JPS63256951A - Method for preventing light discoloration of organic coloring substance - Google Patents

Abstract

PURPOSE:To prevent the discoloration of an organic coloring substance against a light by incorporating the org. coloring substance together with at least one kind of a specified compd. in a color photographic sensitive material. CONSTITUTION:Said material contains the org. coloring substance together with at least one kind of the compd. shown by formula I. In formula I, R<1> and R<2> are each hydrogen atom. or alkyl group, etc., R<3> is a substituent group, (n) is an integer of 0-6, X is oxygen or sulfur atom., Z1 and Z2 are each 1-3C alkylene group. Thus, the decoloration or discoloration of the org. coloring substance, especially, a color matter and a dye, etc., used in the color photographic sensitive material caused by a light is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for preventing photofading of organic coloring substances, and more particularly to a method for preventing photofading of inks, dyes, color photographs, and the like.

[Background of the invention]

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

The present invention aims to prevent photofading of such organic coloring substances,
It is used with great advantage.

The organic coloring substance used in the present invention refers to a substance that appears colored to the human eye under sunlight,
Generally 300nm to 800nm in methanol solution
means an organic substance that has at least one absorption maximum in .

Furthermore, in this specification, the term light refers to approximately 300n
111 to about 800 nm or less, ultraviolet light less than about 400nI11, about 400nm to about 700 nm
visible light of nm and about 700 nm to about 800 nm+++
Includes infrared rays.

There are many reports on methods for improving the light fastness of organic coloring substances, such as pigments or dyes. For example, U.S. Pat. No. 3,432,300 discloses that organic compounds used in color photography, such as indophenol, indoaniline, azo and azomethine dyes, are mixed with phenolic type compounds having fused heterocyclic ring systems.
It is stated that the fastness to visible and ultraviolet light is improved.

In the field of silver halide color photographic materials, dye images obtained from couplers are exposed to light for long periods of time,
It is desirable that the color does not change or fade even when stored under high temperature and high humidity conditions.

However, the fastness of these dye images to mainly ultraviolet rays or visible light is not satisfactory, and it is known that they easily change color and fade when irradiated with these actinic rays. In order to eliminate such drawbacks, conventionally,
Methods have been proposed such as selecting and using various couplers with low fading properties, using ultraviolet absorbers to protect dye images from ultraviolet rays, and introducing groups that impart light resistance into couplers. ing.

However, in order to provide satisfactory lightfastness to a dye image using, for example, an ultraviolet absorber, a relatively large amount of ultraviolet absorber is required, and in this case, the dye image becomes uncolored due to the coloration of the ultraviolet absorber itself. Sometimes it got contaminated. Further, even if an ultraviolet absorber is used, it does not show any effect in preventing fading of a dye image due to visible light, and there is a limit to the improvement in light resistance by an ultraviolet absorber. Furthermore, methods using dye image fading inhibitors having a 7-ethyl hydroxyl group or a group that can be hydrolyzed to produce a phenolic hydroxyl group are known.
No. 1625, No. 51-30462, Japanese Unexamined Patent Publication No. 49-13
No. 4326 and No. 49-134327 contain 7 e/-
and bisphenols, U.S. Pat. No. 3,069,26
No. 2 includes pyrogallol, gallic acid and its esters, U.S. Pat. Nos. 2,360,290 and 4,015,
No. 990 describes α-tocopherols and their acyl derivatives, JP-B No. 52-27534, JP-A No. 52-147.
51 and U.S. Pat. Nos. 2'735 and 765, hydroquinone derivatives;
No. 3,574,627 describes 6-hydroxychromans, U.S. Pat. - It has been proposed to use subirobichromans 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, it is disadvantageous because it has a large effect on the hue of the colored substance. In addition, the use of metal complexes to prevent photodegradation of polymers has been reported in the Journal of Polymer Science, edited by Polymer Chemistry (J, Pol.
ym, Sci, rPolyIIl, CI+eLI1.
Ed, ) vol. 12, p. 993 (1974), Journal of Polymer Science, edited by Polymer Letters.
(J, Polym, Sci, Polym, Lett
, Ed, )* Vol. 13, p. 71 (1975), etc., and methods for stabilizing dyes against light using metal complexes are described in JP-A-50-87649 and Research Disclosure.
Closure) No. 15162 (1976), these complexes do not have a great anti-fading effect and are not highly soluble in organic solvents; Unable to add quantity. Furthermore, since these complexes themselves have a strong coloring property, when added in large amounts, they adversely affect the hue and purity of organic coloring substances, especially pigments.

Furthermore, methods for photostabilizing dyes using various metal complexes are disclosed in JP-A-54-62826, JP-A-54-62987, and JP-A-54.
-65185, 54-69580, 54-72
No. 780, No. 54-82384, No. 54-82385
No. 54-82386, No. 54-136581,
No. 54-136582, No. 55-12129, No. 5
No. 5-152750, No. 56-168652, No. 56
-167138, 57-161744, Special Publication No. 5
No. 7-19770, etc.

However, even the above methods are still insufficient to reduce the coloration of the complex itself, and organic coloring substances,
In particular, the negative influence on the hue and purity of the pigment or dye cannot be eliminated.

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 uncolored areas of the developed color photographic materials. 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 or dyes, without deteriorating their hue and purity.

Yet another object of the present invention is to provide a method for improving the light stability of color images forming color photographic images without contaminating the uncolored areas of the color photographic material.

[Structure of the invention]

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

General formula (1) In the formula, R1 and R2 are each a hydrogen atom, an alkyl group,
It represents an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, or an oxycarbonyl group, and R3 represents a substituent. n represents an integer from 0 to 6, and when n is 2 or more,
A plurality of R3s may be the same or different. X represents an oxygen atom or a sulfur atom, and Z and Z2 each represent a fullkylene group having 1 to 3 carbon atoms. However, ZI and Z
The total number of carbon atoms in the alkylene group represented by 2 is 3 to 5
It is.

The present invention will be explained in more detail below.

In the above general formula (1), the alkyl group represented by R' and R2 has 1 to 32 carbon atoms, the alkenyl group and alkynyl group have 2 to 32 carbon atoms,
The cycloalkyl group and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched. Moreover, these groups may have a substituent. Specifically, methyl, ethyl, t-butyl, pentadecyl, 1-hexylnonyl, 2-chloro-t-butyl, benzyl, 2-4-di-t-alumiphenoxymethyl, 1-
Examples include groups such as ethoxytridecyl, allyl, impropenyl, ethynyl, 2-propynyl, cyclopentyl, cyclohexyl, and cyclohexenyl.

The aryl group represented by R1 and R2 is preferably a phenyl group or a naphthyl group, which may have a substituent. Specifically, phenyl, 4-nitro-7enyl, 4-t-butylphenyl, 2,4-di-t-7mylphenyl, 3-
Examples include groups such as hexadecyloxyphenyl and a-su7tyl.

The heterocyclic group represented by R1 and R2 is preferably a 5- to 7-shell heterocyclic group, which may be substituted or fused. Specifically, 2-7lyl group, 2-chenyl group,
Examples include 2-pyrimidinyl group and 2-benzothiazolyl group.

Examples of the acyl group represented by R1 and R2 include acetyl group, phenylacetyl group, dodecanoyl group, α-
Examples include furkylcarbonyl groups such as 2,4-sheet t-amylphenoxybutanoyl group, arylcarbonyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and 1)-chlorobenzoyl group.

Examples of the sulfonyl group represented by R1 and R2 include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-)luenesulfonyl group.

The phosphonyl group represented by R1 and R2 includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. and arylphosphonyl groups.

The carbamoyl group represented by R' and R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, N,N
-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoy)kM, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-not-
7mil7eth/xy)propyl)carbamoyl group and the like.

The sulfamoyl group represented by R' and R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, an N-propylsulfamoyl group,
, N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sul77moyl group, N-ethyl-N
-dodecylsulfamoyl group, N-phenylsulfamoyl group and the like.

The oxycarbonyl group represented by R1 and R2 is preferably an alkoxycarbonyl group or an aryloxycarbonyl group. The alkoxycarbonyl group may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group, etc. . Further, the aryloxycarbonyl group may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, an I-pentadecyloxyphenoxycarbonyl group, and the like.

R1 and R2 may be bonded to each other to form 5 to 7 shell rings.

There are no particular restrictions on the substituent represented by R3, but R1
In addition to representing the same groups as R2, halogen atoms and anilino, acylamino, sulfonamide, alkylthio, arylthio, sulfinyl, cyano, alkoxy, aryloxy, heterocyclic oxy, heterocyclic thio, siloxy, acyloxy, carbamoyloxy, ami/ , alkylamino, imide, ureido, sul7-amoylamino, alkoxycarbonylamino, and aryloxycarbonylamino groups, as well as spiro compound residues, endowed hydrocarbon compound residues, and the like.

Examples of the acylamino group represented by R3 include 7 alkylcarbonylamide groups and 7 arylcarbonylamide groups.

Examples of the sulfonamide group represented by R3 include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R3 include the alkyl group and aryl group represented by R1 and R2 above.

Sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; acyloxy groups include alkylcarbonyloxy groups,
Arylcarbonyloxy group ring; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; 7 amoylami 7 groups, etc. The heterocyclic oxy group preferably has 5 to 7 heterocyclic rings, such as 3,4,5.6-tetrahydropyranyl-2-oxy group, 1-7 enyltetrazole-5 −
Oxy group, etc.; As the polycyclic thio group, a 5- to 7-shell heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5- ) Riazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; Imide groups include succinimide group, 3-heptadecylsuccinimide group, 7-talimide group, glutarium Imide group, etc.; Spiro compound residues include spiro [3,3]hebutan-1-yl, etc.; endowed hydrocarbon compound residues include bicyclo [2゜2.
11 Hebutan-1-yl, tricyclo [3°3.1.
13.7]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

In general formula (1), when two R'' are located at adjacent positions, two R3 may be bonded to each other to form a 5 to 7 shell ring.Also, alkylene represented by Zl and Z2 The present invention also includes cases where the carbon atoms constituting the group are spiro atoms.

Next, typical examples of the nitrogen-containing heterocyclic anti-fading agent represented by the general formula [I] used in the present invention (hereinafter referred to as the compound of the present invention) will be shown, but the present invention is not limited thereto.

De-゛-1hi- A-26A-27 A-28 A-29A-30 Synthesis methods for these compounds of the present invention are known, for example, Chimia butylotiflicheskii soedine (Kl+
im, Geterotsikl, 5oedin, ),
1971, 7(3).

pp. 301-308, same magazine, 1978, (10),
pp. 1427-1428, same magazine, 1978, (11),
Pages 1569-1570, Tournal Organiceskoy Kimmy (Zh, Org, Kh 1I11.)
t 1971.

7(1), pp. 16-25, Borland Patent No. 97062, Borland Patent No. 97064, etc.

The amount of the compound of the present invention used is preferably 5 to 400 mol%, more preferably 10 to 300 mol%, based on the organic coloring substance used in the invention.

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 were mixed with 300n in methanol solution.
m to 800 nm, preferably 400 n + n to 7
It has at least one absorption maximum at 00 nTtl.

Among these dyes, the dyes preferably used in the present invention include quinone imine dyes (azine dyes, oxanone dyes, thiazine dyes, etc.), methine and polymethine dyes (cyanine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, and indoamine dyes. and dyes belonging to chemical structural categories such as indigo dyes, indigoid 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,
These include polymethine, indoamine, indophenol and formazan dyes. The dyes most preferably used in the present invention are methine and polymethine dyes and indoamine and indoenol 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, or an amide group.

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.
The so-called 4-equivalent type as described in No. 3,458,315, or the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction (split-off group). It may also be a 2-equivalent type.

In the present invention, preferred yellow dye image-forming couplers include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type, imigzovirazole type, Pyrazolo pyrazole series,
There are pyrazolotetrazole-based, birazolinobenzimigzole-based, and ingzolone-based couplers, and cyan dye image-forming couplers include phenol-based, naphthol-based, and pyrazoloquinazolone-based 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, yellow couplers that can be used in the present invention l rθ =23- O l L ('1) These yellow couplers are described in, for example, West German Published Patent Application No. 2.
05), No. 941, West German Published Patent Application No. 2,163,812, Japanese Patent Application Publication No. 47-26133, Japanese Patent Application Publication No. 48-29432,
No. 50-65321, No. 51-3631, No. 51-
No. 50734, No. 51-102636, No. 48-66
No. 835, No. 48-94432, No. 49-1229, No. 49-10736, Special Publication No. 51-33410,
It includes the compounds described in No. 52-25733 and the like, and can be synthesized according to the methods described therein.

Next, what is the remaining magenta turnip that is lighter because it is used in the present invention? CI J CI 2H5 Hs 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. 40-8035, British Patent No. 44-15
No. 754, No. 45-40757, No. 46-19032
No., JP-A-50-13041, JP-A No. 53-129035
No. 51-37646, No. 55-62454, U.S. Patent No. 3.

725,067, British Patent No. 1,252,418, British Patent No. 1,334,515, Japanese Patent Application Publication No. 171956/1983,
No. 59-162548, No. 60-43659, No. 6
No. 0-33552, Research Disclosure No.
, 24626 (1984), patent application No. 59-24300
No. 7, No. 59-243008, No. 59-243009
No. 59-243012, No. 60-70197,
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.

Below□'Bottom□・Brown White C-1 Ct' I C&H 2H5 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. It can be synthesized according to

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 developer.

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

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

[Example developer]

D-I D-2 D-3D-4 D-5D-6 Examples of other dyes that can be used as coloring compounds in the present invention include the following.

H C H3 NH502CH9 Further, other types of dyes preferably used in the present invention include υ, S, B551,673, U.S. Pat. No. 3,932
, No. 381, No. 3,928,312, No. 3,931,
No. 144, No. 3,954,476, No. 3,929,7
No. 60, No. 3,942,987, No. 3,932゜38
No. 0, No. 4,013,635, No. 4,013,633
No., JP-A-51-113624, JP-A No. 51-10992
No. 8, No. 51-104343, No. 52-4819,
No. 53-149328, Research Disclosure +
-No. 15157 (1976), same magazine No. 13
Examples include dyes formed by oxidation of DRR compounds described in, for example, 024 (1975).

Furthermore, other types of dyes that may be used in the present invention include:
For example, British Patent No. 840,731, British Patent No. 904,364, British Patent No. 932,272, British Patent No. 1,014,725, British Patent No. 1
, No. 038,331, No. 1,066.352, No. 1,
No. 097,064, JP-A-51-133021, tl
sT900,029 (U, S, Defensive
Publication), U.S. Patent 3,227,55
A dye released by the reaction of a light DDR coupler with an oxidized product of a color developing agent as described in No. 0, or
Mention may be made of dyes formed by reaction with oxidants of color developing agents.

Other types of dyes preferably used in the present invention include Japanese Patent Publications No. 35-182, No. 18332, No. 48-
No. 32130, No. 46-43950, No. 49-261
Examples include the dye developers described in No. 8 and the like.

Furthermore, other dyes used in the present invention include various dyes used in silver dye bleaching methods. Yellow dyes that can be used for this purpose include Direct 7T Yellow and C (C).

1.29000), glisophenin (C, 1,2489
5) Azo dyes such as Indigo Golden Yellow IG
K (C, I.

59101), Incicosol Yellow 2 GB (
C, I, 81726), Arbosol Yellow GC^-
Benzoquinone dyes such as CF (C01,67301), Genthrene Yellow CF (C,I, 68420), Mikathrene Yellow GC (C01,87300), and Genthrene Yellow 4 GK (C,1,68405); anthraquinone dyes , polycyclic soluble vat dyes, and other vat dyes.

As a magenta dye, Sumilite Sabralbinol B
(C0I, 29225), 7zo dyes such as PenzoBrilliant Galanin B (C,I, 15080), Indigosol Brilliant Pink JR (C, 1,73361
), Indigosol Violet 15R (C,!, 59
321), Indigosol Red Violet IRRL
(C,1,59:1116), Indanthrene Red Violet RRK (C,L67895), Mikethrene Brilliant Violet BBK (C,I.

6335); soluble vat dyes made of benzoquinone-based and anthraquinone-based heteropolycyclic compounds; and other vat dyes.

As a cyan dye, Direct Sky Blue 6 B
(C, 1, 24410>, Direct Brilliant Blue 28 (C01, 22810), Sumilight Subrable-C (C.

1.34200), Sumilite Sabra Turkey Blue G (C01,74180), Mikethrene Brilliant Blue 4 (C,1,74140)
7 talocyanine dyes, such as Indanslen Turkey'
Souffle 5G (C, I, 69845), Indan Stremblu-GCD (C, 1° 73066), Indigosol 04G (C, I, 73046), Anthrazole Green IB (C, 1, 59826), etc. Can be done.

The compounds of the present invention are generally oil-soluble and are typically used in U.S. Pat.
, 801゜171, 2,272,191 and 2,304,940 by dissolving and dispersing it in a high boiling point solvent, using a low boiling point solvent as necessary. It is preferable to add it to a colloidal solution, and if necessary, a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor may be used in combination with this without any problem. At this time, there is no problem even if two or more of the compounds of the present invention are used as a mixture. To further explain in detail the method of adding the compounds of the present invention, one or more of the compounds are added with an organic acid, if necessary, a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor. Amides, carbamates, esters, ketones, hydrocarbons and urea derivatives, especially dibutyl heptatarate, tricresyl phosphate, di-
If necessary, add to a high boiling point solvent such as octyl azelate, dibutyl sebacate, trihexyl phosphate, decalin, N,N-noethyl brylamide, N,N-diethyl laurylamide, pentadecyl phenyl ether or fluoroparaffin. These high boiling point solvents and low boiling point solvents which are soluble in low boiling point solvents such as ethyl acetate, butyl acetate, butyl propionate, cyclohexyl, cyclohexane and tetrahydrofuran may be used alone or in combination. ) Hydrophilic binders such as gelatin containing anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. It can be used by mixing it with an aqueous solution and emulsifying and dispersing it using a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc., and adding the resulting dispersion to a hydrophilic colloid solution (for example, a silver halide emulsion).

Both the colorant and the compounds of this invention can be present in any or several of the parent colloid layers in 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 coloring 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 have a molecular form that allows them to be retained in the mordant layer of the image receptor so that they do not migrate away from the dye to be stabilized. must be maintained.

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, Silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof.

These silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Further, chemical sensitization can be carried out by a conventional method in the field of photography.

Silver halide emulsions are known as anti-capri agents or stabilizers in the photographic industry for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or to maintain stable photographic performance. Compounds that are present can be added.

In addition, various photographic additives such as hardeners, plasticizers, optical brighteners, antistatic agents, and coating aids may be used alone or in combination.
More than one species can be added and used in combination.

The color photographic material to which the present invention is applied may be a turnip-2-containing internal color photographic material or an external color photographic material containing a coupler in a developer.

The above-mentioned turnip 2-containing internal color photographic material is processed in accordance with conventional methods to obtain 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 carried out in one bath. Color development is usually carried out in an alkaline solution containing an aromatic primary amine developing agent. Preferred specific examples of these aromatic primary amine developing agents are described above as exemplified developers D-1 to D-6.

When the color photographic material to which the method of the invention is applied is a film unit for color diffusion transfer, processing of the photographic material takes place automatically within the light-sensitive material. In this case, the developing agent is contained in a rupturable container. As the developing agent, in addition to the compounds represented by D-1 to D-6 above,
N-methylaminophenol, 1-phenyl-3-birasoliton, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 3-methoxy-N,N -diethyl-p-phenylenediamine, etc. can be used.

When applying the method of the present invention to photographic light-sensitive materials, various types 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, color light-sensitive material for heat development, etc. Examples include color photographic materials.

〔Example〕

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

Example 1 0.5 g of magenta dye having the following structure (absorption maximum 583 r + m in methanol solution) was dissolved in 4 ml of dibutyl 7-thalerate and 8 v 11 of ethyl acetate, and this solution was mixed with 2 ml of a 0.5% aqueous solution of sodium dodecylbenzenesulfonate. It was emulsified and dispersed in 10v11 of a 10% gelatin solution.

Next, this emulsified dispersion was added to a 5% gelatin solution at 30++N
A sample was obtained by mixing the mixture with the following materials and coating it on a paper support laminated on both sides with polyethylene. This sample is No.

Set to 1.

When preparing the above emulsified dispersion in a similar manner, 3% of the comparative compounds represented by the following structural formulas (a) and (b) were each used.
Samples No. 2 and No. 013 were prepared by adding 50 zg and coating in the same manner as the above sample No. 1.

Further, when preparing the emulsified dispersion liquid by the method of the above sample No. 1, as shown in Table 1, 350 ipg 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-55-12129...Same as above Each of the above samples was exposed to a xenon fade meter for 200 hours to determine the light resistance of the dye image. I looked into it. The results are shown in Table 1. However, the light resistance of the dye image was determined based on the dye residual rate.

Table 1 As is clear from Table 1, the samples using the anti-fading agent of the present invention (Nos. 4 to 15) had better anti-fading properties than the samples using known metal complexes (Nos. 2 and 3). It was effective, and almost no blackish-brown discoloration was observed.

Example 2 In Example 1, the magenta dye was used as a magenta dye having the following structure (maximum absorption 536nw in methanol solution).
15 types of samples (No. 16 to 30) were prepared in the same manner as in Example 1 except that the sample was changed to .

The obtained sample was exposed to a xenon fade meter for 150 hours to examine the light resistance of the dye image. The results are shown in Table 2.

(Magenta dye) Table 2 Table 2 also shows that the sample using the anti-fading agent of the present invention has a better photofading prevention effect than the sample using the known metal complex. It can be seen that it has In addition, the sample according to the present invention showed almost no blackish-brown discoloration and maintained a favorable hue even after the light fastness test.

Example 3 25 g of exemplified coupler (M-8) as magenta coupler
A solution of tricresylphos 7A) 25+++1 and ethyl acetate 100+o1 was added to 500ml of a 5% gelatin aqueous solution containing 2.5g of sodium dodecylbenzenesulfonate, and then dispersed with a homogenizer.
The obtained dispersion was added to a green photosensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion 1, 0OOIn1, and N,N',N'-triacryloylhexahydro-8 was added as a hardening agent.
- 10 vol of a 2% methanol solution of triazine was added, coated on polyethylene coated paper and dried to obtain a sample of a monochromatic color photographic material. This sample is designated as No. 31.

When preparing the above emulsified dispersion in the same manner, 25 g of comparative compounds (C) and (d) each having the following structures were added and applied in the same manner to prepare samples No. 32 and No.

33 was created.

Furthermore, as shown in Table 3, exemplified compounds of the present invention were each added to 20. 7 types of samples (NO134
-40) were created.

Comparative compound (c)... Compound described in JP-A No. 54-48538 Comparative compound (d)... Compound described in JP-A-56-159644 After each of these samples was exposed, the following treatment was performed. Processed with liquid and processing steps.

[Developer]

Benzyl alcohol 12.0 l Sodium hexametaphosphate 2.5 g Anhydrous sodium sulfite 1.9 fl Sodium bromide 1.4 g Potassium bromide
0.5g sodium carbonate
30.0gN-ethyl-N-β-notanesulfonamidoethyl-4-7minoaniline sulfate 5
．． Add 0 g of water to bring the total volume to 11, and adjust the pH to 0.30 using sodium hydroxide.

[Bleach-fix solution]

Ethylenecyaminetetraacetic acid iron ammonium 61, Og Ethylenediaminetetraacetic acid diammonium 5.0g Ammonium thiosulfate 124.5g Ammonium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g Add water to 1
1 and adjust the pH to 6.5 using aqueous ammonia.

[Processing process] (30℃) Processing time Development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Washing with water
Dry for 3 minutes. Apply a UV cut filter, Kodak Wratten Filter N, to each sample with a dye image formed in this way.
A fading test was conducted for 150 hours using a xenon 7ade meter with 2A attached. The results are shown in Table 3.

The degree of fading was indicated by the change in density of the 1.0 density portion before the fading test.

Table 3 (The maximum absorption of the colored magenta dye in a methanol solution was 536 nm.) As is clear from the results in Table 3, the anti-fading agent of the present invention has a superior light resistance to conventional organic anti-fading agents. It has an anti-fading effect.

Example 4 As a cyan coupler, 35 g of the exemplary coupler (C-6) was mixed with dioctyl 7 clay) 35+nZ and ethyl acetate 100 g.
Add the solution dissolved in a+1 to 500ml of a 5% gelatin aqueous solution containing 2.5g of sodium dodecylbenzenesulfonate.
After adding to 1, it was dispersed with a homogenizer, and the resulting dispersion was added to red-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion 1, OOO+o1, and N was added as a hardening agent.
A 2% methanol solution 10I111 of N',N'-)lyacryloylhexahydro-5-)lyazine was added, coated on polyethylene coated 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, 12 g of each of the comparative compound (e) having the following structure and the exemplary compound of the present invention as shown in Table 4 were added to prepare 9 types of samples (No.
42-50) were created.

Comparative compound (e): Compound described in JP-A No. 59-87456 After exposing each of these samples, the dye image obtained by processing in exactly the same manner as in Example 3 was filtered with an ultraviolet cut filter (
A fading test was carried out for 250 hours using a xenon fade meter using the same material as used in Example 3. The results are shown in Table 4.

Table 4 (Maximum absorption of colored cyan dye in methanol solution is 6
It was 520 koma. ) As is clear from Table 4, the anti-fading agent of the present invention also has a large effect of preventing photofading of cyan coloring dyes.

Example 5 Next, an example in which the present invention is applied to a heat-developable photosensitive material will be shown.

Preparation of heat-developable photosensitive elements> The heat-developable photosensitive elements shown in Table 5 were prepared using the following materials.

Gelatin: Photographic lime-processed gelatin and phenylcarbamoylated gelatin (manufactured by Rousslow, type 17819)
PC) mixed at a ratio of 2:1 (weight ratio).

PvP...Polyvinylpyrrolidone (K-30) solid heat solvent...p-butoxybenzamide liquid heat solvent...
1,2.4-butanetriol reducing agent: A mixture of the following reducing agents A and B at a 7:3 molar ratio.

Below 1F meeting (A) (B) Organic silver salt...5-methylbenzotriazole silver photosensitive silver halide...Same as that described in the examples of Japanese Patent Application No. 61-254257. Using.

Yellow dye-providing substance (Y-CPM) Cho ■ x:y=80:20 (weight ratio) More than 1,000 hours Magenta dye donor (M-CPH) C.I.

Cyan dye-providing substance (C-CPN) CHl H
x is a silver equivalent value) <Preparation of heat-developable image-receiving element> Photographic baryta paper (thickness 170 μm 1 weight 190 g/l)
l2) Apply the following image-receiving layer coating solution to a wet film thickness of 137.2
A heat-developable image-receiving element was prepared by coating in μl and drying (Sample No. 51).

(Image-receiving layer coating liquid) Polyvinyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., n = 1,100) 21
, Og Tetrahydro 7 Run 190 Summer l When preparing the above image-receiving layer coating solution in the same manner, as shown in Table 6, 0.8 g each of the comparative compound, ultraviolet absorber, and exemplary compound of the present invention (combined) 0.4fI for each
In addition, nine types of samples (Nos. 52 to 60) were prepared by coating in the same manner as Sample No. 51 above.

The heat-developable photosensitive element was exposed to 4,000 cm s of tungsten light through a step wedge and a green filter, the coated surfaces of which were overlapped with the heat-developable image-receiving element, and preheated at 100° C. for 4 seconds.
Pressure heating (thermal development) was performed at 0° C. for 90 seconds. The preheating and compression heating are described in Japanese Patent Application Laid-Open No. 61-153651.
A thermal development apparatus shown in Figure 2 of the issue was used.

After the heating was completed, the image receiving element was quickly peeled off from the photosensitive element, and a magenta image was obtained on the surface of the image receiving element. The photographic properties and light stability of this color image were investigated. The results are also shown in Table 6.

(Evaluation of Photographic Characteristics) The maximum reflection density and minimum reflection density of the magenta image were measured using a Sakura densitometer PD-65 (manufactured by Konishiroku Photo Industry) using green light.

(Evaluation of edge resistance stability) A sample with a magenta image was irradiated with light for 5 and 10 days using a xenon fade meter (Suga Test Iso WE-6X-HC), and the dye concentration residual rate (%) was examined. .

,″X, Nari below m----'/ Table 6 This ultraviolet absorber (UV-1) This comparative compound (e) is the same as that used in Example 3.

Table 6 shows that the anti-fading agent of the present invention exhibits an excellent anti-fading effect without impairing photographic properties even when used in heat-developable photosensitive materials. Further, by using the anti-fading agent of the present invention and an ultraviolet absorber together, the anti-fading effect is further improved.

〔Effect of the invention〕

By allowing the photofading inhibitor according to the present invention to exist with an organic coloring substance, it is possible to significantly reduce the light-induced discoloration and fading of the organic coloring substance, particularly pigments, dyes, etc. used in color photographic materials.

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 compound represented by the following general formula [I]. How to prevent fading. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. group, heterocyclic group, acyl group, sulfonyl group, phosphonyl group, carbamoyl group, sulfamoyl group or oxycarbonyl group, R^
3 represents a substituent. n represents an integer from 0 to 6, and when n is 2 or more, the plurality of R^3s may be the same or different. X represents an oxygen atom or a sulfur atom, and Z_1 and Z_2 each represent an alkylene group having 1 to 3 carbon atoms. However, the total number of carbon atoms in the alkylene groups represented by Z_1 and Z_2 is 3 to 5. ]