JPS62131257A - Method for preventing photofading of organic coloring substance - Google Patents

Abstract

PURPOSE:To improve the stability of the org. coloring substance against a light by incorporating jointly a specific compd. to the titled substance. CONSTITUTION:At least one kind of the compds. shown by the formula is sued jointly with the org. coloring substance for the titled substance. The used amount of the metallic complex shown by the formula is preferably 5-300mol%, further preferably 10-200mol% on the weight basis of the org. coloring substance. Said org. coloring substance comprises all dyestuff classified according to a property of the dyestuff such as a basic dyestuff and an acidic dyestuff, etc. Said org. coloring substance has at least one of the max. absorption within a wavelength of from 300nm to 800nm, preferably from 400nm to 700nm, in a methanol solution of said org. coloring substance.

Description

[Detailed description of the invention] Ru.

It is generally known that organic coloring substances tend to fade due to light. Research is being conducted to prevent photofading of organic coloring substances such as inks, textile dyes, and color photography in the fields of color photography.

The present invention aims to prevent photofading of such organic coloring substances,
It is used in quite a few issues.

The organic four-color substance used in the present invention is a substance that appears a-color to the human eye under sunlight.
Generally 300nm to 800nm in methanol solution
Ti',4- refers to an organic substance that exhibits at least 61 absorption maxima in Ti',4-.

Furthermore, in this specification, the term light refers to approximately 300n
Colors electromagnetic waves from m to approx. 800nm or less, approx. 400n
It includes ultraviolet light of less than m, visible light Yj of about 4 Q Onm to about 700 r+m, and infrared light of about 700 nm to about 800 nm.

It has long been known that organic four-color substances, such as pigments or dyes, have a tendency to fade when exposed to light.

However, there are many reports on methods for reducing complementary colors and improving light fastness. For example, in U.S. Pat. No. 3,432,300, organic compounds such as indophenol, indoaniline, azo and azomethine dyes are combined with phenolic type compounds containing fused heterocyclic ring systems to produce visible and ultraviolet light. It is stated that the robustness against In the field of silver halide color photographic materials, The Theory by Mies et al.
Of Photography Ink Process 3rd Edition (The
Theory orPhotographic Pr
azomethine dyes or indoaniline dyes are formed by the reaction of an oxide of an aromatic primary amine compound with a coloring agent (coupler), as described in Chapter 17 of ``OceSs, 3rd Edition'' (1967). Ru.

It is desired that the dye image obtained from such a coupler does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity.

However, the fastness of these dye images to mainly ultraviolet rays or visible light is not satisfactory, and it is known that the color changes and fades a little when exposed to these actinic rays. In order to eliminate such shortcomings,
Conventionally, various couplers with low fading properties have been selected and used, ultraviolet absorbers have been used to protect dye images from ultraviolet rays, or groups that impart light resistance have been introduced into the couplers. Several methods have been proposed.

However, in order to provide satisfactory lightfastness to a dye image using, for example, a UV absorber, a relatively large amount of UV absorber is required, and in this case, the dye image becomes significantly contaminated due to the coloration of the UV absorber itself. There have been times when I have been Further, even if an ultraviolet absorber is used, it does not show any effect in preventing fading of the dye image due to visible light, and there is a limit to the improvement of light resistance by the ultraviolet absorber. Furthermore, a method is known in which a dye image fading inhibitor having a phenolic hydroxyl group or a group that can be hydrolyzed to produce a phenolic hydroxyl group is used. Regarding these, for example,
-31256, 48-31625, 51-30
No. 462, JP-A-49-134326 and JP-A-49-134326
No. 134,327 describes phenols and bisphenols, U.S. Pat. ca9,262s6 contains bi[J galol, gallic acid and its esters, U.S. Pat.
, 29Q issue 1, 'il 4, (l l 5
, 99 Q-shi) is α-tocofe [J-ru and its anol derivatives, Japanese Patent Publication No. 52-27534, Japanese Unexamined Patent Application Publication No. 52-1989
14751s;- and U.S. Pat. No. 2,735.765, hydroquinone derivatives, U.S. Pat.
No. 0, No. 3,574゜627 inch, 6-hydroquine chromans; US Pat. No. 3,573, oso-;
No. 77 proposes the use of 6.6'-dihydroxy-2'2'-bisspi [1 chromans and the like. However, although these compounds can be seen to some extent to be effective as dye fading and discoloration inhibitors, they are not sufficient.

British Patent No. 1,451,000 also describes improving the light stability of organic colored compounds using an azomethine quenching compound whose absorption peak is more bathochromic than that of the colored compound. However, since the azomethine quenching compound itself is colored, the (r
1 phase; sharp brown brim), - = "c (, l ke 1-7- kite. Also, metal complexes can be used to prevent premature aging of polymers. 11. J.B. Guillory, R. ·varnish·
Becker (J, P, GuillorY, R,S
r3ecker), Journal of Polymer Science.

Polymer Chemistry C (J, Polym, Sci,
, Polym, Chem, Ed.) Volume 12, 9
93 pages (1974), R.P.R.Ranaweera, G.S.
Ra, G, Scott), Journal of Polymer Science, Polymer Letter RQ (, J, P
olym, Sci,, P olym, L et
t, Ed., Vol. 13, p. 71 (1975), and methods for stabilizing dyes against light using metal complexes are described in JP-A-50-87649 and Research Disclosure 15162 (+976). However, since these complexes do not have a great anti-fading effect and are not highly soluble in Tj't4 solvents, they cannot be added in an amount sufficient to exhibit an anti-fading effect.

Furthermore, since these complexes themselves have a large coloring property, if they are added multiple times, they will adversely affect the hue and purity of the a-coloring substance, especially the pigment.

Furthermore, methods for photostabilizing dyes using each intercalated 2ft body are described in JP-A Nos. 54-62826, 54-62987, 54-65185, 54-69580, and 5
No. 4-72780, No. 54-82384, No. 54-8
No. 2385, No. 54-82386, No. 54-1365
No. 81, No. 54-136582, No. 55-12129
No. 55152750, No. 56-168652,
It is described in No. 56-167138, No. 57-161744, Japanese Patent Publication No. 57-19770, etc.

However, even the method described in ``-'' is still insufficient to reduce the coloration of the tit body itself to a low F, and it is not possible to eliminate the adverse effects on the hue and purity of organic coloring substances, especially dyes.

Furthermore, when these known metal complexes are applied to silver halide color photographic materials (hereinafter referred to as color photographic materials), stains are likely to occur in the uncolored areas of the color photographic materials that have been subjected to color photographic processing. In particular, when a developed color photographic material is stored under conditions of high temperature and high humidity, the occurrence of contamination increases significantly.

[Purpose of the invention]

It is an object of the present invention to provide a method for improving the light stability of organic coloring substances.

Another object of the invention is to provide a method for improving the light stability of organic coloring substances, especially pigments, without deteriorating the hue and purity of these substances. That's true.

Furthermore, it is another object of the present invention to provide a method for improving the stability to light of a color image forming a color photographic image without causing contamination of uncolored areas of color photography. .

[Structure of the invention]

The above object of the present invention is to combine an organic coloring substance and the following general formula [+3
This is achieved by coexisting with at least one of the compounds shown in the following.

In the formula, M represents Co, Cu, Ni, Pd or PL,
R2 and R1 each represent an alkyl group or an aryl group. xn- represents a monovalent organic or inorganic anion, and n represents an integer of 1 to 3.

The present invention will now be described in more detail.

In General Formula [1] of No. 16, the alkyl group represented by rll and R is preferably an alkyl group having 1 to 20 carbon atoms (and may be linear or branched, and may be substituted Specific examples of straight chain or branched alkyl groups include methyl, trifluoromethyl, ethyl, propyl, isopropyl, butyl, L-butyl, heginol, octyl, decyl, dodenyl, tetradecyl, hexadecyl, octadecyl, eikonol, etc. The following groups can be mentioned.

The aryl group represented by 111 and R7 is preferably an aryl group having 6 to 14 carbon atoms, and may have a substituent. For example, phenyl group, tolylgami, naphthyl group, etc. can be mentioned.

M represents Cu, Co, Ni, Pd or PL, but Cu
Or Ni is particularly preferred.

X (for i-machine anions, for example, t C
sl! +7+O+-, Cl211250&0*-, (e
O)2PO-0°, and examples of inorganic anions represented by xn- include CQ-, Br-, I-, 01l-, CN-
, C (104-.

Ple-, NO+P0.3-, sot'-, CO3
Examples include "-, BO,-", 13F,-, and the like.

In general formula (1), the first . The part shown below shows that it is a resonance system due to the double bond 3.

Next, representative examples of the compound represented by the above general formula (1) used in the present invention (hereinafter referred to as the compound of the present invention) will be shown.

The above compounds are published in Proceedings of the 49th Spring Annual Meeting of the Chemical Society of Japan,
It contains the compounds described in p. 420, Proceedings of the 50th Spring Annual Meeting, p. 48g, and can be synthesized according to the methods described therein.

Furthermore, among these compounds of the present invention, the compounds whose anion moiety is an organic anion can be mixed with the compounds of the present invention whose anion moiety is an inorganic anion in an aqueous medium (an aqueous solution or an aqueous solution containing a water-affinity organic solvent). It is obtained by reacting a salt of an organic anion (for example, Li'', Ha'', + or N tl 4- salt) and filtering the precipitated crystals.

The use of the metal complex represented by the general formula CI) of the present invention is 5 to 30% of the organic coloring substance used in the present invention.
It is preferably 0 mol%, more preferably 10 to 200 mol%.

The organic coloring substances used in the present invention include basic dyes, acid dyes, direct dyes, soluble vat dyes, water-soluble dyes such as mordant dyes, sulfur dyes, vat dyes, oil-soluble dyes, disperse dyes, azoic dyes, It includes all dyes belonging to the classification of dyeing properties such as insoluble dyes such as oxidative dyes or reactive dyes.

These organic coloring substances are 300n in methanol solution.
m to 800nm, preferably 400nm to 700n
There is at least one absorption maximum at m.

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 (dianine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoamine dyes, and It includes dyes belonging to chemical structural classes such as indophenol dyes, innocoid dyes, carbonium dyes, and formazan dyes.

The organic coloring substance used in the present invention is an image-forming dye used in the field of photography, such as color coupler, DRR.
It includes all dyes formed from compounds, DDR couplers, amitracine compound dye developers, dyes for silver dye bleaching methods, etc.

Preferred dyes for use as organic colorants of the present invention include anthraquinone, quinone imine, azo, methine,
Polymethine, indoamine 1. These include indophenol and formazan dyes. The dyes most preferably used in the present invention are methine and polymethine dyes and indoamine and indophenol dyes. This dye includes compounds having the following groups.

Among the above groups, 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 this invention include yellow, magenta and cyan dye-forming types. This coupler is described in US Pat. No. 3,277.155, for example.
It may be a so-called 4-equivalent type or a 2-equivalent type as described in No. 3,458,315.

Preferred yellow dye image-forming couplers in the present invention are benzoylacetanilide type, pivaloylacetanilide type, or substituted with a substituent (so-called split-O group) in which the carbon atom at the coupling position can be separated during the coupling reaction. There are two types of dye image-forming couplers, and magenta dye image-forming couplers include 5-pyrazolone, pyrazolotriazole, imidazopyrazole, pyrazolopyrazole, pyrazolotetrazole, and bira. There are two-power magenta dye image-forming couplers having a zolinohentzimidazole type, an indacylon type, or a split-off group, and cyan dye image-forming couplers having a phenol type, naphthol type, pyrazoloquinazolone type, or a split-off group. There are two existing cyan dye image-forming couplers.

Specific examples of these yellow, magenta, and cyan dye-forming couplers are known in the photographic industry, and the present invention encompasses all of these known couplers.

Next, typical examples of yellow couplers that can be used in the present invention are listed.

・-2＼, CI lower white-I Y-2 ■ し1!3 Y-13 Y-14 しν I13 Y-25 Y-26 ゝ0' These yellow couplers are described, for example, in West German Published Patent Application No. 2.
No. 057,941, West German Publication No. 2.163,812, Japanese Patent Application Publication No. 47-26133, West German Publication No. 4g-29432,
No. 50-65231, No. 51-3631, No. 51-
No. 50734, No. 51-102636, No. 4g-66
No. 835, No. 48-94432, No. 49-1229, No. 49-10736, Special Publication No. 51-33410,
52-25733, etc., and can be easily synthesized according to the method described in A1 et al.

Next, a typical example of magenta tap J blur that can be used in the present invention will be given.

M″-ICQ Shishi Cθ Shishi Cθ L Cθ Shishi Shishi M-9 Cσ ShiQ Cθ Shishi Cσ Cθ ShiQ O ShiQ I Shishi I Shishi Cθ Shishi Cθ Shishi Cθ M-21 Cθ Shig ShiQ ~1-23 Shishi ShiQ ShiQ ShiQ Cθ ShiQ C.O. ShiQ ~1-34 I しν S-cho-35 Q ~1-36 Q I ShiQ ~1-39 ~1-40 vl-41 Cθ Shishi I Shishi M-45 ShiQ M-60 M-61 ~1-62 ell.

lls M-76 M-77 M-92 These magenta couplers are described, for example, in U.S. Pat.
No. 4,514, British Patent No. 1,183,515, Japanese Patent Publication No. 40-6031, No. 40-6035, No. 44-15
No. 754, No. 45-40757, No. 46-19032
No., JP-A-50-130.41, JP-A No. 53-12903
No. 5, No. 51-37646, No. 55-62454,
U.S. Patent No. 3.725,067, British Patent No. 1.252,
No. 418, No. 1.334, 515, JP-A-59-17
No. 1956, No. 59-162548, No. 60-436
No. 59, No. 60-33552 Research Disclosure
) 24626 (1984), patent application No. 59-2430
No. 07, No. 59-243008, No. 59-24300
No. 9, No. 59-243012, No. 60-70197, No. 60-70198, etc., and can be synthesized according to the methods described therein.

Although there are no particular limitations on the cyan coupler used in the present invention, a phenolic cyan coupler is preferred.

Next, typical examples of cyan couplers that can be used in the present invention will be given.

(, -2 n■ Convex +1 01 [ n++ ShiV Shishi σ (’)II C-12 Shishi Shishi ShiQ ll Shit Shishi ShiQ 0 ■ teeth H fal+ 0 ■ C-28 II 0I+ t,,H.

し＋Jts CQ C-44 C-45 しH31,,12 These cyan couplers are described, for example, in U.S. Pat.
．． No. 730, No. 2,801.171, Japanese Unexamined Patent Publication No. 1973-1
No. 12038, No. 50-134644, No. 53-10
No. 9630, No. 54-55380, No. 56-6513
4, No. 56-80045, No. 57-155538, No. 57-204545, No. 58-98731, No. 59-31953, etc., and methods described therein. Synthesize according to the following.

When such couplers are used in the present invention, dyes are formed from these couplers by reaction with an oxidized aromatic primary amine silver halide phenomenon agent.

The above developers include aminophenol and phenylenenoamine, and these developers can be used in combination.

Representative examples of phenomenon agents that can be combined with various couplers to produce colored compounds in accordance with the present invention are listed below.

(Exemplary developer) (5) [:6) (9
) (to) (11)
[12] Examples of other dyes that can be used as coloring compounds in the present invention include the following.

[Example dye]

1l (+-6) rθ CQ (+-18) (+-21) (+-26) (+-28) (1-2'l) Furthermore, other types of dyes preferably used in the present invention include , U.S., No. 8351.673, U.S. Patent 3
, No. 932.381, No. 3,928,312, No. 3,
931,144, 3゜954.476, 3.9
No. 29,760, No. 3,942,987, No. 393
2.3'80, 4,013,635, 4,0
No. 13,635, No. 4.013,633, Japanese Unexamined Patent Publication No. 1973
-113624, 51-109928, 51-
No. 104343, No. 52-4819, Patent Application No. 1982-6
No. 4533, rResearch Disclosure
eJ magazine (Research Eyelid Disclosure) (November 1976 issue) pages 68-74, magazine No. 13024 ('
Examples include dyes formed by oxidation of DRR compounds described in 75) and others.

Furthermore, other types of dyes that can be used in the present invention include, for example, British Patent Nos. 840,731; 904,364; 932,272; 1,014,725;
, No. 038,331, No. 1,066.352, No. 1,
No. 097,064, JP 51133021, U.S.
T 900,029 (U, S, Defensi
ve I' publication), U.S. Patent 3.2
Dyes released by the reaction of DDR couplers such as those described in No. 27,550 with oxidized forms of color developing agents include dyes formed by reaction with oxidized forms of color developing agents.

Other types of dyes preferably used in the present invention include Japanese Patent Publications Nos. 35-182, 18332, and 48.
-32130, 46-43950, 49-26
Can you name the dye developers listed in No. 18?

Furthermore, other dyes used in the present invention include various dyes used in silver dye bleaching methods.

Color dyes that can be used for this purpose include Direct Fast Yellow G O (CI 29000);
azo dyes such as glisophenine (CI 24895);
Indigo Golden Yellow rGKccI 59101
), Indigosol Yellow 2GB (CI61726)
, Arbosol Yellow 0CA-CI” (C16730
1), Indanthrene Yellow GI? '(C[68
420), Mikethrene Yellow GC (CI 6730)
0), Intanthrene Yellow 4 G K (CI 6
Examples include benzoquinone dyes such as 8405); anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes. Magenta dyes include Sumilite Subralpinol B (CI 29225), Penzobrilliant Keranin B (CI 15080)
Azo dyes such as Innovosol Brilliant Pink I
R (CI 73361), Indigosol Violet 15R (CI 59321), Innovosole Red Violet IRRL (C159316), Indanthrene Red Violet RRK (CI 67895)
, Mikethren Brilliant Bioleft B B K (
Examples include indigoid dyes such as C[6335], soluble vat dyes made of benzoquinone and anthraquinone heteropolycyclic compounds, and other vat dyes.

As a cyan dye, Direct Sky Blue 6 B
(CI 24410), Direct Brilliant Blue 28 (CI 22610), Azo dyes such as Sumilight Zabra Blue-G (CI 34200), Sumilight Sabra Turkey Blue (CI 74180)
, Mikethren Brilliant Plue 4 G (CI 7
phthalocyanine dyes such as Indance Lenkey Sprue 5 G (CI 6911145),
Mention may be made of indanthremble-GCD (CI 73066), indigosol 04 G (CI 73046), anthrazole green [r3 (CI 59826), and the like.

As mentioned above, the compounds of the present invention stabilize organic color substances.These compounds of the present invention may be present in any emulsion layer of a color photographic light-sensitive material, or in the entire emulsion layer. The compounds of the present invention may also be present in any of the non-photosensitive layers of the color transfer material.An effective method for dispersing these compounds of the present invention is the formation of couplers. The method is the same as described for dispersion.

The compounds of the present invention are generally oil-soluble and are commonly found in U.S. Pat. l7 (No. 1, 2.80I.

No. 171, No. 2,272,191 and No. 2.304
, No. 940, it is preferable to dissolve the coupler in a high boiling point solvent, optionally using a low boiling point solvent in combination, disperse it, and add it to the hydrophilic colloid solution. There is no problem if an itoquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor is used in combination. At this time, there is nothing wrong with using a mixture of two or more compounds of the present invention. Further, to explain in detail the method of adding the compounds of the present invention, one or more of the compounds may be added with an organic acid at the same time as a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor, etc., as required. Amides, carbamates, esters, ketones, hydrocarbons and urea derivatives, especially di-n-butyl phthalate, tricresyl phosphate,
Jimmy octyl azelate, di-n-butyl sebacate, tri-n-hequinolaj nisphate, decalin,
Ethyl acetate, butyl acetate, butyl propionate, if necessary, in a high boiling point solvent such as N,N-di-ethyl-caprylamide, N,N-didylaurylamide, n-pentadecyl phenyl ether or fluoroparaffin. Alkyl/benzenesulfonic acid and Mix with an aqueous solution containing a hydrophilic binder such as gelatin containing an anionic surfactant such as alkylnaphthalene sulfonic acid and/or a nonionic surfactant such as solhitane sesquioleate and sorbitan monolaurate, and rotate at high speed. A mixer, a colloid mill, and a colloid mill are used to emulsify and disperse the resulting f-2 dispersion using an ultrasonic dispersion device, etc.
il aqueous colloid solution (e.g. silver halide emulsion),
・, 6 can be added and used.

Both the colorant and the compound of the invention 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 light-absorbing substances and compounds of the invention are included in such non-light-sensitive image-recording elements, they are preferably mordanted. Therefore, for such uses, the compounds of the present invention should be in any molecular form that can be retained in the mordant layer of the receiver without migrating away from the dye to be stabilized. L).

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 such application is an Invivision transfer film unit such as that described in US Pat. No. 2,882.156. Yet another application is U.S. Patent 2゜087.8
No. 17, No. 3,185,567, No. 2,983,60
No. 6, No. 3゜253.915, No. 3,227.550
No. 3,227,551, No. 3227.552, No. 3,415,644, No. 3,415,645,
3゜415.646, 3,594,164 and 3,594.165 and Belky patent 757,9
59 and 757,960.

The coloring substances used in the present invention and the compounds of the present invention are subject to Product Licensing Index (Product Licensing Index).
uct licensing index),
92@ (December 1971), No. 9232, 107-
The method can be used with materials such as those listed on page 110. In this regard, Nos. t and n of the above-mentioned document.

III, IV, V, ■, 'v'1. IX,X,X
I , XI [, X [I , X IV , X V .

Sections xvr, x■, X■, and XXIII are applicable.

Any type of compound of the invention that should result in the improvements of the invention could theoretically be used! There is no upper limit for n. When the invention is applied to photographic materials, it is preferred that at least 1 micromole of the compound of the invention is present per square meter of the material, with about 10 to I x 10' micromole of the compound of the invention per square meter of the material. It is more preferable if the compound exists.

Generally, the colorant concentration should be equal to that commonly used in color photography techniques. These densities are well known to those skilled in color photography. Preferably, the colorant is present in a range of about 10 to 104 micromoles per square meter of light-sensitive material. More preferably, it is present in the range of 100 to about 600 micromoles of I'IZ of the photosensitive material.

The colored substances used in the present invention generally have a maximum wavelength absorption peak of less than 800 nm in methanol solution.

The maximum wavelength absorption peak of this substance is preferably in the range of 300 to 800 nm in methanol solution, and 40 nm to 800 nm.
The most preferred range is 0 to 700 nm.

In the photographic light-sensitive material used in the method of the present invention, the silver halide emulsion is generally one in which silver halide grains are dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, silver iodide, These include silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof, and these silver halides can be produced by various methods such as an ammonia method, a neutral method, a so-called conversion method, and a simultaneous mixing method. Hydrophilic colloids for dispersing silver halide are generally gelatin and derivative gelatin such as phthalated gelatin and malonated gelatin. Gum arahia, alginic acid, casein, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, imidized polyacrylamide, polyhinylpyrrolidone, and copolymers of these vinyl compounds can also be used. Further, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity of 1.j to a desired wavelength range.

Preferred L1 sensitizing dyes include, for example, banyanine dyes, merocyanine dyes, and coldanine dyes, which may be used alone or in combination of two or more. Chemical sensitization can also be carried out by a conventional method. Examples of chemical sensitizers include gold compounds such as chloroauric acid salts and gold trichloride, noble metals such as platinum, palladium, and iridium, and sodium thiosulfate. Sulfur compounds such as sulfur compounds, stannous salts, amines, and other reducing compounds that react with silver sulfide to form silver sulfide are hated.

In addition, stabilizers such as triazoles, imidazoles, azaindenes, benzothiazoliums, zinc compounds, cadmium compounds, mercaptans, chromium salts, zirconium salts, mucochloric acid, aldehyde series, trianone series, polyevoquine compounds, triedeyl Hardeners such as lemposamide and edylenimine; plasticizers such as dihydroxyalkanes such as glycerin and 15-bentanediol; optical brighteners; antistatic agents: various photographic additives such as coating aids; These can be used singly or in combination of two or more.

Further, the above-mentioned compound of the present invention, etc. is dispersed in the obtained silver halide emulsion, and the dispersion is impregnated, and if necessary, cellulose acetate, nitric acid, etc. A color photograph +4 material can be obtained by coating on a support such as a synthetic resin film such as cellulose, polycarbonate, polyethylene terephthalate, or borisdylene, baryta paper, polyethylene cover, glass temporary, or the like.

The color photographic material to which the present invention is applied may be an internal color photographic material containing a coupler or an external color photographic material containing a coupler in the phenomenon liquid.

” - In the coupler-containing color photograph 1,
It is processed according to conventional methods to obtain a color image. In the second case, the main processes are color development, bleaching, and fixing, and if necessary, water washing, stabilization, and other processes are included. These processes, such as bleach-fixing, can involve performing two or more steps in one bath. Color development is usually carried out in 1' alkaline solutions containing aromatic treated amine developing agents. Preferred specific examples of the aromatic first-handling amine developing agents are described as exemplified developers [1] to [12] in the electronic publication.

When the color photographic material to which the method of the invention is applied is a film unit for color expansion transfer, processing of the photographic feed is automatically carried out inside the photographic material. In this case, the developing agent is stored in a rupturable container. In addition to the compounds represented by [1] to [12] above, examples of developing agents include N-methylaminophenol, ■-phenyl-3
-pyrazolitone, 1-phenyl-4,4-dimethyl-3
-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazoli), 3-methquine-N,N
-diethyl-p-phenylenediamine, etc. can be used.

In order to form a color image in the color photographic material used in the method of the present invention, a method using a coupling reaction between the aforementioned dye-forming color coupler and an oxidized form of a p-phenylenediamine color developing agent; A method using a dye developer, a method using an oxidative rupture reaction of a DIR compound, a method using a dye separation reaction due to a coupling reaction of a DDI' (coupler), a method using a dye forming reaction due to a coupling reaction of a DDR coupler, or a method using a dye forming reaction due to a coupling reaction of a DDR coupler. Known methods such as a bleaching method can be used.

Therefore, when applying the method of the present invention to photosensitive materials, color positive film, color paper,
Three types of color photographic materials include color negative film, color reversal film, film unit for color diffusion transfer, silver dye bleaching, and photosensitive feed.

The present invention will be described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A magenta dye having the following structure (maximum absorption in methanol solution: 538 nm) was dissolved in 4 mQ and 8 mρ of ethyl acetate, and the solution was dissolved in 0.5% dodecyl phosphate. The mixture was emulsified and dispersed in 10 mρ of a 1O% gelatin solution containing 2II112 of an aqueous solution of sodium benzenesulfonate.

Next, this emulsified dispersion was mixed with 30 mL of a 5% geladine solution and applied onto a paper support laminated on both sides with polyethylene to obtain a sample. This sample is designated as No.1.

When preparing the above emulsified dispersion liquid in the same manner, 50B of each of the comparative compounds represented by the following tM formulas (a) and (1+) were added and applied in the same manner as the above sample Nos. and 1. t4No, 2 & N083 were created.

Further, when preparing the emulsified dispersion liquid by the method of the above sample No. 1, as shown in Table 1, 50 m9 of each of the exemplary compounds of the present invention were added and applied in the same manner as the above sample No. 1. Seed samples (No. 4 to 15) were prepared.

Comparative compound (a): Metal complex comparative compound (b) described in JP-A No. 55-12129. Each sample described in 1. above was exposed to a xenon fade meter for 71 hours to determine the light resistance of the dye image. ,1. I'm tired. Table 1 shows the results.
Shown below. However, the light resistance of the dye image was determined based on the dye residual rate.

The samples used (No. 4 to 15) were known metals 611
It shows a better photofading prevention effect than the samples using the body (Nos. 2 and 3).

Example 2 In Example 1, a magenta dye having the following structure (maximum absorption of 536n in methanol solution) was used.
Fifteen types of samples (Nos. 16 to 30) were prepared in the same manner as in Example 1, except for changing to Example 1. The obtained sample was exposed to a xenon fade meter for 5 days to examine the light resistance of the dye image. The results are shown in Table 2 (magenta dye) 1. (i ・3) Table 2 Also in Table 2, the samples using the metal complex of the present invention were
It can be seen that this sample has a superior photofading prevention effect compared to samples using known metal complexes.

Example 3 Exemplary coupler (M-65) 2 as magenta coupler
8 g dibutyl phthalate 28 and ethyl acetate 100
The solution dissolved in mQ was mixed with 5% gelatin aqueous solution 5001T containing 2.5 g of sodium dodecylbenzenesulfonate.
IQ, and then dispersed with a homogenizer, and the resulting dispersion was mixed with green photosensitive silver chlorobromide (containing 30 mol% silver chloride).
]') Added to 1000ffi12 of emulsion and added N as a hardener.

10 mL of a 2% methanol solution of N',N''-triacryloylhexahydro-8-triazine was added, coated on polyethylene coated paper and dried to obtain a sample of a monochromatic color photographic material.This sample was designated as No. 31. do.

When preparing the above emulsified dispersion liquid in the same manner, Comparative Compounds (c) and (d) having the following structures were added in 10y each and applied in the same manner to prepare samples No. 32 and No.

33 was created.

Furthermore, as shown in Table 3, 10 g of each of the exemplary compounds of the present invention were added and applied in the same manner to seven types of samples (No.

34-40) were created.

Comparative compound (c): Compound described in JP-A No. 54-48538 Comparative compound (b): Compound described in JP-A-56-1596=14 After exposing each of these samples, the following It was treated with the following treatment solution and treatment steps.

[Developer]

Potassium monobromide 0.59 Add water to bring it to lσ, use sodium hydroxide to adjust pH to 10,
Adjust to 30.

[Bleach-fix solution]

[Two-handed diamine tetraacetate iron metabisulfite ammonium 13.31! Anhydrous) sodium sulfite 2.79 Add water and 1i! Close and adjust the pH to 6.5 using aqueous ammonia.

[Processing process] (30°C) Processing time Bleach ankle 1 minute 30 seconds Wash with water 3 minutes dry
Drying: The dye image formed in this way is applied to the sample using Kodanoku Latchin Filter N, an ultraviolet cut filter.
A fading test was conducted for 7 days using a xenon phase meter with 2A attached.

The results are shown in Table 3.

The degree of fading was shown by the change in density of the 1.0 al and f portions before the fading test.

The absorption maximum was at 536 nm. ) As is clear from the results in Table 3, the metal complex of the present invention has superior anti-fading +1-effects over conventional organic anti-fading agents.

Fruit: 1lli Example 4 Illustrated coupler (C-50) 35 as a Noan coupler!
? Luphthalate 35m & ethyl acetate 1
A 5% aqueous gelatin solution containing 2.59% of dodecylbenzenesulfonate, I.
After adding to mQ, it was dispersed with a homogenizer, and the resulting dispersion was mixed with red-sensitive silver chlorobromide (M chloride 130 mol%).
Added to 1000m& of γf) emulsion and added N as a hardening agent.

N, N”,-triacryloylhexahydro-S
- 10 mQ of a 2% methanol solution of triazine was added, coated on polyethylene foot paper and dried to obtain a sample of a monochromatic color photographic material. This sample is designated as No. 41.

When preparing the emulsified dispersion liquid in the same manner as in Example 3, 10 samples each of the comparative compound (e) having the following structure and the exemplified compound of the present invention as shown in Table 4 were added to prepare 9 samples (No. ,
42-50) were created.

)+Toge(hi A ?rA (ρi−+,”p IT
FI F SQ-R7JRA-t”L Iy
, i-, Satsuma After exposing each of these 8 compounds to light, I11! A dye image obtained by processing exactly as in Example 3 was fitted with an ultraviolet cartridge filter (same as that used in Example 3); a 10 day fading test was carried out using a xenon fade meter. The results are shown in Table 1.

(The absorption maximum of the colored cyan dye in methanol solution is 6
It was 52 nm. ) As is clear from Table 4, the compound of the present invention has a greater photofading prevention effect than the Noan coloring dye.

Claims (1)

[Claims] An organic coloring substance that prevents the organic coloring substance from fading due to light by coexisting the organic coloring substance and at least one of the compounds represented by the following general formula [I]. How to prevent fading. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, M represents Co, Cu, Ni, Pd or Pt, and R_1 and R_2 each represent an alkyl group or an aryl group. X^n^- represents an n-valent organic or inorganic anion, and n represents an integer of 1 to 3. ]