disadvantageous in respect that the azomethine quenching compound itself is colored, thus largely affecting the hue of the colored substance. Also, the use of a metallic complex for preventing a polymer from being deteriorated by light is described in J. Polym. Sci., Polym. Chem. Ed., Vol. 12, p. 993 (1974), and J. Polym. Sci., Polym. Lett. Ed., Vol. 13, p.71 (1975). And a method for stabilizing a dye against light by use of a metallic complex is described in Research Disclosure No. 15162 (1976). However, their antifading effect in itself is poor. Therefore, these metallic complex compounds cannot be used in a quantity sufficient to show their antifading effect because they are less soluble in organic solvents. In addition, these complex compounds themselves are conspicuously colored, so that when used in a large quantity, they adversely affect the hue as well as the color purity of colored substances, particularly, dyes.
Further, other methods of stabilizing dyes against light by use of various metallic complex compounds are described in Japanese Patent O.P.I. Publication Nos. 62826/1979, 62987/1979, 65185/1979, 69580/1979, 72780/1979, 82384/1979, 82385/1979, 82386/1979, 136581/1979, 136582/1979, 12129/1980, 152750/1980, 168652/1981, 167138/1981 and 16174/1982, and Japanese Patent Examined Publication No. 19770/1982.
However, even the above methods are still inadequate to reduce the color of complex compounds themselves, thus being unable to remove the adverse effect on the hue and color purity of organic colored substances, particularly, dyes. These metallic complex compounds of the prior art, when applied to a silver halide light-sensitive photographic color material (hereinafter referred to as a color photographic material), tend to produce a stain on the un-color-formed area of the color photographic material processed. The stain is remarkably increased particularly when the processed color photographic material is stored under a high temperature/high humidity condition.
It is an object of the present invention to provide a method for improving organic colored substances in the stability thereof against light.
It is another object of this invention to provide a method which, without deteriorating both the hue and the color purity of organic colored substances, particularly, organic dyes, is capable of improving the stability thereof against light.
It is a further object of this invention to provide a method for improving the stability to light of a dye image forming a color photographic image without producing any stain on the un-color-formed area of the color photographic material.
The above objects or the present invention can be accomplished by having an organic colored substance which has at least one absorption maximum in the spectral region of 300 nm to 800 nm when dissolved in methanol be present together with at least one compound having the following Formula (I):

wherein R is a substituent, and n is an integer of 0 to 6, provided that where n is 2 or more, the plurality of Rs may be either the same or different from each other and that they may be combined with each other to form a ring.
The present invention will be described in detail below:
The substituent represented by the R of the above Formula (I) is not particularly restricted, but typical examples thereof include alkyl aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl and cycloalkyl groups, and in addition, other examples thereof include halogen atoms, cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, hydroxyl, alkoxy, cycloalkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and heterocyclic thio groups, and spiro compound residues and cross-linked hydrocarbon compound residues.
The alkyl group represented by R is preferably one having from 1 to 32 carbon atoms and may be either a straight-chain group or a branched-chain group.
The aryl group represented by R is preferably a phenyl group.
The acylamino group represented by R is, e.g., an alkylcarbonylamino group or arylcarbonylamino group.
The sulfonamido group represented by R is, e.g., an alkylsulfonylamino group or arylsulfonylamino group.
The alkyl constituent and the aryl constituent in the alkylthio and arylthio groups, respectively, represented by R include the above-mentioned alkyl and aryl groups represented by R.
The alkenyl group represented by R is preferably one having from 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having from 3 to 12 carbon atoms, and more particularly from 5 to 7 carbon atoms. The alkenyl group may be either straight-chain or branched-chain.
The cycloalkenyl group represented by R is preferably one having from 3 to 12 carbon atoms, and more preferably from 5 to 7 carbon atoms.
The sulfonyl group represented by R is, e.g., an alkylsulfonyl group or arylsulfonyl group. The sulfinyl group is, e.g., an alkylsulfinyl group or arylsulfinyl group.
The phosphonyl group is, e.g., an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group or an arylphosphonyl group.
The acyl group is, e.g., an alkylcarbonyl group or an arylcarbonyl group.
The carbamoyl group is, e.g., an alkylcarbamoyl group or an arylcarbamoyl group.
The sulfamoyl group is an alkylsulfamoyl group or an arylsulfamoyl group.
The acyloxy group is, e.g., an alkylcarbonyloxy group or an arylcarbonyloxy group.
The ureido group is, e.g., an alkylureido group or arylureido group.
The sulfamoylamino group is, e.g., an alkylsulfamoylamino group or an arylsulfamoylamino group.
The heterocyclic group is preferably a 5- to 7-member heterocyclic group, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group or a 2-benzothiazolyl group.
The heterocyclic oxy group is preferably one having a 5- to 7-member heterocyclic ring, such as a 3,4,5,6-tetrahydropyranyl-2-oxy group or 1-phenyltetrazolo-5-oxy group.
The heterocyclic thio group is preferably a 5- to 7-member heterocyclic thio group such as a 2-pyridylthio group, a 2-benzothiazolylthio group or 2,4-diphenoxy-1,3,5-triazolo-6-thio group.
The siloxy group is, e.g., a trimethylsiloxy group, triethylsiloxy group or dimethylbutylsiloxy group.
The imido group is, e.g., a succinemido group, a 3-heptadecylsuccinimido group, phthalimido group or glutarimido group.
The spiro compound residue is, e.g., a spiro[3.3]heptane-1-yl.
The cross-linked hydrocarbon compound residue is, e.g., a bicyclo[2.2.1]heptane-1-yl, tricyclo[3.3.1.1^3'7]decane-1-yl or 7,7-dimethyl-bicyclo[2.2.1]heptane-1-yl.
In Formula (I), if two Rs are adjacent to each other, these wo Rs may combine with each other to form a 5- to 7-membered ring. The case where the carbon atom in the second position and/or the carbon atom in the fourth position become spiro carbon atoms is also included in this invention.

Formula (I)

The following are typical examples of the compounds having Formula (I) to be used in this invention (hereinafter referred to as the compound of this invention), but the present invention is not limited to or by the examples.

Methods for synthesizing these compounds of this invention are of the prior art, and these compounds can be synthesized in accordance with those methods as described in, e.g., U.S. Patent No. 4,056,540 and West German OLS Patent Nos. 2,637,947, 2,749,279.
The amount of the compound of this invention to be used is preferably from 5 to 400 mole % based on the organic colored substance to be used in this invention, and more preferably from 10 to 300 mole %.
The term 'colored substances' to be used in this invention implies those materials whose color is visible to the human eye in sunlight, and, generally, organic materials which, in a methanol solution, have at least one absorption maximum in a spectral region of from 300 nm to 800 nm.
The organic colored substances usable in this invention includes all dyes belonging to groups classified according to their dyeing nature; examples are; water-soluble dyes such as basic dyes, acid dyes, direct dyes, solubilized vat dyes, mordant dyes; water-insoluble dyes such as sulfur dyes, vat dyes, solvent dyes, disperse dyes, azoic dyes, oxidation dyes; and reactive dyes.
Further, the organic colored substance to be used in this invention also includes all image-forming dyes known in the prior art such as, a dye formed by the oxidative coupling reaction between a dye-forming coupler for use in the photographic field and a color developing agent, a dye formed by the oxidation of a DRR (dye releasing redox) compound, a dye released or formed by the reaction of the oxidation product of a color developing agent with a DDR diffusable dye releasing coupler, a dye formed from an amidrazon compound, a dye developer and a dye for use in the silver dye bleach process.
The following are examples of the compound usable as the organic colored substance in accordance with the present invention:

(I-10) A dye formed by the oxidation of a DRR compound as described in, e.g., U.S.B351,673, U.S. Patent Nos. 3,932,381, 3,928,312, 3,931,144, 3,954,476, 3,929,760, 3,942,987, 3,932,380, 4,013,635 and 4,013,633, Japanese Patent O.P.I. Publication Nos. 113624/1976, 109928/1976, 104343/1976, 4819/1977 and 149328/1978, Research Disclosure Nos. 15157 (1976), 13024 (1975).
(I-11) A dye released or formed by the reaction of the oxidation product of a color developing agent with a DDR coupler as described in British Patent Nos. 840,731, 904,364, 932,272, 1,014,725, 1,038,331, 1,066,352 and 1,097,064, Japanese Patent O.P.I. Publication No. 13302/1976, UST900,029 (U.S. Defensive Publication), and U.S. Patent No. 3,227,550.
(I-12) A dye developer as, e.g., described in Japanese Patent Examined Publication Nos. 182/1960, 18332/1960, 32130/1973, 43950/1971, 2618/1974.
(I-13) Various dyes for use in the silver dye bleach process: Yellow dyes including azo dyes such as Direct Fast Yellow GC (C.I. 29000), Crysophenine (C.I. 24895), benzoquinone-type dyes such as Indigo Golden Yellow IGK (C.I. 59101), Indigosol Yellow 2GB (C.I. 61726), Algosol Yellow GCA-CF (C.I. 67301), Indanthrene Yellow GF (C.I. 68420), Mikethrene Yellow GC (C.I. 67300), Indathrene Yellow 4GK (C.I. 68405), anthraquinone-type dyes, polycyclic-type solubilized vat dyes and other vat dyes; magenta dyes including azo dyes such as Sumilight Supra Rubinol B (C.I. 29225), Benzo Brilliant Keranin B (C.I. 15080), indigoid-type dyes such as Indigosol Brilliant Pink IR (C.I. 73361), Indigosol Violet 15R (C.I. 59321), Indigosol Red Violet IRRL (C.I. 59316), Indanthrene Red Violet RRK (C.I. 67895), Mikethrene Brilliant Violet BBK (C.I. 6335), and solubilized vat dyes comprised of benzoquinone-type and anthraquinone-type compounds; and cyan dyes including azo dyes such as Direct Sky Blue 6B (C.I. 24410), Direct Brilliant Blue 2B (C.I. 22610), Sumilight Supra Blue G (C.I. 34200), phthalocyanine dyes such as Sumilight Supra Turquoise Blue G (C.I. 74140), Indanthrene Turquoise Blue 5G (C.I. 69845), Indanthrene Blue GCD (C.I. 73066), Indigosol 04G (C.I. 73046) and Anthrasol Green IB (C.I. 59826).
(I-14) A dye formed by the oxidative coupling reaction between a dye-forming coupler for use in the photographic field and color developing agent.
The dye-forming couplers which are to form the dyes of (I-14) include the yellow, magenta and cyan dye-forming-type couplers. These couplers may be of either the so-called 4-equivalent type as described in, e.g., U.S. Patent Nos. 3,277,155 and 3,458,315 or the 2-equivalent type wherein the carbon atom in the coupling position is substituted by a substituent (split-off group) that can split off at the time of the coupling reaction.
Useful examples of the yellow dye-forming coupler include benzoylacetanilide-type couplers and pivaloylacetanilide-type couplers. Examples of the magenta dye-forming coupler include 5-pyrazolone-type couplers, pyrazolotriazole-type couplers, imidazopyrazole-type couplers, pyrazolopyrazole-type couplers, pyrazolotetrazole-type couplers, pyrazolinobenzimidazole-type couplers and indazolone-type couplers. And examples of the cyan dye-forming coupler include phenol-type couplers, naphthol-type couplers and pyrazoloquinazolone-type couplers.
Concrete examples of these yellow, magenta and cyan dye-forming couplers are known to those skilled in the art in the photographic field, and all these dye-forming couplers of the prior art may be used in the present invention.
The following are examples representative of the yellow couplers capable of forming the yellow dyes of (I-14):

These yellow couplers include those compounds described in, e.g., West German OLS Patent Nos. 2,057,941 and 2,163,812, Japanese Patent O.P.I. Publication Nos. 26133/1972, 29432/1973, 65321/1975, 3631/1976, 50734/1976, 102636/1976, 66835/1973, 94432/1973, 1229/1974 and 10736/1974, and Japanese Patent Examined Publication Nos. 33410/1976 and 25733/1977, and can be synthesized according to those methods as described in these publications.
The following are examples representative of the magenta couplers capable of forming the magenta dyes of (I-14):

These magenta couplers include those compounds described in, e.g., U.S. Patent No. 3,684,514, British Patent No. 1,183,515, Japanese Patent Examined Publication Nos. 6031/1965, 6035/1965, 15754/1969, 40757/1970 and 19032/1971, Japanese Patent O.P.I. Publication Nos. 13041/1975, 129035/1978, 37646/1976 and 62454/1980, U.S. Patent No. 3,725,067, British Patent Nos. 1,252,418 and 1,334,515, Japanese Patent O.P.I. Publication Nos. 171956/1984, 162548/1984, 43659/1985 and 33552/1985, Research Disclosure No. 24626 (1984), Japanese Patent Application Nos. 243007/1984, 243008/1984, 243009/1984, 243012/1984, 70197/1985 and 70198/1985, and may be synthesized in accordance with those methods as described in these publications.
The cyan couplers for forming the cyan dyes of (I-14), although not specially restricted, are desirably phenol-type cyan couplers.
The following are examples representative of the cyan couplers capable of forming the cyan dyes of (I-14):

These cyan couplers include those compounds described in, e.g., U.S. Patent Nos. 2,423,730 and 2,801,171, Japanese Patent O.P.I. Publication Nos. 112038/1975, 134644/1975, 109630/1978, 55380/1979, 65134/1981, 80045/1981, 155538/1982, 204545/1982, 98731/1983 and 31953/1984, and may be synthesized in accordance with those methods as described in these publications.
In the present invention, where such couplers are used, dyes are formed from them by reaction with the oxidation product of a color developing agent.
The above color developing agent includes aminophenols and phenylenediamines, and these color developing agents may be used in admixture.
The following Formula (II) is representative of suitable aminophenols. The aminophenol can also used in the form of a complex with a mineral acid, for example, H₂SO₄, HCℓ, HN₃, or a hydrate of the complex, for example, $\frac{3}{2}$
H₂SO₄.H₂O.

wherein R₁ is as alkyl or alkoxy group or halogen atom, and m is an integer of 0 to 4; R₂ and R₃ each represents hydrogen, an alkyl group (e.g., methyl, ethyl, propyl and butyl) or a substituted alkyl group. (e.g., an alkoxy alkyl, hydroxy alkyl or alkylsulfonamino alkyl group).
The following Formula (III) is representative of suitable phenylenediamines. The phenylenediamine can also used in the form of a complex with a mineral acid for example, H₂SO₄, HC , HNO₃, or a hydrate of the complex for example, $\frac{3}{2}$
H₂SO₄.H₂O.

wherein R₄ is an alkyl or alkoxy group or a halogen atom, and is an integer of 0 to 4; R₅ represents hydrogen or -SO₃X (wherein, X represents an alkali metal atom.); R₆ and R₇ each represents hydrogen an alkyl group (e.g., methyl, ethyl, propyl, butyl and octyl), or a substituted alkyl group (e.g., a hydroxyalkyl group, a alkoxyalkyl group, and an alkyl sulfonylamino alkyl group.
Typical examples of such color developing agents capable or producing colored materials or substances by combining with various couplers will be given below:

Exemplified Developing Agents

The developing agents D-1 - D-8 can also be used in the form of a complex with a mineral acid, for example H₂SO₄, HCℓ, HNO₃, or a hydrate of the complex, for example, $\frac{3}{2}$
H₂SO₄.H₂O.
Examples of different other dyes which may also be used as the colored substance of the present invention will be given below:
Compounds suitably usable as the organic colored substance of this invention include anthraquinone, quinoneimine, azo, methine, azomethine, polymethine, indoamine, indophenol and formazan dyes. The organic colored substances more suitably usable in this invention are methine, polymethine, indoamine and indophenol dyes, and those compounds having the following group:

In the above group, the phenyl group is an unsubstituted phenyl group or a phenyl group which is substituted by, e.g., an alkyl group, alkoxy group, a halogen atom or an amino group.
In the present invention, more preferably, those dyes usable as the organic colored substance are the foregoing dyes of (I-14), and most preferably, the dyes of (I-14) which are formed by the reaction between those pyrazolotriazole-type magenta dye-forming couplers given in M-5, M-6, M-7, M-8, M-9, M-10, M-12, M-13 and M-14 and those phenylenediamine color developing agents given in D-1 through D-8.
In the present invention, as long as the compound of this invention is in the state of reducing the fading of an organic colored substance by light, no restrictions are put on the condition of the presence of the compound together with the colored substance. The compound may be dissolved uniformly along with the organic colored substance in one and the same solvent, or it may also be mordanted along with the organic colored substance in one and the same mordant. Also, the compound of this invention or the organic colored substance may be impregnated into a solid-solution or semi-solid-solution layer of the organic colored substance or the compound of this invention.
A specially preferred method is such that, in accordance with those methods as described in U.S. Patent Nos. 2,332,027, 2,801,170, 2,801,171, 2,272,191 and 2,304,940, the compound of this invention and organic colored substance are dissolved into a high-boiling solvent, if necessary, in combination with a low-boiling solvent, and the solution is then added to and dispersed into a hydrophilic colloid solution, for example a gelatine solution; and the resulting liquid is then coated on a substrate and dried. In this instance, if necessary, hydroquinone derivatives, ultraviolet abosorbing agents, or known agents for preventing the fading of dye images, may be used in combination, and in this case, two or more kinds of the compound of this invention may also be mixed to be used.
In this instance, favorable results of this invention can also be obtained even if the compound of this invention and organic colored substance are separately dissolved into divided parts of a high-boiling solvent (if necessary, in combination with a low-boiling solvent) and the prepared solutions are separately added to and dispersed into one and the same hydrophilic colloid solution.
Another particularly preferred method is such that, in accordance with those methods as described in U.S. Patent Nos. 2,322,027, 2,801,170, 2,801,171, 2,272,191 and 2,304,940, the compound used in accordance with this invention and a precursor of an organic colored substance such as a dye-forming coupler a DDR compounds, or a DDR couplers are dissolved into a high-boiling solvent, if necessary, in combination with a low-boiling solvent, the solution is then added to and dispersed into a hydrophilic colloid solution, and the resulting liquid is then coated on a substrate and dried, and after that, the precursor of the organic colored substance is converted into an organic colored substance. In this instance, if necessary, hydroquinone derivatives, ultraviolet absorbing agents or known agents for preventing the fading of dye images may be used in combination, and in this case, two or more kinds of the compounds may also be mixed to be used.
In this instance, favorable results of this invention may also be obtained even if the compound usable in accordance with this invention and the precursor of the organic colored substance are separately dissolved into divided parts of a high-boiling solvent (if necessary, in combination with a low-boiling solvent), and the two solutions are separately added to and dispersed into one and the same hydrophilic solution.
A further particularly preferred method of adding the compound will be described in detail below:
One or two or more kinds of the compound usable in accordance with this invention, precursors of organic colored substance such as dye-forming couplers, DRR compounds and DDR couplers, and, if necessary hydroquinone derivatives, ultraviolet absorbing agents or known agents, e.g., for preventing the fading of dye images, are simultaneously dissolved into a high-boiling solvent such as an organic acid amide, carbamate, ester, ketone, hydrocarbon or urea derivative; particularly, dibutyl phthalate, tricresyl phosphate, di-iso-octyl azelate, dibutyl sebacate, trihexyl phosphate, decalin, N,N-diethylcaprylamide, N,N-diethyllaurylamide, pentadecyl-phenyl ether or fluoroparaffin, if necessary, in combination with a low boiling solvent such as ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane or tetrohydrofuran (these high-boiling solvents and low-boiling solvents may be used alone or in admixture), and the resulting solution is then mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing an anion-type surface active agent such as an alkylbenzenesulfonic acid or an alkylnaphthalenesulfonic acid and/or a nonionic surface active agent such as a sorbitan-sesquioleiate or sorbitan-monolaurate, and the mixture is emulsifiedly dispersed by means of a high-speed rotary mixer, colloid mill or ultrasonic disperser, and the thus obtained dispersed liquid is then added to a hydrophilic colloid solution (such as a silver halide emulsion). The resulting liquid is then coated on a substrate and dried.
In the case where the method of this invention is applied to a photographic color material, both the colored substance precursor and the compound of this invention may be present in any of or some of the hydrophilic colloid layers of the photographic color material. These materials may also be present in both a light-sensitive element and a non-light-sensitive element. Where the colored substance and the compound of this invention are incorporated in such a non-light-sensitive element, such as the dye-image receiving element to be used in a photographic diffusion transfer film unit, it is desirable that these be mordanted. Accordingly, in such application, the compound used in accordance with this invention is preferred to be in such a molecular form as can be retained in the mordant layer of the image-receiving element so as not to move away from the colored substance to be stabilized.
In a color photographic material to be used in the method of this invention, the silver halide emulsion thereof is one prepared generally by dispersing silver halide grains into a hydrophilic colloid. Suitable silver halides include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures of these silver halides.
These silver halide emulsions, in order to be sensitized to desired spectral wavelength regions, may be optically sensitized by using various sensitizing dyes. These silver halide emulsions may also be chemically sensitized in the usual manner in the photographic field.
To the silver halide emulsion may be added a compound known as an antifoggant or stabilizer to the photographic field for the purpose of preventing fogging of and/or stabilizing the characteristics of the color photographic material during its manufacturing process, storage or photographic processing. In addition, various photographic additives such as hardening agents, plasticizers, brightening agents, antistatic agents and coating aids, may be added alone or in combination of two or more kinds of them.
A color photographic material to which this invention is to be applied may be either a coupler-in-emulsion-type color photographic material containing dye-forming couplers or a coupler-in-developer-type color photographic material to be processed in a dye-forming-coupler-containing developer.
The above-mentioned coupler-in-emulsion-type color photographic material containing dye-forming couplers may be processed in the usual manner, whereby a color image is obtained. The principal processes in this instance are color developing, bleaching and fixing and, if necessary, washing, stabilizing, and the like processes. Of these processes, two or more processes may take place in a monobath such as in the bleach-fix process. The color developing takes place usually in an alkaline solution containing an aromatic primary amine developing agent. The preferred examples of those aromatic primary amine developing agents are Exemplified Developing Agents D-1 through D-6 which have been disclosed hereinabove.
Where the color photographic material to which this invention is to be applied is a color diffusion transfer film unit, the processing of the photographic material takes place automatically inside the light-sensitive material. In this instance, the developing agent is contained in a rupturable container. Examples for developing agents usable, in addition to the foregoing D-1 through D-6 are N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone and 3-methoxy-N,N-diethyl-p-phenylenediamine.
Where the method of this invention is applied to a color photographic material, the color photographic materials can be various color light-sensitive photographic materials such as color positive film, color photographic paper, color negative film, color reversal film, color diffusion transfer film units and color photographic materials for the silver dye bleach process.

EXAMPLES

The present invention will be illustrated by the following examples, but the invention is not limited thereto.

EXAMPLE 1

0.5 Gram of a magenta dye (the absorption maximum of it in its methanol solution: 538 nm) having the following structural formula:

was dissolved into 4 ml of trioctyl phosphate and 8 ml of ethyl acetate, and this solution was then emulsifiedly dispersed into 10 ml of an aqueous 10% gelatin solution containing 2 ml of an aqueous 0.5 % sodium dodecylbenzene sulfonate solution.
Subsequently, this emulsifiedly dispersed liquid was mixed with 300 ml of an aqueous 5% gelatin solution, and the mixture was then coated on a both-side-polyethylene-laminated paper support, whereby a sample was obtained. This sample was designated as Sample No.1.
Further, Samples No.2 and No.3 were prepared by coating in the same manner as in Sample No.1 except that comparative compounds having the following structural formulas (a) and (b) were added each in a quantity of 0.5 g in place of the above compound in preparing the emulsifiedly dispersed liquid.
And twelve samples (No.4 through No.15) were prepared by coating also in the same manner as in Sample No.1 except that 0.5 g each of the exemplified compounds of this invention given in Table 1 was added in preparing the emulsifiedly dispersed liquid.

Each of the above samples was exposed over a period of 200 hours to the light of a xenon fadeometer to thereby examine the light resistance of the dye image of each sample. The results are shown in Table 1. The light resistance of the dye image is expressed as a dye residual rate.
As is apparent from Table 1, Samples No.4 to No.15 which use the antifading agents of this invention show more excellent light-fading-preventive effect than do Samples No.2 and No.3 which use metallic complex compounds of the prior art, and show little or no change of color to dark brown.

EXAMPLE 2

15 different samples (No. 16 through No. 30) were prepared in quite the same manner as in Example 1 except that the magenta dye of Example 1 was replaced by a magenta dye having the following structural formula (the absorption maximum of it in its methanol solution: 536 nm). Each of the obtained samples was exposed over a period of 150 hours to the light of a xenon fadeometer to thereby examine the light resistance of each sample. The results are shown in Table 2.
As is apparent also from Table 2, the samples which use the antifading agents of the present invention show more excellent light-fading-preventive effect than do the comparative samples which use metallic complex compounds of the prior art, and the samples of the invention show little or no change of color to dark brown, and their satisfactory color remained intact even after the light resistance test.

EXAMPLE 3

30 Grams of Exemplified Coupler M-8 as a magenta coupler were dissolved into 30 ml of triphenyl phosphate and 100 ml of ethyl acetate, this solution was added to 500 ml of an aqueous 5 % gelatin solution containing 2.5 g of sodium dodecyl benzene-sulfonate, this mixture was dispersed by a homogenizer, the obtained dispersed liquid was added to 1,000 ml of a green-sensitive silver chlorobromide emulsion (containing 30 mole % silver chloride), and to the emulsion were further added 10 ml of a 2 % methanol solution of N,Nʹ,Nʺ-triacryloylhexahydro-s-triazine as a hardening agent, and the resulting coating liquid was coated on a polyethylene-coated paper support and then dried, whereby a monochromatic color photographic material sample was obtained. This sample was designated as Sample No.31.
Samples No.32 and No.33 were prepared by coating in the same manner as in the above except that 24 g each of Comparative Compounds (c) and (d) having the following structural formulas were added, respectively, in preparing the above emulsifiedly dispersed liquid.
Further, seven different samples (No.34 to No.40) were prepared by coating in the same manner as the above except that 20 g each of the exemplified compounds of this invention indicated in Table 3 were added.

Each of these samples was exposed and then processed in the following procedure by using the following processing solutions:

Developer:

Benzyl alcohol	12.0 ml
Sodium hexametaphosphate	2.5 g
Anhydrous sodium sulfite	1.9 g
Sodium bromide	1.4 g
Potassium bromide	0.5 g
Sodium carbonate	30.0 g
N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline sulfate	5.0 g

Water to make 1 liter. Use sodium hydroxide to adjust the pH to 10.30.

Bleach-Fix Bath:

Iron-ammonium ethylenediaminetetraacetate	61.0 g
Diammonium ethylenediaminetetraacetate	5.0 g
Ammonium thiosulfate	124.5 g
Ammonium metabisulfite	13.3 g
Anhydrous sodium sulfite	2.7 g

Water to make 1 liter. Use aqueous ammonia to adjust the pH to 6.5.

Processing Steps:

(at 30°C)	Processing time
Developing	3 minutes and 30 seconds
Bleach-fix	1 minute and 30 seconds
Washing	3 minutes
Drying

Each of the thus dye-image-formed samples was subjected to a fading test by being exposed over a period of 150 hours through an ultraviolet-absorbing filter 'Kodak Wratten Filter No.2A', to the light of a xenon fadeometer. The results are as given in Table 3.
In the table, the faded degree of each sample is given in terms of the change in the density of the portion that had had an initial density of 1.0 before being subjected to the fading test.
As is apparent from the results given in Table 3, the antifading agents according to this invention have more excellent light-fading-preventive effect than do the conventional organic antifading agents.

EXAMPLE 4

35 Grams of Exemplified Coupler C-6 as a cyan coupler were dissolved into 35 ml of dioctyl phthalate and 100 ml of ethyl acetate, this solution was added to an aqueous 5 % gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate, this mixture was then dispersed by means of a homogenizer, and the resulting dispersed liquid was added to 1,000 ml of a red-sensitive silver chlorobromide emulsion (containing 30 mole % silver chloride). To this emulsion were further added 10 ml of a 2 % methanol solution of N,Nʹ,Nʺ-triacryloylhexahydro-s-triazine as a hardening agent, and the thus obtained coating liquid was coated on a polyethylene-coated paper support, whereby a monochromatic color photographic material was obtained. This material was desegnated as Sample No.41.
Subsequently, nine different samples (No.42 to No.50) were prepared in the same manner as in Example 3 except that 15 g each of a Comparative Compound (e) having the following structural formula, and the exemplified compounds of this invention given in Table 4 were added in preparing the above emulsifiedly dispersed liquid.

Each of these samples was exposed and then processed in quite the same manner as in Example 3 to thereby obtain a dye image. The dye image of each sample was then subjected to a fading test by being exposed over a period of 250 hours through an ultraviolet absorbing filter (the same filter as was used in Example 3) to the light of a xenon fadeometer. The results are as given in Table 4.
As is apparent from Table 4, the antifading agents of this invention have a large light-fading-preventive effect also on the cyan color-formed dye.

EXAMPLE 5

The following is an example where the present invention is applied to a thermally developable light-sensitive element.

Preparation of a Thermally Developable Light-Sensitive Element:

A thermally developable light-sensitive element was prepared by using the following materials:
Gelatin ... A mixture of limed gelatin for photographic use and phenylcarbamoylated gelatin (Type 17819PC, produced by Ruthlow Co.) mixed in the ratio by weight of 2 : 1.
PVP ... Polyvinyl pyrrolidone (K-30)
Solid thermal solvent ... p-butoxybenzamide
Liquid thermal solvent .. 1,2,4-butane-triol
Color developing agent ... A mixture of the following color developing agent
A and B mixed in the molar ratio of 7 : 3.

Organic silver salt ... 5-methylbenzotriazole silver salt
Light-sensitive silver halide ..... The same silver halide as described in the example of Japanese Patent Application No. 254257/1986 was used.

The above numerical values are in g/m², provided, however, that the organic silver salt and light-sensitive AgX are in silver equivalence.

Preparation of a Thermally Developed Image-Receiving Element:

On a photographic baryta paper (170 µm in thickness, weight: 190 g/m²) was coated the following image-receiving layer coating liquid so that its wet layer thickness was 137.2 µm, and then dried, whereby a thermally developed image-receiving element was prepared. This was designated as Sample No. 51.

Image-Receiving Layer Coating Liquid:

Polyvinyl chloride (n = 1,100, produced by Wako Junyaku Co.)	21.0 g
Tetrahydrofuran	190 ml

Subsequently, nine different samples (No.52 to No.60) were prepared by coating in the same manner as in the above except that 0.8 g each of the comparative compound, ultraviolet absorbing agent and the compounds of this invention as shown in Table 6 were added in preparing the above image-receiving layer coating liquid.
The foregoing thermally developable light-sensitive element was subjected to 4000 CMS exposure by being exposed through a step wedge and a green filter to a tungsten light, and then it was superposed on each of the above thermally developed-image receiving elements with their coated surfaces brought into contact with each other, and the unit was preheated for 4 seconds at 100°C, and then heated under pressure (thermally developed) at 150°C for 90 seconds. In this case, the preheating and the heating under pressure were performed by using a thermal developing apparatus as shown in Figure 1 of Japanese Patent O.P.I. Publication No. 153651/1986.
After completion of the heating, when the image-receiving element was quickly peeled apart from the light-sensitive element, a magenta color image was obtained on the surface of the image-receiving element. This magenta color image was examined with respect to its photographic characteristics and its stability against light. The results are also given in Table 6.

Evaluation of Photographic Characteristics

The maximum reflection density and the minum reflection density of the magenta color image of each sample were measured with a green light by using a SAKURA Densitometer PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.).

(Evaluation of Stability against Light)

The dye density residual rate (%) of each magenta color image was examined in the manner that each magenta image-having sample was exposed over periods of 5 days and of 10 days to the light of a xenon fadeometer (SUGA Tester WE-6X-HC).

The absorption maximum of the formed magenta image in its methanol solution was 528 nm.
From Table 6, it is understood that the antifading agent of this invention, even when used in a thermally developable light-sensitive material, is excellently effective in preventing the dye image of the light-sensitive material from fading. Also, by using the antifading agent of this invention and the ultraviolet absorbing agent in combination, the antifading effect can be further improved.

Claims

A method for preventing an organic colored substance which has at least one absorption maximum in the spectral region of 300 nm to 800 nm when dissolved in methanol from fading by light, characterised by
making said organic colored substance coexist with a compound of the formula (I)
wherein R is a substituent and n is an integer of 0 to 6, provided that when n is 2 or more, the plurality of Rs' may be either the same or different from each other and that they may be combined with each other to form a ring.
The method of claim 1, wherein the amount of said compound of the formula (I) used is from 5 to 400 mole% based on said organic colored substance.
The method of claim 1, 2 or 3, wherein said organic colored substance is selected from the group consisting of a basic dye, an acid dye, a direct dye, a vat dye or a solubilized vat dye, a mordant dye, a sulfur dye, a solvent dye, a disperse dye, an azoic dye, an oxidation dye, and a reactive dye.
The method of claim 1 or 2, wherein said organic colored substance is selected from the group consisting of a dye formed by the oxidation of a dye releasing redox compound, a dye released or formed by the reaction of the oxidation product of a color developer agent with a diffusable dye releasing coupler, a dye developer, a dye formed from an amidrazon compound, a dye for use in the silver dye bleach process and a dye formed by the oxidative coupling reaction between a dye-forming coupler for use in the photographic field and a color developing agent.
The method of claim 1 or 2, wherein said organic colored substance is a dye formed by the oxidative coupling reaction between a dye-forming coupler for use in the photographic field and a color developing agent.
The method of claim 5, wherein said dye-forming coupler is selected from the group consisting of a benzoylacetanilide-type coupler, a pyraloylacetanilide-type coupler, a 5-pyrazolone-type coupler, a pyrazolotriazole-type coupler, an imidazopyrazole-type coupler, a pyrazolopyrazole-type coupler, a pyrazolotetrazole-type coupler, a pyrazolinobenzimidazole-type coupler, an indazolone-type coupler, a phenol-type coupler, a naphthol-type coupler, and a pyrazoloqunazolone-type coupler.
The method of claim 5, wherein said color developer is a compound of the following (III), a complex of said compound of formula (III) with a mineral acid, or a hydrate of said complex.
wherein R₄ represents an alkyl or alkoxy group or halogen atom, and is an integer of 0 to 4; R₅ represents hydrogen or -SO₃X wherein, X represents an alkali metal atom; and R₆ and R₇ each represents hydrogen an alkyl group.
The method of claim 5, wherein said dye forming coupler is a pyrazolotriazole-type magenta dye-forming coupler, and said color developing agent is selected from the following groups D-1 to D-8, a complex of said color developing agent with a mineral acid, or a hydrate of said complex.
A stabilized colored composition comprising an organic colored substance which has at least one absorption maximum in the spectral region of 300 nm to 800 nm when dissolved in methanol characterised by the content of a stabilizing amount of a compound of the formula (I)
wherein R is a substituent and n is an integer of 0 to 6, provided that when n is 2 or more the plurality of Rs' may be either the same or different from each other and that they may be combined with each other to form a ring.
The stabilized colored composition of claim 9, wherein said organic colored substance and said compound of the formula (I) are dissolved in a high-boiling solvent, or in a high-boiling solvent in combination with a low boiling solvent, and the solution is then dispersed into a hydrophilic colloid solution.
A stabilized composition comprising a precursor of an organic colored substance which is selected from the group consisting of a dye-releasing redox compound, diffusable dye releasing coupler and a dye-forming coupler, characterised by the content of a stabilizing amount of a compound of the formula (I)
wherein R is a substituent and n is an integer of 0 to 6, provided that when n is 2 or more the plurality of Rs' may be either the same or different from each other and that they may be combined with each other to form a ring.
The stabilizer composition of claim 11, wherein said precursor of the organic colored substance and said compound of the formula (I) are dissolved into a high-boiling solvent, or in a high-boiling solvent in combination with a low-boiling solvent, and the solution is then dispersed into a hydrophilic colloid solution.
A substrate coated with a composition of claims 9 to 12.
A photographic element comprising a support and, provided thereon, a layer containing an organic colored substance having at least one absorption maximum in the spectral region of 300 nm to 800 nm when dissolved in methanol and characterised in that the organic colored substance coexists with a compound of the formula (I);
wherein R is a substituent and n is an integer of 0 to 6, provided that when n is 2 or more the plurality of Rs' may be either the same or different from each other and that they may be combined with each other to form a ring.
The photographic element of claim 14, wherein said organic colored substance is selected from the group consisting of a dye formed by the oxidation of a dye releasing redox compound, a dye released or formed by the reaction of the oxidation product of a color developing agent with a diffusable dye releasing, a dye developer, a dye for use in the silver dye bleach process and a dye formed by the oxidative coupling reaction between dye-forming coupler for use in the photographic field and a color developing agent.
A color photographic material comprising a support and, provided thereon, a layer containing a precursor of an organic colored substance characterised in that the layer also contains a compound of the formula (I);
wherein R is a substituent and n is an integer of 0 to 6, provided that when n is 2 or more the plurality of Rs' may be either the same or different from each other and that they may be combined with each other to form a ring.
The color photographic material of claim 16, wherein said precursor of the organic colored substance and said compound of the formula (I) are dissolved into a high-boiling solvent, or in a high-boiling solvent in combination with a low-boiling solvent and the solution is then dispersed into a hydrophilic colloid solution.
The color photographic material of claim 16 or 17, wherein said precursor of the organic colored substance is selected from the group consisting of a dye releasing redox compound, a diffusable dye releasing coupler and a dye-forming coupler.
The color photographic material of claim 16 or 17, wherein said precursor of the organic colored substance is a dye-forming coupler.
The color photographic material of claim 17, wherein said precursor of the organic colored substance is a dye-forming coupler which is selected from the group consisting of a benzoylacetanilide-type coupler, a pyraloylacetanilide-type coupler, 5-pyrazolone-type coupler, a pyrazolotriazole-type coupler, an imidazopyrazole-type coupler, a pyrazolopyrazole-type coupler, pyrazolotetrazole-type coupler, a pyrazolinobenzimidazole-type coupler, an indazolone-type coupler, a phenol-type coupler, a naphthol-type coupler and a pyrazoloqunazolone-type coupler.
The color photographic material of claim 17, wherein said precursor of the organic colored substance is a dye-forming coupler which is a pyrazolotriazole-type dye forming coupler.