JPS6228182B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the stabilization of organic substrates against light, and more particularly to the stabilization of organic compounds, particularly organic dyes, against light. It is generally known that organic base materials, such as organic dyes, tend to fade or change color when exposed to light. To prevent fading or discoloration of
That is, research has been conducted to improve light resistance. The present invention can be very advantageously used for the purpose of improving the light resistance of the above-mentioned organic base material. In this specification, the term organic base substance or base compound includes substances that appear colored or colorless to the human eye under irradiation with sunlight, and includes not only substances that simply have an absorption maximum in the visible range, but also include, for example, Also included are optical brighteners or substances with an absorption maximum in the infrared. In the present invention, the organic substrate material includes an organic material having an absorption maximum from about 300 nm in the ultraviolet region to about 800 nm in the infrared region. As used herein, the term pigment or dye includes organic substances that appear colored to the human eye under sunlight. As used herein, the term light refers to approximately
It means electromagnetic waves of less than 800 nm, including ultraviolet light of less than about 400 nm, visible light of about 400 nm to about 700 nm, and infrared light of about 700 nm to about 800 nm. It has long been known that organic substrate materials, such as pigments or dyes, have a tendency to fade or change color when exposed to light, and methods for reducing this fading or discoloration, that is, methods for improving light resistance, are as follows. There are many reports. For example, in U.S. Patent No. 3,432,300, organic compounds such as indophenols, indoanilines, azo and azomethine dyes are made to be robust to visible and ultraviolet light by mixing them with phenolic-type compounds having fused heterocyclic ring systems. It is stated that the properties are improved. In general, in the field of silver halide photographic materials, "The
Theory of the Photographic Process”
(Macmillan, 1967), azomethine dyes or indoaniline dyes are formed by the reaction of the oxidized product of an aromatic primary amine developing agent with a color former (coupler). However, many methods are known for improving the light stability of images made from these dyes, ie, color images. For example, US Patent No. 2360290, US Patent No. 2418613, US Patent No.
No. 2675314, No. 2701197, No. 2704713, No. 2728659, No. 2732300, No. 2735765,
No. 2710801, No. 2816028, British Patent No.
Hydroquinone derivatives described in U.S. Patent No. 1363921, etc., gallic acid derivatives described in U.S. Pat.
p-alkoxyphenols described in U.S. Patent No. 2735765 and U.S. Patent No. 3698909;
No. 3432300, No. 3573050, No. 3574627, No. 3764337, No. 3574626, No. 3698909,
Derivatives such as chromans and coumarans as described in No. 4015990 are known. but,
Although these compounds are effective as agents for preventing fading and change of color images, they are not sufficient. In addition, the stability of organic base compounds against light,
British Patent No. 1451000 describes an improvement method using an azomethine quenching compound whose absorption maximum is more bathochromic than that of the base compound, but this azomethine quenching compound itself is strongly colored. Therefore, it is disadvantageous in that it has a large influence on the hue of the base material. Furthermore, the use of metal complexes to prevent photodegradation of polymers was reported by JP Guillory and RSBecker.
J.Polym.Sci., Polym.Chem.Ed., 12 , 993
(1974), by RPRRanaweera and G. Scott.
J.Polym.Sci., Polym.Lett.Ed., 13 , 71 (1975)
The method for stabilizing dyes using metal complexes is described in JP-A No. 50-87649 and Research
Disclosure 15162 (1976). However, since these complexes do not have a great anti-fading effect and do not have high solubility in organic solvents, they cannot be added in an amount sufficient to fully exhibit the anti-fading effect. Moreover, these complexes have the disadvantage that, because of their high coloration, when added in large amounts they have an adverse effect on the hue and purity of the organic substrate, especially the dye. Accordingly, one object of the present invention is to provide a method for improving the light stability of organic substrate materials. Another object of the present invention is to provide a method for improving the light stability of organic substrate materials, especially pigments or dyes, without deteriorating their hue and purity. Another object of the present invention is to provide a method for improving the light stability of an organic substrate using an organic substrate stabilizer that has high solubility in organic solvents and high miscibility with the organic substrate. It is to provide. Another object of the present invention is to provide a method for improving the light stability of color images forming color photographic images. Another object of the present invention is to provide a method for improving the light stability of dyes formed by the reaction of aromatic primary amine developing agents with color couplers. Other objects of the present invention will become apparent from the following description of the specification. The above and other objects of the present invention are to provide an organic base material having an absorption maximum in a range of about 300 nm to about 800 nm and the following general formulas (), (), ().
Or, it was achieved by coexisting at least one type of complex represented by (). In the formula, M represents Cu, Co, Ni, Pd or Pt. R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom,
Halogen atom, cyano group, alkyl group, aryl group, cycloalkyl group, heterocyclic group, or R ¹ and R ² , R ² and R ³ or R ³ and R ⁴ combined with each other to form a 6-membered ring represent a necessary group of nonmetallic atoms. R ⁵ and R ⁸ each represent a hydrogen atom, an alkyl group or an aryl group. R ⁶ represents a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group. R ⁷ represents an alkyl group or an aryl group. Z represents a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring. The halogen atoms represented by R ¹ , R ² , R ³ and R ⁴ include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The alkyl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably an alkyl group having 1 to 19 carbon atoms, and may be either a straight-chain alkyl group or a branched alkyl group, and may be a substituted or substituted alkyl group. , or may be unsubstituted. The aryl group represented by R ¹ , R ² , R ³ and R ⁴ preferably has 6 to 14 carbon atoms.
is an aryl group, which may be substituted or unsubstituted. The heterocyclic group represented by R ¹ , R ² , R ³ and R ⁴ is preferably a 5-membered ring or a 6-membered ring, and may be substituted or unsubstituted.
The cycloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably a 5-membered ring group or a 6-membered ring group, and may be substituted or unsubstituted. The six-membered ring formed by bonding R ¹ and R ² , R ₂ and R ³ or R ³ and R ⁴ to each other is preferably a benzene ring, and this benzene ring may be substituted or unsubstituted. It may also be a condensed one. Examples of the linear or branched alkyl group represented by R ¹ , R ² , R ³ and R ⁴ include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Examples include a tetradecyl group, a hexadecyl group, and an octadel group. Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include a phenyl group and a naphthyl group. The heterocyclic group represented by R ¹ , R ² , R ³ and R ⁴ is a 5- to 6-membered heterocyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom in the ring as a hetero atom. For example, furyl group, hydrofuryl group, thienyl group, pyrrolyl group, pyrrolidyl group, pyridyl group, imidazolyl group, pyrazolyl group, quinolyl group, indolyl group,
Examples include oxazolyl group and thiazolyl group. Examples of the cycloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ include cyclopentyl group,
Examples include a cyclohexyl group, a cyclohexenyl group, and a cyclohexadiene group. Examples of the 6-membered ring formed by bonding R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ include a benzene ring, a naphthalene ring, an isobenzothiophene ring, an isobenzofuran ring, and an isobenzofuran ring. Examples include the indoline ring. The alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R ¹ , R ² , R ³ and R ⁴ above is a divalent linking group, such as an oxy group (-o-), a thio group (- s-), amino group, oxycarbonyl group, carbonyl group, carbamoyl group,
Via a sulfamoyl group, carbonylamino group, sulfonyl group or carbonyloxy group,
It may be bonded to a carbon atom on the benzene ring. Examples of an alkyl group represented by R ¹ , R ² , R ³ and R ⁴ bonded to a carbon atom on a benzene ring via the above-mentioned divalent linking group include an alkoxy group (for example, a methoxy group, ethoxy group, butoxy group, propoxy group, n-decyloxy group, n-dodecyloxy group, or n-hexadecyloxy group), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group,
butoxycarbonyl group, n-decyloxycarbonyl group or n-hexadecyloxycarbonyl group), acyl group (e.g. acetyl group, valeryl group, stearoyl group, benzoyl group or toluoyl group etc.), acyl group (e.g. acetoxy group) or hexadecylcarbonyloxy group), alkylamino group (e.g.
n-butylamino group, N·N-diethylamino group, or N·N-didecylamino group), alkylcarbamoyl group (e.g., butylcarbamoyl group, N·N-diethylcarbamoyl group, or n-dodecylcarbamoyl group, etc.), alkyl Sulfamoyl group (e.g., butylsulfamoyl group, N.N-diethylsulfamoyl group, n-dodecylsulfamoyl group, etc.), sulfonylamino group (e.g., methylsulfonylamino group, butylsulfonylamino group, etc.) ), sulfonyl groups (e.g., mesyl or ethanesulfonyl), or acylamino groups (e.g., acetylamino, valerylamino,
palmitoylamino group, benzoylamino group, toluoyl amino group, etc.). An example of a cycloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ bonded to a carbon atom on the ring of the compound of the present invention via the above-mentioned divalent linking group is a cyclohexyloxy group. , cyclohexylcarbonyl group, cyclohexyloxycarbonyl group, cyclohexylamino group, cyclohexenylcarbonyl group, or cyclohexenyloxy group. Examples of aryl groups represented by R ¹ , R ² , R ³ and R ⁴ bonded to carbon atoms on the ring of the compound of the present invention via the above-mentioned divalent linking group include aryloxy groups (e.g. , phenoxy or naphthoxy groups), aryloxycarbonyl groups (e.g. phenoxycarbonyl or naphthoxycarbonyl groups), acyl groups (e.g. benzoyl or naphthoyl groups), anilino groups (e.g. phenylamino, N -methylanilino group or N-acetylanilino group), acyloxy group (e.g. benzoyloxy group or toluoyloxy group etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group etc.), arylsulfamoyl group (e.g. phenylsulfonylamino group, etc.), arylsulfonylamino group (phenylsulfonylamino group, p
-tolylsulfonylamino group, etc.), an arylsulfonyl group (benzenesulfonyl group, tosyl group, etc.), or an acylamino group (eg, benzoylamino group, etc.). The alkyl group, aryl group, heterocyclic group, cycloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ above, or R ¹ and R ² , R ² and R ³ or R ³ and R ⁴ are mutually The 6-membered ring formed by bonding can be a halogen atom (for example, a chlorine atom, a bromine atom, or a fluorine atom), a cyano group, a linear or branched alkyl group (for example, a methyl group, an ethyl group, a propyl group,
Butyl group, hexyl group, octyl group, decyl group,
dodecyl group, tetradecyl group, hexadecyl group,
heptadecyl, octadecyl, or methoxyethoxyethyl), aryl (such as phenyl, tolyl, naphthyl, chlorophenyl, methoxyphenyl, or acetylphenyl), alkoxy (such as methoxy) , ethoxy group, butoxy group, propoxy group or methoxyethoxy group), aryloxy group (such as phenoxy group, triloxy group, naphthoxy group or methoxyphenoxy group),
Alkoxycarbonyl groups (e.g., methoxycarbonyl, butoxycarbonyl, or phenoxymethoxycarbonyl groups), aryloxycarbonyl groups (e.g., phenoxycarbonyl, triloxycarbonyl, or methoxyphenoxycarbonyl groups), Acyl groups (e.g. formyl, acetyl, valeryl, stearoyl, benzoyl, toluoyl, naphthoyl or p-methoxybenzoyl), acyloxy (e.g. acetoxy or acyloxy), acylamino groups (e.g. ,
acetamido group, benzamide group, or methoxyacetamide group), anilino group (e.g., phenylamino group, N-methylanilino group,
N-phenylanilino group, N-acetylanilino group, etc.), alkylamino group (e.g.
n-butylamino group, N/N-diethylamino group, 4-methoxy-n-butylamino group, etc.),
Carbamoyl group (e.g., n-butylcarbamoyl group, N.N-diethylcarbamoyl group, n-
butylsulfamoyl group, N/N-diethylsulfamoyl group, n-dodecylsulfamoyl group,
or N-(4-methoxy-n-butyl)sulfamoyl group), a sulfonylamino group (e.g., methylsulfonylamino group, phenylsulfonylamino group, or methoxymethylsulfonylamino group), or a sulfonyl group (e.g. , mesyl group, tosyl group, methoxymethanesulfonyl group, etc.). The alkyl group represented by R ⁵ , R ⁶ , R ⁷ or R ⁸ includes both substituted and unsubstituted alkyl groups, and may be either a straight-chain alkyl group or a branched alkyl group. These alkyl groups preferably have 1 to 20 carbon atoms, excluding the carbon atoms in the substituent moiety, such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, etc. group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, or octadecyl group. The aryl group represented by R ⁵ , R ⁶ , R ⁷ or R ⁸ includes both substituted aryl groups and unsubstituted aryl groups, and preferably has 6 to 14 carbon atoms, excluding the carbon atoms in the substituent moiety. is an aryl group,
For example, phenyl group, tolyl group, naphthyl group, etc. can be mentioned. The nonmetallic atomic groups necessary to form the 5-membered ring or 6-membered ring represented by Z are the following (a), (b), (c),
Includes nonmetallic atomic groups represented by formula (d) or (e). In the formula, R ⁹ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ⁹ includes both substituted alkyl groups and unsubstituted alkyl groups, and is preferably an alkyl group having 1 to 20 carbon atoms excluding the carbon atoms in the substituent part, and these are straight-chain alkyl groups, It may be any branched alkyl group. Specific examples of these alkyl groups include the same specific examples as exemplified for R ¹ , R ² , R ³ and R ⁴ . Among the complexes represented by the general formula (), (), () or (), the complexes preferably used in the present invention are the following general formulas (a), (b), (
It can be represented by a), (a), (b), or (a). In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group bonded directly or indirectly to a carbon atom on the benzene ring via a divalent linking group, or an aryl group. group, cycloalkyl group, heterocyclic group, or R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ represent a group of nonmetallic atoms necessary to combine with each other to form a 6-membered ring. R ⁵ and R ⁸ each represent a hydrogen atom, an alkyl group, or an aryl group. R ⁶ represents a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group. R ⁷ represents an alkyl group or an aryl group. M represents Cu, Co, Ni, Pd or Pt. n represents 2 or 3. Specific examples of the alkyl group or aryl group represented by R ⁷ or R ⁸ include the same examples as the alkyl group or aryl group represented by R ¹ , R ² , R ³ , R ⁴ or R ⁵ . General formulas (a), (b), (a), (a), (

Among the complexes represented by b) or (a), those particularly preferably used in the present invention are:
It is a complex represented by general formula (a), (b) or (a). Among the complexes represented by general formula (a), (b) or (a), those in which at least one of the groups represented by R ¹ , R ² , R ³ or R ⁴ is an alkyl group are more preferably used. Or it is a complex which is an alkoxy group. General formula (a),
Among the complexes represented by (b) or (a), those more preferably used in the present invention are:
It is a complex in which the total number of carbon atoms in the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , or R ⁷ is at least 4 or more. The compounds represented by the following structural formulas are complexes that fall within the scope of the general formula (), (), (), or (), and are described for the purpose of illustrating those that are effective in carrying out the present invention. However, the present invention is not limited to these compounds. Compound A general method for synthesizing the above complexes is, for example, RH
Holm, GWEverett, A.Chakravorty, Metal
Complexes of Schiff Bases and β−
Ketoamines, Progr.Inorg.Chem. 783 (1966)
L, Sacconi Coord.Chem.ReV, 1 , 126
(1966), S. Yamada, bid. 1 415 (1966), etc. Synthesis example (1) Synthesis method of compound-1. Dissolve 2 g of sodium hydroxide in 130 ml of methanol. 2-lauroyl-5-methylphenol 14.5g
Add to this methanol solution and dissolve completely. Add this solution to 12 g of nickel chloride hexahydrate and 100 g of water.
Gradually add to the aqueous solution dissolved in ml. The pale-colored precipitate formed is filtered, washed with water, and air-dried. This precipitate

[Formula]. Take 5 g of the dried nickel complex, add 100 ml of concentrated ammonia water, and stir at room temperature for 72 hours to obtain a red colored precipitate. After this, wash with water. After air drying, recrystallize from benzene. 3 g of red crystals are obtained. Synthesis method of compound-33 Dissolve 3.06 g of 2-hydroxy-4-methylphenyl undecyl ketoxime obtained by reacting 2-lauroyl-5-methylphenol and hydroxyamine sulfate in 26 ml of ethanol and reflux. let Slowly add dropwise a solution of 1.10 g of nickel chloride hexahydrate dissolved in 7 ml of ethanol. After the addition is complete, the solvent is concentrated and the obtained dark green solid is recrystallized from benzene. −33 microcrystals
Obtain 2.4g. The organic base material according to the present invention includes basic dyes,
Dyeing with water-soluble dyes such as acid dyes, direct dyes, soluble vat dyes, mordant dyes, insoluble dyes such as sulfur dyes, vat dyes, oil-soluble dyes, disperse dyes, azoitsk dyes, oxidation dyes, or reactive dyes. It includes all dyes belonging to the classification based on physical properties. These organic base materials are not limited to dyes that appear colored when exposed to sunlight, but also include colorless or pale yellow fluorescent whitening dyes. Among these dyes, the dyes preferably used in the present invention include quinone imine dyes (azine dyes, oxazine dyes, thiazine dyes, etc.), methine and polymethine dyes (cyanine dyes, adimethine dyes, etc.), azo dyes, anthraquinone dyes, indoamine dyes, and It includes dyes belonging to chemical structural classes such as indophenol dyes, indigoid dyes, carbonium dyes, and formazan dyes. The organic substrate material according to the present invention includes image-forming dyes used in the field of photography, such as color dyes, DRR compounds, DRR couplers, amidrazone compounds, dyes formed from dye developers, etc.
Includes all dyes used in silver dye bleaching methods. Preferred dyes for use as organic substrates in accordance with the present invention include anthraquinone, quinoneimine, azo, methine, polymethine, indoamine,
Indophenol and formazan dyes.
In practicing the present invention, the dyes most preferably used are methyl and polymethine dyes, and indoamine and indophenol dyes. The methine and polymethine dyes and indoamine and indophenol dyes include compounds having the following groups. In the above, the phenyl group represents an unsubstituted phenyl group or a substituted phenyl group, such as a phenyl group substituted with an alkyl group, an alkoxy group, a halogen atom, an amino group, or the like. Dye-forming couplers suitable for use in the present invention include yellow, magenta and cyan dye-forming types. The coupler may be of the so-called 4-equivalent type or of the 2-equivalent type, as described for example in US Pat. Nos. 3,277,155 and 3,458,315. Yellow dye-forming couplers generally contain a methylene group activated by at least one carbonyl group (e.g., an open-chain ketomethylene group) and include beta-diketones and beta-ketoacylamides, such as benzoylacetanilide, and alpha pivalyl acetanilide. do. Specific examples of yellow dye-forming couplers that can be used in the present invention include, for example, U.S. Pat.
No. 3265506, No. 3408194, No. 3408194, No. 3265506, No. 3408194, No.
3551155, 3582322, 3725072, 3891445, West German Patent No. 1547868, West German Patent Application (OLS) No. 2213461, 2219917, West German Patent No.
2261361, 2263875, 2414006, British Patent No. 1421123, 1421126, British Patent No.
No. 1425020, Special Publication No. 51-10783, Japanese Patent Publication No. 51-
No. 102636, No. 50-6341, No. 50-123342,
Same No. 50-130442, Same No. 51-21827, Same No. 50-
It is described in issues such as No. 87650. Magenta dye-forming couplers, such as 5-pyrazolone type couplers, can also be used in the present invention. Specific examples of magenta dye-forming couplers that can be used in the present invention include, for example, U.S. Pat.
No. 2600788, No. 2983608, No. 3062653, No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, Same No. 3558319, Same No. 3582322
No. 3615506, No. 3834908, No. 3834908, No.
3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, OLS No. 2417945, OLS No.
No. 2418959, No. 2424467, Special Publication No. 40-6031
No. 51-45990, Japanese Patent Application Publication No. 50-159336,
Same No. 52-42121, Same No. 49-74028, Same No. 50-
It is described in No. 60233, No. 51-26541, etc. Other magenta dye-forming couplers are Vittum and
“Journal of Photographic” by Weissberger
6 (1958), pages 158 et seq., e.g.
pyrazolinobenzimidazole as described in Belgian Patent No. 724427, and pyrazolinobenzimidazole as described in Belgian Patent No. 724427 and
- Cyanoacetylcoumaron. Cyan dye-forming couplers that can be used in the present invention include phenolic and alpha-arnaphthol compounds. Specific examples of cyan dye-forming couplers include, for example:
U.S. Patent No. 2369929, U.S. Patent No. 2434272, U.S. Patent No.
No. 2474293, No. 2521908, No. 2895826, No. 3034892, No. 3311476, No. 3458315, No. 3476563, No. 3583971, No. 3591383,
OLS No. 3767411, OLS No. 4004929, West German Patent Application (OLS) No. 2414830, OLS No. 2454329, JP-A-Sho No.
No. 48-59838, No. 51-26034, No. 48-5055
No. 51-146828, etc. In addition, U.S. Patent No. 3476560, U.S. Patent No. 2521908
No. 3034892, Special Publication Show No. 44-2016, No.
No. 38-22335, No. 42-11304, No. 44-32461
Colored couplers described in U.S. Pat. No. 51-26034, U.S. Pat.
No. 3614291, No. 3701783, No. 3790384, No. 3632345, West German patent application (OLS) 2414006
No. 2454301, No. 2454329, British Patent No.
953454, JP-A No. 52-69624, JP-A No. 49-
DIR couplers described in Japanese Patent Publication No. 122335, No. 52-69624, and Japanese Patent Publication No. 51-16141 can also be used. Such couplers as a general type are further described, for example, in Kirk-Othmer's Encyclpedia.
of Chemical Technology, Vol. 5, pp. 822-825 and
Glafkides' Photographic Chemistry, 2 volumes,
It is described on pages 596-614. As previously mentioned, when such couplers are used in the practice of this invention, dyes are formed by the reaction of these couplers with oxidized aromatic primary amine silver halide developing agents. The above-mentioned developing agents include aminophenol and phenylenediamine, and a mixture of these developing agents can also be used. Representative examples of developing agents that can be combined with various couplers to form base compounds in accordance with the present invention are described in TH James, ed. The Theory of the
p-phenylenediamine and derivatives thereof described in Photographic Poocess (4th edition), published by Macmillan (1977), pages 315 to 320. p-phenylenediamines in which at least one amino group is substituted with a lower alkyl group having 1 to 3 carbon atoms or a derivative thereof, such as 4-amino-N.
N-dimethylaniline, 4-amino-N・N-diethylaniline, 4-amino-3-methyl-N・
N-diethylaniline, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 4-amino-N-ethyl-N
p-phenylenediamine derivatives such as -(β-hydroxyethyl)aniline and 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline can be preferably used in the present invention. Among the couplers mentioned above or capable of reacting with other developing agents to form a base compound,
Those that can be preferably used in the present invention are:
It can be represented by the following general formula (), () or (). In the formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each represent a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (for example,
Methyl group, ethyl group, octyl group, dodecyl group,
tetradecyl group, octadecyl group, etc.),
Carbamoyl groups (e.g. methylcarbamoyl, ethylcarbamoyl, dodecylcarbamoyl, tetradecylcarbamoyl, octadecylcarbamoyl, N-phenylcarbamoyl or N-tolylcarbamoyl), sulfamoyl groups (e.g. methylsulfamoyl) group, ethylsulfamoyl group, dodecylsulfamoyl group, tetradecylsulfamoyl group, octadecylsulfamoyl group, N-phenylsulfamoyl group, or N-tolylsulfamoyl group) or amide group ( For example, it represents an acetamide group, a propionamide group, a benzamide group, a phenacetetamide group, a sulfonamide group, a phosphoramide group, a ureido group, etc.). R ¹⁰ and R ¹¹ may be combined with each other to form 6 main rings (eg, phenyl group). X ₁ is a hydrogen atom, a halogen atom, (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom)
or a group that can be released by reacting with an oxidized product of a developing agent (for example, an alkoxy group, an aryloxy group, a sulfonamido group, a sulfonyl group, a carbamoyl group, an imido group, an aminosulfonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, (alkylthio group, arylthio group, heterocyclic thio group, etc.). The alkyl group, carbamoyl group, sulfamoyl group, amide group represented by R ¹⁰ , R ¹¹ , R ¹² or R ¹³ , or the 6-membered ring formed by combining R ¹⁰ and R ¹¹ with each other, may be substituted with other substituents. , for example, alkyl groups (e.g., methyl, ethyl, propyl, octyl, dodecyl, tetradecyl,
or octadecyl group, etc.), aryl groups (e.g., phenyl, tolyl, or naphthyl groups, etc.), aryloxy groups (e.g., phenoxy, 2,5-di-(t)amylphenoxy, etc.), halogen atoms (e.g., chlorine atom, , bromine atom, fluorine atom, etc.). In the formula, ^R14 is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, or fluorine atom, etc.), an alkyl group (e.g., methyl group, ethyl group, n-propyl group, etc.), or an alkoxy group (e.g.,
methoxy group, ethoxy group, etc.), ^R15 is an alkyl group (for example, methyl group, ethyl group, octyl group,
dodecyl group, tetradecyl group or octadecyl group), amide group (e.g. butaneamide group, decanamide group, tetradecaneamide group or nodecanamide group etc.), imide group (e.g. tetradecylsuccinimide group or octadecenylsuccinimide group etc.) , an alkylcarbamoyl group (for example, a decylcarbamoyl group, a tetradecylcarbamoyl group, an octadecylcarbamoyl group, etc.), an N-alkylsulfamoyl group (for example, a decylsulfamoyl group, a tetradecylsulfamoyl group, or an octadecylsulfamoyl group) ), alkoxycarbonyl groups (e.g. adesyloxycarbonyl, tetradecyloxycarbonyl or octadecyloxycarbonyl), acyloxy groups (e.g. valeryloxy, palmitoyloxy, stearoyloxy, oleoyloxy, benzoyloxy), group, toluoyloxy group, etc.), a sulfonamide group, or a urethane group. R ¹⁶ represents an aryl group (eg, phenyl group, naphthyl group, etc.). D represents an amino group, carbonylamino group or ureido group. X is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or a group that can be released by reacting with an oxidized product of a developing agent (for example, an arylazo group, an aryloxy group, an acyloxy group, an alkylthio group, or an arylthio group) etc.). An alkyl group or alkoxy group represented by R ¹⁴ , an alkyl group or amide group represented by R ¹⁵ ,
The N-alkylcarbamoyl group, N-alkylsulfamoyl group, alkoxycarbonyl group or acyloxy group, or the aryl group represented by R ¹⁶ may be substituted with other substituents, such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, It may be substituted with an amide group, N-alkylcarbamoyl group, N-alkylsulfamoyl group, acyloxy group, carboxy group, sulfo group, halogen atom, or the like. In the formula, R ¹⁷ is an alkyl group (for example, a methyl group,
ethyl group, (t)-butyl group, or (t)-octyl group), and an aryl group (eg, phenyl group). R ¹⁸ represents an aryl group (eg phenyl group). ^and Dimethylhydantoinyl group, 2.4
-oxalidinedione group, imide group, pyridone group, pyridazone group, etc.) acyloxy group, sulfonyloxy group, aryloxy group, urethane group, etc.}
represents. The alkyl group or aryl group represented by R ¹⁷ or the aryl group represented by R ¹⁸ may be substituted with other substituents, such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amide group, an N-alkylcarbamoyl group, or an N-alkyl group. Sulfamoyl group, acyloxy group, carboxy group, sulfo group,
It may be substituted with a sulfonamide group or a halogen atom. As couplers which can form base compounds, in particular organic dyes, by the method of the invention,
For example, the following can be mentioned. Examples of other dyes that can be used as the base material in practicing the present invention include the following. Other types of dyes preferably used in the present invention include USB351673, U.S. Pat.
Same No. 3928312, No. 3931144, No. 3954476, Same No.
No. 3929760, No. 3942987, No. 3932380, No.
No. 4013635, No. 4013633, JP-A-51-113624,
No. 51-109928, No. 51-104343, No. 52-4819
No. 52-64533, “Research
Disclosure magazine (Research Disclosure) (November 1976 issue) pp. 68-74, No. 13024 ('
Examples include dyes formed by oxidation of DRR compounds described in 75) and others. Other types of dyes used in the present invention include:
For example, British Patent No. 840781, British Patent No. 904364, British Patent No. 932272
No. 1014725, No. 1038331, No. 1066352,
No. 1097064, JP-A-51-133021, UST900029
(USDefensive Publication), US Patent 3227550
Examples include dyes released by the reaction of DDR couplers such as those described in No. 1 with oxidized products of color developing agents, or dyes formed by the reaction of DDR couplers with oxidized products of color developing agents. Other types of dyes preferably used in the present invention include Japanese Patent Publications Nos. 35-182, 18332, and 48-
Examples include dye developers such as those described in No. 32130, No. 46-43950, and No. 49-2618. Other types of dyes used in the present invention include:
Various dyes used in the silver dye bleaching method can be mentioned. Yellow dyes that can be used for this purpose include Direct Fast Yellow GC
(CI29000), azo dyes such as chrysophenine (CI24895), indigo golden yellow IGK
(CI59101), Indigosol Yellow 2GB
(CI61726), Argosol Yellow GCA-CF
(CI67301), Indanthrene Yellow GF
(CI68420) Mikethren Yellow GC (CI67300),
Examples include benzoquinone dyes such as Indanthrene Yellow 4GK (CI68405); anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes. Magenta dyes include azo dyes such as Sumilite Sapra Rubinol B (CI29225) and benzobrilliant gelanin B (CI15080), and indigosol brilliant pink IR.
(CI73361), Indigosol Violet 15R
(CI59321), Indigosol Lettuce Violet
Indigoid dyes such as IRRL (CI59316), Indanthrene Ret Violet RRK (CI67895), Mikethrene Brilliant Violet BBK (CI6335); Soluble vat dyes consisting of benzoquinone and anthraquinone heteropolycyclic compounds, etc. vat dyes can be mentioned. As cyan dye, Direct Sky Blue 6B
(CI24410), Direct Brilliant Blue 2B
(CI22610), Sumilight Subrable-G
Azo dyes such as (CI34200), phthalocyanine dyes such as Sumilite Sabra Turkey Blue-G (CI74180), Mikethlene Brilliant Blue 4G (CI74140), Indansulent Turkey Blue-G
5G (CI69845), Indanthrene Blue GCD
(CI73066), Indigosol 04G (CI73046), Anthrazole Green IB (CI59826), etc. As mentioned above, the metal complex according to the present invention stabilizes the base material. These compounds can be present in any or all of the emulsion layers of a color photographic film. These compounds can also be present in any of the layers included in the non-light-sensitive portions of the color transfer material. These complexes can be used in low-boiling organic solvents or water-miscible organic solvents, such as alcohols (methanol, ethanol, isopropanol,
butanol, etc.), ethers (dimethyl ether, ethyl methyl ether, diethyl ether,
1-ethoxypropane, etc.), glycols (1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, etc.), ketones (acetone, ethylmethylketone, 3-pentanone, etc.), esters (ethyl formate, methyl acetate, ethyl acetate, etc.), amides (formamide, acetamide, succinic acid amide, etc.) that do not adversely affect photographic properties, and as a solution, it becomes a hydrophilic colloid that makes up the photographic layer. The addition can serve to stabilize the substrate material. This step is preferably a step beyond coating, such as a step of producing a silver halide photographic emulsion, a step of emulsifying and dispersing a coupler, and a step of preparing a photographic coating solution. Also, the same methods described for coupler dispersion can be used to incorporate these complexes into the hydrophilic colloids that make up the photographic layers. Thus, US Pat. No. 2,304,939 and US Pat. No. 2,322,027 disclose the use of high boiling organic solvents to dissolve this material. Other applicable methods are U.S. Pat. No. 2,801,170, no.
No. 2801171 and No. 2949360, in which low-boiling or water-soluble organic solvents are used together with high-boiling solvents. High-boiling solvents useful for dispersing the base compounds and metal complexes of the present invention include di-n-butyl phthalate, benzyl phthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl mono-p-tert- Butylphenyl phosphate, monophenyl di-p-tert-butylphenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, 2,4-di-n-amylphenol, 2,4 -di-t-amylphenol, N.N-diethylrauramide, and trioctyl phosphate and trihexyl phosphate as described in US Pat. No. 3,676,137. Low-boiling or water-soluble organic solvents that can be advantageously used with these high-boiling solvents are described, for example, in U.S. Pat.
It is disclosed in No. 2949360. These organic solvents include (1) low-boiling organic solvents substantially insoluble in water, such as methyl, ethyl, propyl and butyl acetate, isopropyl acetate, ethyl propionate, sec-
Butyl alcohol, ethyl formate, butyl formate, nitromethane, nitroethane, carbon tetrachloride, chloroform, etc., and (2) water-soluble organic solvents such as methyl isobutyl ketone, β-ethoxyethyl acetate, β-adipate.
-butoxytetrahydrofurfuryl, diethylene glycol monoacetate, methoxytriglycol acetate, acetonyl acetone, diacetone alcohol, ethylene glycol, diethylene glycol, dibropylene glycol, acetone, methanol, ethanol, acetonitrile, dimethylformamide, dioxane, etc. Both the substrate material and the complex can be present in any or several of the hydrocolloid layers of the photographic element. These materials may be present in light-sensitive elements as well as non-light-sensitive elements such as dye image receivers used in photographic diffusion transfer film units. When the substrate material and complex are included in such a non-photosensitive image recording element, the substrate material is preferably mordanted. Therefore, for such applications, the complex has a molecular form that allows it to be retained in the mordant layer of the receiver without diffusing away from the dye to be stabilized. It is preferable. There are several types that may be effective when using the method of the present invention to improve the lightfastness of photographic elements such as image transfer film units. One application is an invisibility transfer film unit as described in US Pat. No. 2,882,156. One use is U.S. Patent No.
No. 2087817, No. 3185567, No. 2983606, No. 3253915,
No. 3227550, No. 3227551, No. 3227552, No. 3415644,
3415645, 3415646, 3594164 and 3594165 and Belgian patents 757959 and 757960. The complexes and basic materials used in the practice of the invention are
Product Licensing Index, Volume 92 (1971.12)
May), No. 9232, pp. 107-110. Any amount of complex should provide the improvements of the present invention, and there is theoretically no upper limit to the amount that can be used. Preferably, at least 1 micromole of complex is present per square meter of photosensitive material;
More preferably, about 10 to 1×10 ⁴ micromoles of complex are present per square meter. In general, the base material density should be equal to that commonly used in color photography. These densities are well known to those skilled in color photography. Preferably, the substrate material is present in an amount ranging from about 10 to 10 ⁴ micromoles per square meter of photosensitive material. More preferably, it is present in an amount ranging from about 100 to about ^{3.times.10.sup.3} micromoles per square meter of photosensitive material. The substrate materials used in the practice of this invention are generally about
It has a maximum wavelength absorption peak smaller than 800 nm. The maximum wavelength absorption peak of this base material is approximately 300
It is preferably in the range of ~800nm, approximately 400~
Preferably, the wavelength is in the range of 800 nm. As the photographic material used in the method of the present invention, all those commonly used as supports for photographic materials can be used. For example, cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film,
Other materials include laminates of these materials and paper. Baryta or α-olefin polymers, especially polyethylene,
Paper coated or laminated with a polymer of α-olefin having 2 to 10 carbon atoms, such as polypropylene, can be mixed with other polymeric substances by roughening the surface as shown in Japanese Patent Publication No. 19068/1983. A support such as a plastic film is also suitable because it improves the adhesion of the material. Various hydrophilic colloids are used in the photographic material used in the method of the present invention, and hydrophilic colloids used as binders for photographic emulsions and/or other photographic constituent layers include, for example, gelatin, colloidal albumin, Cellulose derivatives such as casein, carboxymethyl cellulose, and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymers, and maleic anhydride. Examples include acid copolymers, polyacrylamide, and derivatives/partial hydrolysates thereof. Compatible mixtures of two or more of these colloids are used if desired. Among these, gelatin is the most commonly used, but gelatin can be partially or completely replaced with synthetic polymeric substances, and it can also be made into so-called gelatin derivatives, which include amino groups, imino groups, etc. as functional groups contained in the molecule. hydroxyl groups, hydroxyl groups, and carboxyl groups treated or modified with a reagent that has one group that can react with them, or may be used by replacing them with graft polymers bonded with molecular chains of other polymeric substances. good. The photographic emulsion layer and other layers used in the present invention contain synthetic polymer compounds, such as latex-like water-dispersed vinyl compound polymers, in particular compounds that increase the dimensional stability of photographic materials, either singly or in combination. (of different types of polymers) or in combination with hydrophilic water-permeable colloids. The silver halide photographic emulsions used in the method of the present invention typically include a solution of a water-soluble silver salt (e.g. silver nitrate) and a water-soluble halide salt (e.g. potassium bromide).
solution in the presence of a water-soluble polymer solution such as gelatin. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. These silver halide grains are produced according to known and commonly used methods. Of course, it is also useful to use the so-called single or double jet method, controlled double jet method, or the like. Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed. Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. Those compounds are 4-hydroxy-6-methyl-
Many heterocyclic compounds including 1,3,3a,7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole,
A large number of compounds have been known for a long time, including mercury-containing compounds, mercapto compounds, and metal salts. The silver halide emulsion used in the method of the present invention can also be chemically sensitized by conventional methods. Chemical sensitizers include metal chlorides, gold compounds such as gold trichloride, salts of noble metals such as platinum, palladium, iridium, or rhodium, and silver salts such as sodium thiosulfate to form silver sulfide. Examples include sulfur compounds, stannous salts, amines, and other reducing substances. The photographic emulsion used in the method of the present invention may be spectral sensitized or superchromically sensitized by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc., as necessary. You can do the feeling. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, the sensitivity, etc., and the purpose and use of the photosensitive material. Of the photosensitive material used in the method of the present invention,
The hydrophilic colloid layer can be cured with various crosslinking agents, if necessary. For example, it can be selected from aldehyde compounds, active halogen compounds, vinyl sulfone compounds, carbodiimide compounds, N-methylol compounds, epoxy compounds, and the like. In one embodiment when the method of the present invention is applied to a color photographic light-sensitive material, after imagewise exposure, the material is processed according to a conventional method to form a color image. The main steps in this case are color development, bleaching, and fixing, and if necessary, steps such as washing with water and stabilization may be included. Two or more of these steps, such as bleach-fixing, can be performed in one bath. Color development is usually carried out in an alkaline solution containing an aromatic primary amine developing agent. Another embodiment in which the method of the present invention is applied to a color photographic light-sensitive material is that when this color photographic light-sensitive material is a film unit for color diffusion transfer, the processing of the light-sensitive material is automatically carried out inside the light-sensitive material. It will be held in In this case, the developing agent is contained in a rupturable container. In addition to the above-mentioned aromatic primary amine developing agent, N-
Methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-
3-pyrazolidone, 1-phenyl-4-methyl-
Hydroxymethyl-3-pyrazolidone, 3-methoxy-N·N-diethyl-p-phenylenediamine, and the like can be used. In order to form a color image in the photographic light-sensitive material used in the method of the present invention, a method using a coupling reaction between the dye-forming color coupler described above and an oxidized product of a p-phenylenediamine-based color developing agent; A method using a developer, a method using an oxidative rupture reaction of a DRR compound, a method using a dye elimination reaction due to a coupling reaction of a DDR coupler, a method using a dye formation reaction due to a coupling reaction of a DDR coupler, or a method using a silver dye bleaching method. A known method can be used. Therefore, when the method of the present invention is applied to photographic light-sensitive materials, various color photographs such as color positive film, color paper, color negative film, color reversal film, film unit for color diffusion transfer, light-sensitive material for silver dye bleaching, etc. Applicable to photosensitive materials. Preferred embodiments of the present invention are listed below. 1. At least one type of complex represented by the general formula (), (), () or () described in the claims is contained in a medium containing a dye having an absorption maximum between about 300 nm and about 800 nm. A method of stabilizing the dye against light. 2. In the item 1 above, the dye is at least one dye selected from anthraquinone dyes, quinoneimine dyes, azo dyes, methine or polymethine dyes, indoamine and indophenol dyes, and formazan dyes. A method for stabilizing dyes against light. 4. In the description of Items 1 and 2 above, the dye is a dye-forming coupler, a DDR coupler,
A method for stabilizing dyes against light, characterized in that the color image is made from a DRR compound, a dye developer or a silver dye bleaching method dye. 4 In the claims, the complex represented by the general formula (), (), () or () is defined by the following general formula (a), (b), (
A method for stabilizing a dye against light, characterized in that it is represented by a), (a), (b), or (a). In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a halogen atom, a cyano group, or an alkyl group bonded directly or indirectly to a carbon atom on a benzene ring via a divalent linking group. , aryl group, cycloalkyl group, heterocyclic group, or R ¹
and R ² , R ² and R ³ , and R ³ and R ⁴ represent a group of nonmetallic atoms necessary for bonding with each other to form a 6-membered ring. R ⁵ and R ⁸ each represent a hydrogen atom, an alkyl group, or an aryl group. R ⁶ is a hydrogen atom, an alkyl group, an aryl group,
Or represents a hydroxyl group. R ⁷ represents an alkyl group or an aryl group. M represents Cu, Co, Ni, Pd or Pt. n represents 2 or 3. 5. The dye-forming coupler according to item 3 above is a yellow dye-forming coupler selected from benzoylacetanilides and alpha-apivalylacetanilides, 5-pyrazolones, indazolones, pyrazolinobenzimidazoles, pyrazolo-s-triazoles. a magenta dye-forming coupler selected from the classes and cyanoacetylcoumarons, and a cyan dye-forming coupler selected from the phenols and naphthols. 6 In the description of item 4 above, the complex is (
A method for stabilizing a dye against light, characterized in that it is represented by a), (b) or (a). 7 In the description of item 4 above, the general formula (
R ¹ , R ² , R ³ in a), (b) or (a)
or at least one of the groups represented by R ⁴
A method for stabilizing a dye against light, the method comprising using a complex in which the group is an alkyl group or an alkoxy group. 8 In the description of item 4 above, the general formula (
R ¹ , R ² in a), (b) or (a),
A method for stabilizing a dye against light, characterized in that the total number of carbon atoms in the groups represented by R ³ , R ⁴ , R ⁵ , R ⁶ , or R ⁷ is at least 4 or more. Example 1 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-tetradecanamido)anilino 4-{4-(N-ethyl-N-β-methanesulfonamidoethyl)aminophenylimino}-5
0.1 g of -oxo-2-pyrazoline was dissolved in 3 ml of tricresyl phosphate and 5 ml of ethyl acetate, and this solution was emulsified and dispersed in 10 g of 10% gelatin containing 1 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate. This emulsified dispersion was then mixed with 10 g of 10% gelatin, coated on a paper support laminated on both sides with polyethylene, and dried. (Sample A). Sample B was prepared by adding 30 mg of the compound (-1) of the present invention to the above emulsified dispersion and applied in the same manner as Sample A, and 2. Samples C and D were prepared by adding 15 mg and 150 mg of 5-di-tert-octylhydroquinone, respectively, and applying the coating in the same manner as sample A. The amount of dye applied was 60 mg/m ² in each case. These samples A to D were subjected to a 48 hour fading test using a xenon tester (illuminance: 200,000 lux) with a Fujifilm ultraviolet cut filter C-40 attached. The results are shown in the table.

[Table] Status was measured using Macbeth Densitometer RD514.
Measured using an AA filter green filter. Sample B, which contains the compound (-1) of the present invention, exhibits extremely little discoloration compared to the other A, C, and D, and in particular, for Samples C and D, di-tert-octylhydroquinone is the compound of the present invention, respectively. (−
It was confirmed that despite adding the same mole or 10 times the mole of 1), it was hardly effective in preventing discoloration. This means that the compound (-1) of the present invention
shows that it has a surprising effect on preventing photobleaching of dyes. Example 2 0.1 g of compound (-2) was dissolved in 0.2 c.c. of 1N-NaOH and 2 c.c. of methanol, and this solution was added to 10 g of 10% gelatin. This was coated onto a paper support laminated on both sides with polyethylene so that the coating amount of compound (-2) was 80 mg/m ² . (Sample E). In a similar manner, the compound of the present invention (-
33) Sample F, which was applied in the same manner as sample E by adding a solution of 40 mg dissolved in 2 c.c. of methanol, and 2,5-di-tert-, a well-known photofading inhibitor for dyes, were used as comparative samples. Octylhydroquinone 20mg
Sample G was prepared by adding and applying in the same manner. These samples were subjected to a 12-hour fading test in the same manner as in [Example 1] with an ultraviolet absorption filter attached. The results are shown in the table.

[Table] Measurements were carried out using a Masbeth densitometer in the same manner as in Example 1. From this experimental result, the compound of the present invention (-
It can be seen that the photobleaching prevention effect of 33) is extremely large. Example 3 Magenta coupler 1-(2,4,6-trichlorophenyl)-3-{(2-chloro-5-tetradecanamido)anilino}-2-pyrazoline-5-
10 g of tricresyl phosphate was dissolved in 30 ml of tricresyl phosphate, 5 ml of dimethylformamide and 15 ml of ethyl acetate, and this solution was emulsified and dispersed in 80 g of a 10% gelatin solution containing 8 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate. Next, this emulsified dispersion was mixed with 145 g (containing 7 g of Ag) of an edge-sensitive silver chlorobromide emulsion (Br 50 mol%), sodium dodecylbenzenesulfonate was added as a coating aid, and a paper support was laminated on both sides with polyethylene. applied on top. (Sample H) Coupler coating amount was 400 mg/m ² . A sample in which 2.5 g of the compound (-3) of the present invention was added to the above emulsified dispersion in the same manner and applied in the same manner as Sample H, and a well-known 2.5 as a dye photofading inhibitor. Sample J was prepared by adding 1.0 g of -di-tert-octylhydroquinone and coating in the same manner as Sample H. 1000 of these samples
The film was exposed to light for 1 second using Lux and processed with the following processing solution. Developer solution Benzyl alcohol; 15ml Diethylenetriaminepentaacetic acid; 5g KBr; 0.4g Na ₂ SO ₃ ; 5g Na ₂ SO ₃ ; 30g Hydroxylamine sulfate; 2g 4-amino-3-methyl-N-β-(methanesulfonamide) Ethylaniline・3/2H ₂ SO ₄・
H ₂ O; 4.5g Make up to 1000ml with water. PH10.1 Bleach-fixing solution Ammonium thiosulfate (70wt%); 150ml Na ₂ SO ₃ ; 5g Na [Fe (EDTA)]; 40g EDTA; 4g Make up to 1000ml with water. PH6.8 Processing process Temperature Time Developing solution 33℃ 3 minutes 30 seconds Bleach-fixing solution 33℃ 1 minute 30 seconds Water washing 28-35℃ 3 minutes For each sample with a dye image formed in this way
It was exposed to sunlight for two weeks with a Fujifilm ultraviolet absorption filter C-40 that cuts out wavelengths below 400 nm. The results are shown in the table. Measurements were performed using a Macbeth densitometer RD-514 model (Status AA filter), and changes in concentration at the initial concentration of 2.0 were measured.

[Table] From these results, it can be seen that the compound (.3) of the present invention is an effective antifading agent.

Claims (1)

[Claims] 1. An organic base material having an absorption maximum in the range of about 300 nm to about 800 nm, and the following general formula (),
A method of stabilizing an organic substrate substance against light by coexisting at least one type of complex represented by (), (), or (). In the formula, M represents Cu, Co, Ni, Pd or Pt. R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group bonded directly or indirectly to a carbon atom on a benzene ring via a divalent linking group, A cycloalkyl group, a heterocyclic group, or R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ represent a group of nonmetallic atoms necessary to combine with each other to form a 6-membered ring. R ⁵ and R ⁸ each represent a hydrogen atom, an alkyl group or an aryl group. R ⁶ represents a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group. R ⁷ represents an alkyl group or an aryl group. Z represents a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring.