JPS6398660A - Method for stabilizing image of photographic sensitive material against light - Google Patents

Abstract

PURPOSE:To enhance stability of an image against light, especially, its lightfastness by incorporating a specified metal complex in a color photographic sensitive material. CONSTITUTION:The photographic sensitive material contains at least one of the metal complexes represented by formula I in which each of R<1>-R<4> is H, halogen, hydroxy, carboxy, cyano, or any of an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, or heterocyclic group optionally linked directly or through a divalent bonding group to the benzene ring; R<5> is alkyl or aryl; n is an integer of 0-2, and when n is 2, each of R<5> may be same or different; and M is Co, Cu, Ni, Pd, or Pt, thus permitting organic materials, especially, a dye or pigment to be used for the photographic sensitive material to be improved in stability against light without deteriorating their hues or purities.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to light stabilization of images of photographic materials, and more particularly to light stabilization of dye images used in color photographic materials.

Back of the Invention Wt5 It is generally known that organic substances, such as organic dyes (or pigments), tend to fade due to light, but this is not the case in the fields of ink, textile dyeing, or photography. Research has been carried out to improve the light resistance of several dyes.The present invention can be very advantageously used for the purpose of improving the light resistance of the above-mentioned organic dyes (or pigments). In the present invention, the term pigment or dye includes organic substances that appear colored to the human mouth in sunlight. It has long been known that organic substances, such as pigments or dyes, tend to fade due to light, and there are many reports on how to reduce this fading.
No. 5732 contains IH-pyrazolo[5,1-c)-1,
A technique has been disclosed in which a phenolic compound is used in combination with a 2,4-) lyazole type magenta coupler to improve the light fastness of a magenta dye image obtained from the dye. However, it has been found that the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light. Further, JP-A-60-97353 discloses a technique for improving the light fastness of an azomethine dye image formed from a magenta coupler by using a magenta coupler and a chelate compound together. When these chelates are used, although they are quite effective in improving the light fastness of dye images, they are still not sufficient and have the disadvantage of large coloration and yellow stain (Y-stain). OBJECTS OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and the first object of the present invention is to prevent deterioration of the hue and purity of growth substances, particularly pigments or dyes, used in photographic light-sensitive materials. Without,
The object of the present invention is to provide a method for improving the light stability of these materials. Another object of the invention is to provide a method for improving the light stability of dye 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 Ia amine developing agents and color couplers. Another object of the present invention is to provide a method for preventing heat or light yellow staining in color photographic images.

h1 composition of the invention The above object of the present invention is to apply the following general formula (1) to a photographic material.
This was achieved by containing at least one of the metal complexes shown below. General formula (1) In the formula, R1%R2, R3 and R4 are each a hydrogen atom,
Halogen atom, hydroxyl group, carboxyl group, cyano group, furkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, or heterocyclic group bonded directly or via a divalent linking group to the carbon atom of the benzene ring. , R% represents an alkyl group or an aryl group, n represents an integer of 0 to 2, ■ is 2, and F! two Rs
1 may be the same or different 0M is Co%Cu, old, P
d or Pt. The present invention will be explained in more detail below. In the above general formula (1), R1, R'', R
The halogen atom represented by 4 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R', R2, R3 and R4 is
R', R2 is preferably an alkyl group having 1 to 20 carbon atoms, and may be either a straight chain furkyl group or a branched alkyl group, and may be substituted or unsubstituted.
, R3 and R4 preferably have 2 to 20 carbon atoms. R', R2,
The aryl group represented by R' and R4 is preferably a 717-l group having 6 to 14 carbon atoms, and may be substituted or p&substituted. The heterocyclic group represented by R', R1, R and R4 is preferably a five-shell or six-shell heterocyclic group, and may be substituted or unsubstituted. The group and the cycloalkenyl group are preferably Il! A or a hexacyclic group, substituted, j!
Ill? Either f-conversion may be used. Examples of linear or branched furkyl groups and alkenyl groups represented by RI, R2, R3 and C/R' include methyl, ethyl, allyl, isopropyl, butyl,
Examples include groups such as t-butyl, hexyl, hexenyl, dodecyl, and octadecyl. Examples of the aryl group represented by R', R2, R3 and R4 include a 7-el group and a naphthyl group. The polycyclic group represented by R1, R2, R3, and R4 is a 5- to 6-shell heterocyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom in the ring as a heteroatom, such as Examples include groups such as 7lyl, hydro7lyl, chenyl, pyrrolyl, pyrrolidyl, pyridyl, imidazolyl, pyrazolyl, quinolyl, indolyl, oxasilyl, and thiazolyl. Examples of the cycloalkyl group and cycloalkenyl group represented by 1'(+, R2, R3, and R4 include cyclopentyl, cyclohexyl, cyclohexenyl, and cyclohexagenyl groups. The above R', R2, The alkyl group, alkenyl group, dichlorofurkyl group, cycloalkenyl group, heptadyl group or heterocyclic group represented by R3 and (/R' is a divalent linking group,
For example, benzene is It may be bonded to a carbon atom on the ring. Examples in which the alkyl groups represented by R', R2, R' and R4 are bonded to the carbon atom on the benzene ring via the above divalent linking group include an alkoxy group, an alkoxycarbonyl group, and an acyl group. , an acyloxy group, a fulkylami 7 group, an alkylcarbamoyl group, an alkylsulfamoyl group, a sulfonyl 7mino group, a sulfonyl group, or an acylami 7 group. Examples of the cycloalkyl group represented by R' t R'' = R3 and R4 bonded to the carbon atom on the ring of the compound of the present invention via the above-mentioned divalent linking group include cycloalkyloxy group, cycloalkylcarbonyl group, cycloalkyloxycarbonyl group, cycloalkylamine 7
group, cycloalkynylcarbonyl group, cycloalkynyloxy group, etc. Examples in which the aryl group represented by Rl, R2, Rs and R4 are bonded to a carbon atom on the ring of the compound of the present invention via the above-mentioned divalent linking group include a 71noroxy group, aryloxycarbonyl group, 7-syl group, anilino group,
Examples thereof include an acyloxy group, an arylcarbamoyl group, a 7lylsul7amoyl group, a 7lylsulfonyl7mino group, an arylsulfonyl group, and an acylamino group. The furkyl group, aryl group, polycyclic ring group, cycloalkyl group, or cycloalkenyl group represented by R1, R'', R3 and R4 above is a halogen atom, a sia7 group, a straight chain or branched furkyl group, Ryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, 7syl7mi7 group, 7nylino group, alkylamino group, carbamoyl group, sulfonyl group, sulfonylamino group or may be substituted with a sulfonyl group, etc. The alkyl group represented by R% or Rs includes both substituted alkyl groups and!! These alkyl groups are preferably furkyl groups having 1 to 20 carbon atoms, excluding the carbon atoms in the substituent moiety.The aryl group represented by R5 or R6 is a substituted 7-aryl group or a p& including both substituted aryl groups, rfIP
Preferably 6 to 1 carbon atoms excluding the carbon atoms in the A group part
It is a 7-reel group of 4. Next, representative examples of the metal complex represented by the general formula (1) used in the present invention (hereinafter referred to as the complex of the present invention) will be shown, but the present invention is not limited thereto. Typical synthesis examples of compounds used in the present invention are shown below. Synthesis Example 1 (Synthesis of Exemplified Compound 1) 2-(2-hydroxy-5-t-butylphenyl)benzotriazole 2,66 was dissolved in 30 ml of ethanol. A solution prepared by dissolving nickel acetate tetrahydrate 1,309 in methanol 1011 was added to this at 50° C. for 10 minutes. Further add 5% sodium carbonate aqueous solution to bring pi to 8.
-9 and stir at 50°C for 2 hours. The precipitated pale green crystals are collected by filtration, washed with water, and dried. Yield: 2.4g. Elemental analysis value (C3JsJsOJi) 1! ! ! Logical value (%) C:65.01 11:5
．． 42 N: 14, 22 actual measurement value (%) C: 6
5.24 11:5.73 N:14.45 Synthesis Example 2 (Synthesis of Exemplary Compound 14) 2-(2-human axy-3,5-di-t-7 milphenyl)-5-methoxybenzotri7 3.7G of sol is dissolved in ethanol 3011. To this, nickel acetate 4
Hydrate 1,25. A solution of 10xl of methanol was added at 50°C for 10 minutes. Further, a 28% sodium methoxide/methanol solution was added to adjust the pH to 8 to 9, and the mixture was stirred at the same temperature for 1 hour. Remove the precipitated pale green crystals, wash with water, and dry. Yield: 3.3g. Elemental analysis values (C,,Il,.NiO,Ni) Theoretical values (%
) C: 67, 42 11 near, 33 N:
10.26 Actual value (%) C: 67,58 +
1Nia, 56N: 10.55 The metal chelate compound used in the present invention is a protective layer of a 7X silver lodenide photographic light-sensitive material, a silver halide emulsion layer, an intermediate layer, a filter layer,
A subbing layer, anti-halation coating, and other auxiliary layers (all of which can be contained in one layer, but preferably a silver halide emulsion layer, more preferably a halogen emulsion layer containing a magenta coupler) The metal chelate compound used in the present invention is added to the magenta coupler-containing layer, and the amount of S, O, t to 4 moles per mole of magenta coupler is suitable, but preferably is 0.5 to 3 moles. The metal chelate compound in the present invention can be used alone or in combination with a generally well-known coupler. It can also be used as a colored coupler with a color correction effect or a development inhibitor releasing (DIR) compound. ) couplers, in which the product formed by the coupling reaction is colorless (Weiss) couplers can also be used in combination with the metal chelate compounds of the present invention. A non-diffusible coupler having a functional group is desirable, but US Pat.
No. 25, No. 3,451,820, No. 4,215.19
No. 5, British Patent No. tjS1.247.688, JP-A-5
No. 7-94752, No. 58-28745, No. 58-4
Polymeric couplers such as those described in No. 2044, No. 58-43955, and water-soluble polymer couplers having a sulfonic acid group or a carboxylic acid group may be used. Non-diffusible magenta couplers preferably used in combination with the metal chelate compound in the present invention include those represented by the following general formula (II) or (III), and polymer magenta couplers include the following: These are polymers derived from monomers represented by general formulas (■) to [■], or copolymers with one or more non-color-forming monomers. General formula (If) General formula ([[)
General formula (IV) -■ ^r General formula (V) General formula (V [) General formula [■]] General formula [■] General formula (I
t) and general formula (I [ It is an aryl group. R2 represents an alkyl group, an alkoxy group, a halogen atom, a phenoxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfo7moyl group, a 7sylamino group or a sulfonylamino group,
R2 is preferably a halogen atom, particularly preferably a chloro atom, and l represents an integer of θ to 4, particularly preferably 2 to 3. When l is 2 or more, R2 may be the same or different. Xl represents -NHCO- or -11-. In the formula, W represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by W may have a substituent. Zl is a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent; L and Z are preferably halogen atoms, particularly preferably chlorine atoms. In the general formula (mV), R- represents a hydrogen atom or an alkyl group, X2 represents -NHCO-1-N11- or -NICONH-, and Yl represents -N II C0-
Or represents -0CO-. B represents a divalent organic group, including a fullkylene group, an arylene group, or an arylenefulkylene group having 1 to 12 carbon atoms, -〇-1-S-1-SO, -1-CO-1-formerly one,
-1 is selected from one or more groups selected from C0-1-〇C〇-, etc. The spear and n represent 0 or 1, and ^' is an aryl group, such as a phenyl group, a naphthyl group, etc. In the general formula (IV), the aryl group represented by ^r is preferably 7enyl. group, and the 7-enyl group includes those having substituents. These substituents may have a plurality of them, and in this case, these substituents may be the same or different. , as criteria for preferred substituents,
It is an electron-withdrawing group. Here, the electron-withdrawing group is a physical group that has nick chemistry (Ph
organic chemistry
), He Gram Ill Book
The σ value defined by Ila+*mett et al., as described in Co., New York (1940), or the Journal of the American Chemical Society (J,^-er
, Chew, Soc, ), 90.4328 (19
68) Swain (Swa) as described in 1.
(in) and Lupton et al. is defined as a substituent having an F value greater than 0. Furthermore, the Journal of Medical Chemistry (J, N
ed. Chew, ), 16.1207 (1973), 2
0.304 (1977) may also be used. Particularly preferable electron-withdrawing groups used in the present invention include M Ct dene atom, dialkylsulfamoyl group, and halidenoalkyl group. basis,
Furkylsulfonyl group, alkyl group. In the general formulas (V) to [■], % R5 represents a hydrogen atom, a halogen atom, or an alkyl group, R6 represents an alkyl group, an aryl group, or a furkylthio group, and J represents 2
% l represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with an oxidation product of a color developing agent. R3 in the above general formulas (V) to [■] is a hydrogen atom,
A halogen atom or an alkyl group, preferably 1 monomer
~4 linear or branched lower alkyl groups, this furkyl group may have a substituent, and R7 is particularly preferably a hydrogen atom or a methyl group. In the general formulas (V) to [■], R1 represents an alkyl group, an aryl group or an alkylthio group, and among these, a preferred one is a furkyl group. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and these furkyl groups are It may have a substituent. The oryl group represented by R1 is preferably a phenyl group, and this phenyl group may have a substituent. The alkylthio group represented by R1 is a linear or branched furkylthio group having 1 to 6 carbon atoms, and the alkyl component of this furkylthio group may further have a substituent. In general formulas (V) to [■], J is a divalent organic group, and this organic group is preferably a divalent organic group represented by the following general formula (IX
). General formula CIX) 1,000R1suX, YaR, YaV, →R9 In the formula, the R1 side is bonded to the polymer main chain, and the R9 side is bonded to the birazolotriazole ring. R7, R1, and R, shown in the general formula (IM) each represent a fullkylene group, an arylene group, or an aralkylene group having 1 to 12 carbon atoms, and these groups may have a substituent. X represented by the general formula ([) is -CONH-1-N
11CO-1-COO-1-OCO-1-SO, -1-
S-1-CO-1-5O-1-〇-, among which preferred is -CONH-1-COO-1-SO,-1
-S-1-〇-. Y2 represented by the general formula (IX) is -CONII-
1-NHCO-1-CON-, -NCO-1-COO-
-0CO-1-NIICONII-1SO,NH-2-
NHSO,-, where RIO and R11
represents an alkyl group having 1 to 4 carbon atoms, and the preferred Y2 is -C0NH-5-C0N-1-COO-1-NIICO
NH-1R3°-SO,NH-. p, q%r and S represent 0 or 1, respectively. In the general formulas (V) to [■], Z2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent. The group represented by Z, which can be separated by a coupling reaction with an oxidized form of a color developing agent, means a group well known in the art as a so-called split-off group of conventional 2-equivalent couplers. Preferred is a halogen atom, particularly preferred is a chlorine atom. When a polymer magenta coupler is synthesized using the monomer units represented by general formulas (IV) to [■], particularly preferably used comonomers are acrylic esters and methacrylic esters. Typical specific examples of the couplers represented by the general formulas (n) to [■] will be described, but the present invention is not limited thereto. Exemplary magenta coupler l7 R1! M-1-NIICOC+sH2t M-2-NHCOC+<Ls H-11-SC+1. CI12Cl12N (C2t15
)2 -5CIJ2s H-13-5CIItCOzCJs H-14-5C112COO)I H-15-SCHzSOJ (CJs) iM-16-SC
H2CONHz M(7-5CIIzCIIzOCJs H-18-5CHzCH20H 14-19-3CH, Cf1.HH3O□C1l. M-33 NHSUICII3 M-1 M-2 M-3 Station H3 M-4 PM-5 ■ CH. M -7 M-9 M-10 M-11 M-12 M-13 M-15 M-16 C4M・M-17 M-18 M-19 M-20 PM-21 PM-22 M-23 M-24 M-25 CH M-26 Below, just own M-28 M-29 M-31 (hri Cki M-32 M-33 M-34 M-35 PM-36 PM-37 M-38 /'IT M-39 M-40 M-41 M-43 M-44 M-45 M-47 M-48 M-49 M-51 j M-52 M-54 8-N-N Exemplary monomer of magenta polymer coupler MC-1 MC-2 C-2) 1 MC-6 C11゜MC-7 MC-8 CH. ■ e-9 CH. MC-10 CH. MC-11 CI. UCH. Examples of colored couplers that can be used in combination are: , U.S. Patent Nos. 3,148.062, 3,227,554, 3,733,201, 3,617,291, 3
, No. 703,375, No. 3,615,506, No. 3,
No. 265,506, No. 3,620.745, No. 3,6
No. 32,345, No. 3,869.291, No. 3,64
No. 2.485, No. 3,770,436, No. 3.808
, No. 945, British Patent No. 1,201,110, No. 1,2
36. Examples include colored couplers described in No. 6F. Further, in the photographic light-sensitive material to which the complex of the present invention is applied, yellow couplers can be used, and among these, benzoyl 7-cetanilide-based compounds and piparoyl 7-7-cetanilide-based compounds are preferably used. Furthermore, both low-molecular yellow couplers and yellow polymer couplers can be used. As the yellow coupler, one represented by the following general formula (X) is used. In the formula, X represents a halogen atom, a flukoxy group, or an alkyl group, and Z represents a group that can be separated by a coupling reaction with an oxidation product of a color developing agent (sometimes simply referred to as a separation component) eR2+ represents a group that can be substituted on the benzene ring, nl represents an integer of 1 or 2, and where n is 2, Rz+ may be the same or different. Preferred as x4 is a den atom or a fluoro group. ``Atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms form a 5- to 6-shell ring together with an elementary atom. Represents the atomic group necessary for. The 7lyl moiety of the aryloxy group is preferably a phenyl group, but this phenyl group may have a substituent,
Examples of the heterocyclic oxy group include 1-phenyl-5-teFrazolyloxy group, inoxasilyloxy group, 4-
Examples include pyridinyloxy groups. ,,d−+. etc. Specifically, R21 is a halogen atom, R22-1, where R21, R23% and R24 may be the same or different, and each is a hydrogen atom, an optionally substituted alkyl group,
Represents a ring group, a heterocyclic group, preferably R,, CO
Old + -, R22SO, NH-1R2□0CONII
(R2□ is an alkyl group that may have a substituent), and most preferably R,2CON11- (R, □ is an alkyl group that has a substituent). A specific example of a yellow coupler is 'vt Leap Showa 60-
Y-1 to Y-25 described in the lower right column of page 5 to the upper left column of page 7 of Publication No. 209735 can be mentioned. Furthermore, as cyankabu 2- which can be preferably used in combination with the complex of the present invention, phenolic compounds and naphthol compounds can be used. Furthermore, either a low molecular weight cyan coupler or a cyan polymer coupler can be used. As the cyan coupler, the following general formula (XI) or (
Xll) is used. In the general formula (XI), R31 represents an aryl group, a cycloalkyl group, or a heterocyclic group, R32 represents an alkyl group or a phenyl group @R33 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and Z4 represents an alkyl group or an alkoxy group. Represents a hydrogen atom or a coupling component that is difficult to remove. General formula (XI[) In general formula (XII), R, is an alkoxy group,
R3S represents a lower alkyl group, RSS represents a hydrogen atom, a halogen atom, or a lower alkyl group mzs represents the general formula (XI
) is synonymous with Z in ). A typical example of a cyan coupler is disclosed in Japanese Patent Application Laid-Open No. 60-
I-1 to l-46 described in the upper left column on page 6 of Publication No. 222853 to the lower right column on page 8 of ttS, n-1 to ll-20, ' described in the lower left column on page 9 to the lower right column on page 10 of the same publication + Kaimei 61-5
C-1 to C-38 described in 0136 publication fjS page 7 lower right column to 10th true upper left column and JP-A-61-122645
C-1 to C described in the lower right column of page 4 to the lower right column of page 7 of the publication
-48 etc. are mentioned. Further, silver halide photographic materials containing the metal chelate compound of the present invention are disclosed in U.S. Pat.
, No. 403,721, No. 2,701,197, No. 3,
7Go, No. 453, British Patent No. 1, 326, 889, U.S. Patent No. 3,432.3
No. 00, No. 3,698,909, No. 3,574,62
No. 7, 3, 573. Dye image stabilizers described in No. 050, No. 3,764,337, West German Diet IJ No. 112,529,350,
British Patent No. 2,448,063, British Patent No. 2°610.546, British Patent No. 3,928,041, British Patent No. 3,958,993, British Patent No. 3,961,959, British Patent No. 4,049,455,
3,379,529, 3,043,690, 3,364,022, 3,297,445, 3
゜287.129, JP 54-145135, JP 52-89624, JP 56-137353, JP 56
-114946, 5 Fu No. 93344, 57-1
No. 54234, No. 5B-205150, No. 59-36
DIR compounds described in No. 249 can also be used in combination. Further, the metal chelate compound described in JP-A-60-51834 and the metal chelate compound of the present invention may be used in combination. The metal chelate compound of the present invention is also disclosed in U.S. Patent No. 2.875,
No. 053, No. 2,917,402, No. 3,052,6
No. 36, No. 3,159.646, No. 3,253,92
No. 1, No. 3,272,891, No. 3,533,794
No. 3,652.284, No. 3.687.671, No. 3,705,805, No. 3,706.700,
No. 3,707,375, No. 3,738.837, No. 3,761. ．． No. 272, No. 3,794,493, No. 3,936,305, No. 3,912.606, No. 3
, No. 988,228, No. 4,072,527, No. 4.
No. 1561046, West German Public Service No. 2.231,531,
British Patent No. 1,321,355, British Patent No. 1,335,068
No., Research Disclosure No. 13719, 1
No. 6748, JP-A-49-26138, JP-A No. 49-26
No. 139, No. 49-24428, No. 49-3626, No. 51.138678, No. 51.138679,
No. 51-149277, No. 52-125836, No. 53-107835, No. 56-501338, No. 5
No. 6-81835, No. 58-27139, No. 58-1
No. 11942, No. 58/19945, No. 58-181
No. 041, No. 58-178351, No. 58-1856
No. 77, No. 58-189204, No. 59-68731
No. 59-23344, as well as Journal Op.
Applied Polymer Science (J, ^pp1.P
It can be used in combination with the ultraviolet absorber described in OLIM, Sci.), 9.903 (1965), etc. In order to introduce compounds such as the above-mentioned couplers and the metal chelate compounds of the present invention into the silver halide emulsion layer, conventionally known methods can be used. After dissolving the compound such as the coupler in a high boiling point organic solvent or a low boiling point solvent such as butyl acetate or butyl propionate alone or in a mixture thereof as necessary, the compound is mixed with an aqueous gelatin solution containing a surfactant, Next, after emulsifying with a high-speed rotating mixer or colloid mill, -ti is added to the silver halide to form the silver halide emulsion layer used in the present invention.
m can be adjusted. High-boiling organic solvents that can be preferably used in the present invention include esters such as heptatarate and phosphoric acid ester, organic acid amides, carbons, hydrocarbon compounds, and the like. Preferably a dielectric constant of 7.5 or less and 1.9 or more at ioo°C
It is a high boiling point solvent with a vapor pressure of 0.5 mm and 11 g or less. Even more preferred are heptatarates or phosphoric acid esters in the high-boiling organic solvent. Furthermore, the high boiling point solvent may be a mixture of two or more types, in which case the Ts'? It is sufficient if the IL rate is 7.5 or less. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C. As the 7-talic acid ester and the phosphoric acid ester that are advantageously used in the present invention, the general formula (I[) and the general formula (
III), and typical examples thereof are listed in the upper right column of page 6 to the upper right column of 7x of the same publication as H-1 to H-
It is listed as 22. When added to the silver halide emulsion used in the present invention,
The coupler used in the present invention is usually 0.07 to 0.7 mol per mol of silver halide, preferably 0.1 to 0.7 mol per mol of silver halide.
It is added in an amount of 4 mol. When the coupler has an acid group such as sulfonic acid or carboxylic acid, it is added to the hydrophilic colloid as an alkaline solution. As the silver halide used in the silver halide emulsion layer according to the present invention, common silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Any used in photographic emulsions is included. Silver halide photographic emulsions can be sensitized with chemical sensitizers. Furthermore, this silver oxide can be optically sensitized to a desired wavelength range. Silver halide emulsions are known as anticapri agents or stabilizers in the photographic industry for the purpose of preventing capri and/or maintaining stable photographic performance during the manufacturing process, storage, or photo processing of photographic materials. It is possible to add compounds that are The photographic light-sensitive materials to which the present invention is applied include color anti-capri agents, dye image stabilizers, anti-capri agents, ultraviolet absorbers, etc., which are commonly used in light-sensitive materials. i? Antistatic agents, matting agents, surfactants, etc. can be used. An image can be formed on the color photographic material according to the present invention by subjecting it to color development treatment known in the art. It is also possible to contain a color developing agent in the hydrophilic colloid layer of the photosensitive material, either as the color developing agent itself or as its precursor, and to process it in an alkaline activation bath. The color photographic material according to the present invention is subjected to a bleaching treatment and a fixing treatment after color development. Bleaching treatment may be performed simultaneously with fixing treatment. After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. (Example) The present invention will be explained in more detail by showing specific examples below, but the embodiments of the present invention are not limited thereto.Example 1 40 g of the above-mentioned exemplified magenta coupler (PM-9) and coupler 1 The metal complex (5) of the present invention at a ratio of 0.2 mol per mol was dissolved in a mixed solvent of 40+*1 organic solvent (S-1) and 100 mj! of ethyl acetate, and this solution was mixed with 25 g of sodium dodecylbenzenesulfonate. 500 g of green-sensitive chlorobromide emulsion was added to 300 liters of a 5% aqueous gelatin solution, and then dispersed with a homogenizer.
A coating solution was prepared by adding a coating aid to the silver (containing 30% silver PAty).Then, this coating solution was coated on a polyethylene-covered paper support, and further on this coated layer, 2
-(2-Hydroxy-3,5-cy-7-milphenyl)benzo(lyazole, gelatin, a coating solution containing a spreading agent and a hardening agent was applied to form a protective film. At this time, 2-(
2-Hydroxy-3,5-not-t-7milphenyl pen'/ ) +77sol was coated at a dosage of 5 B/des" and gelatin was coated at a dosage of 15 mg/d so 2, and exposed to silver halide photography for single color. A material was created (Sample 1). Next, Samples 2 and 3 were created which were the same as Sample 1, except that comparative metal complexes A and B were added at a ratio of 0.2 mol to 1 mol of magenta coupler. Melt aS-1 2Ns 2Hs Comparative metal complex A Comparative metal complex B CH3[;Ha Also, instead of metal complex (5) of sample 1, metal complex (4
), Sample 4, which is the same as Sample 1 except that (17) was added;
Sample 5 was created. Samples 1 to 6 thus prepared were subjected to optical wedge exposure using a sensitometer (Model 91. KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments. Processing process Processing temperature Processing time Color development 32.8℃ 3 minutes 30 seconds Bleach fixing
32.8℃ Wash with water for 1 minute and 30 seconds 32.8
℃ 3 minutes 30 seconds The composition of the treatment liquid used in the above treatment step is as follows.

[Color developer]

4-7 minnow 3-methyl-N-ethyl-N-(β-notanesulfonamidoethyl)aniline sulfate
5g benzyl alcohol
15 theories! Sodium hexametaphosphate 2
．． 5g anhydrous sodium sulfite 1.8
5g Sodium Bromide 1.4g
Potassium bromide 0.5g Borax 39.1g Add water to make the pH 11, and adjust the pH to 3 using sodium hydroxide.

[Bleach fixing a]

Iron ammonium ethylenedi7minetetraacetate ei, og ethylenecyaminetetraacetate a2 Ammonium salt 5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.5° Anhydrous sodium sulfite Z, 7g Add water to make 11. After the treatment, the coloring density of each sample was measured in the following manner to examine the coloring caused by the metal complex. In addition, the increase in yellow stain due to storage was measured as follows. [Measurement of 1 color density 1 The spectral reflection spectrum of the white part of each sample was measured using Color Analyzer Model 607 (Hitachi 91).
Using the spectral reflection density of the blank sample at nm as a reference, the difference between the spectral reflection density of each sample and the 44On fake was measured. Measurement of increase in ti color stain] Each sample was stored at 77° C. without humidification for 14 days, and the increase in blue light density was measured using a Sakura Densitometer Model PD^-60. Furthermore, the light resistance of the sample obtained after the treatment was measured in the following manner.

[Light resistance test]

Underglass outdoor El on the dye image formed on each sample
The fading rate (=X 100 O Do: initial density (1,0), D second density after fading) when exposed to sunlight for 400 hours was measured using an outdoor stand (manufactured by Sukeniso KK). These results are shown in Table 1. Table 1 As is clear from the results in Table 1, the samples using the metal complex of the present invention have almost no coloring compared to the conventional metal complexes (Samples 2 and 3), and also have no yellow stain due to storage. It can be seen that this has been prevented and the light resistance has been greatly improved. Example 2 On a support made of polyethylene i-covered paper, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material. 1st N: Blue-sensitive silver halide emulsion layer yellow coupler α-piparyl α-(1-benzyl-2,4-diorsoimidaridin-3-yl)-
2-chloro-5-

[γ-(2f4-)-t-7milphenoxy)butyramide J acetalinide at 8 B/d
a”, blue-sensitive silver hadenide emulsion (silver chlorobromide emulsion containing 90 mol% silver bromide) converted to silver is 3111 g/d Theory 2
．． 2',4'-not-butyl-7enyl-3,5-di-L-7-mil-4-human a-xybenzoate at 3B/da
2nd N: Intermediate layer 2.4-note t-octylhydroquinone was coated in IBZd theory 2. , diisodecyl 7 tallate was coated at a coating amount of 0.1 B/dm" and gelatin was coated at a coating amount of 4 mg/ds+". Third layer: edge-sensitive silver halide emulsion layer. ) to 4 wg/
dm”, green-sensitive silver chlorobromide emulsion converted to silver, 3-g/d
a'', dioctyl 7-thaleate was applied at a coating amount of 4 mg/dm'' and gelatin at a coating amount of 16 mg/da2. 4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3,5-di-L-
7 milphenylene I) benzotriazole at 3-g/da
”, 2-(2-hydroquine-3,5-no-butylphenyl)benzotrizole 3 mt1/da2,
Dioctyl 7-talate was applied at 4 mg/dI+'' and gelatin was applied at 14-g/d at a coating weight of 2.5th layer: red-sensitive silver halide emulsion layer 2,4-dichloro- as a cyan coupler. 3-methyl-
6-Ea-(2t4-not-7milphenoxy)butyl7mi)'17! The coated amount was 4 mg/dm" of nol, 2 g/d of 9 octyl 7-talate, and 3 mg/da" of red-sensitive silver chlorobromide emulsion in terms of silver. . 6th layer: 2-(2-hydroxy-3°5-; as an intermediate layer ultraviolet absorber;
)-t-7milphenyl)benzotriazole 2mg
/dso2.2-(2-human axy-3,5-t-butylphenyl)pensotriazole 2 mgZd-2
, dioctyl 7-talate was applied at a coating weight of 2 mg/d2 and gelatin was coated at a coating weight of 6-g/da''. Seventh layer: protective layer gelatin was coated at a coating weight of 9-g/d112. The sample prepared in this manner is referred to as sample 6 (comparison). Next, the 3rd M of sample 7 contains the exemplified metal complex (5) according to the present invention.
Samples 7.8.9 were prepared which were the same as Sample 6 except that , (4) and (3) were added at a ratio of 0.2 mol to 1 mol of magenta coupler. Also, the metal complex of sample 7
), the following comparative compounds A and B are used as conventionally known anti-fading agents.
, C, D, and E were added at 0.3 moles per mole of coupler. Samples 10.11.12.13.14 were prepared. Below are blank spaces Comparative compound A Comparative compound B Comparative compound C Samples 15 and 16, which were the same as Sample 7, were prepared. Samples 6 to 16 thus prepared were subjected to the same exposure treatment as in Example 1. (However, in order to obtain a magenta monochromatic sample, light exposure was performed using green light.) For each sample obtained after processing, the color density was measured and the occurrence of yellow stain was investigated in the same manner as in Example 1. . In addition, the light resistance of the samples obtained after the treatment and the samples stored for a long period of time was measured in the following manner. [1 is a photosensitive test] The same as Example 1 except that the exposure time by sunlight was 380 hours. [Lightfastness test after storage] The dye image formed on each sample was stored at 77° C. without humidification for 13 days, and then the above lightfastness test was conducted. These results are shown in Table 2. As is clear from the results in Table 2, in the samples of the present invention, the molar loss of the metal complex added is lower than in Samples 10 to 14 containing conventional antioxidants (comparative compounds ASB, C, D, and E). Nevertheless, it can be seen that the light resistance has been greatly improved. It was also found that the samples of the present invention not only showed little fading due to light, but also had almost no coloration and little yellow staining. [Effects of the Invention] By incorporating the metal complex of the present invention into a color photographic light-sensitive material, the stability of an image against light, particularly the light resistance, can be improved. That is, it exhibits the excellent effects of significantly reducing fading of the dye image due to light, almost no coloring, and suppressing the occurrence of dark spots and yellow stains.

Claims (1)

[Scope of Claims] A method for stabilizing images of a photographic material against light by incorporating at least one metal complex represented by the following general formula [I] into the photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, R^3 and R^4 are respectively,
A hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group that is bonded to a carbon atom of a benzene ring directly or via a divalent linking group, or It represents a heterocyclic group, and R^5 represents an alkyl group or an aryl group. n represents an integer from 0 to 2, and when n is 2, the two R^5s may be the same or different. M is Co,
Represents Cu, Ni, Pd or Pt. ]