JPH02196239A - Method for preventing photofading of organic coloring material - Google Patents

Abstract

PURPOSE:To improve stability to org. coloring materials and compds. expressed by the general formula I without degrading the hue and purity of dyestuffs or dyes by allowing the org. coloring materials and one kind of the above- mentioned compd. to coexist. CONSTITUTION:The photofading of the org. coloring materials is prevented and the stability thereof is improved without degrading the hue and purity of the dyestuffs or dyes by allowing the org. coloring materials and at least one kind of the compds. expressed by the general formula I to coexist. In the general formula I, R1 denotes a hydrogen atom, alkyl group, alkenyl group, alkinyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, phosphonyl group, carbamoyl group, sulfamoyl group, or oxycarbonyl group. R2 denotes a substituent, n denotes 0 to 3 integer, plural R1 to R3 may be respectively the same or different.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for preventing photofading of organic coloring substances.

[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 photofading 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,
-30゜nl in methanol solution inside the membrane! 1-800
refers to an organic substance that has at least one absorption maximum in nm.

Furthermore, in this specification, the term light refers to approximately 30 On
+++ means electromagnetic waves of approximately 800 nm or less, approximately 40 nm.
Ultraviolet light less than 0nm, about 400nl11 to about 700nm
visible light and infrared light from about 70 nm to about 800 nm.

There are many reports on methods for improving the light resistance 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 to produce visible It is also stated that the fastness to ultraviolet light is improved.

In the field of silver halide color photographic materials, the dye image obtained from the coupler is exposed to light for a long period of time, resulting in f-'
It is desirable that the color does not change or fade even when stored under high temperature and high humidity conditions.

However, it is known that the fastness of these dye images to mainly ultraviolet rays or visible rays is not at a satisfactory level, and the color easily changes and fades when irradiated with these actinic rays. In order to eliminate such drawbacks, conventionally, various couplers with low fading properties have been selected and used,
In order to protect the dye image from ultraviolet rays, methods have been proposed in which an ultraviolet absorber is used or a group imparting light resistance is introduced into the coupler.

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 noticeably brighter due to the coloring of the ultraviolet absorber itself. ．． <There were cases of contamination. 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, phenolic hydroxyl group or hydrolysis 1. A method using a dye image fading inhibitor having a group that produces a phenolic hydroxyl group is known, for example, Japanese Patent Publication No. 4L312
No. 56, No. 48-31625', No. 51-30462
No., JP-A-49-134326 and JP-A No. 49-1343
No. 27 contains phenol and bisphenols; US Pat. No. 3,069.262 contains pyrogallol, gallic acid and its esters; US Pat. No. 2,360.290 and US Pat. No. 4,015,990 contain α-41.・1 ferols and their acyl derivatives, Japanese Patent Publication No. 52-27534, Japanese Patent Application Laid-Open No. 52-14751, and U.S. Patent No. 2,735,
765-! - is a hydroquinone derivative, U.S. Patent 3,
No. 432.300, No. 3, No. 574, and No. 627 of 6
-Hydroxychromans, U.S. Patent 3,573.050
No. 1: ″ is a 5-hydroxychroman derivative and
No. 9-20977 has 6j3'-dihydroxy-2.
It has been proposed to use 2'-subirobichromans and the like. However, these compounds are 1. anti-fading and anti-tarnishing agents for pigments. Although some effects can be seen, it is 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, Po
lym, Sei,.

Polym, Chem, Ed.) Volume 12, Page 993
(1974), Journal of Polymer Science, Holimar Letters 1i (J, r'olym, Sci.
,, Polym, Lett, Ed,) + 13 volumes,
71 (1975), etc., and a method for stabilizing dyes against light using metal complexes is described in JP-A No. 5 (L87649 and Research Disclosure) No.
15162 (1976), these complexes do not have a large anti-fading effect and do not have high solubility in organic solvents, so they cannot exhibit an anti-fading effect. I can't add enough amount to make it. Furthermore, since these complexes themselves have a large coloring property, when added in large amounts, they have an adverse effect on 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 with the above method, it is still insufficient to reduce the leaf color of the complex itself, and organic coloring substances,
Especially when it comes to dyes, when L<<, it is not possible to remove the adverse effects on the hue and purity of the dye.

Furthermore, when these known metal complexes are applied to silver halide color photographic materials*4 (hereinafter referred to as color photographic materials), stains are likely to occur in uncolored areas of the developed color photographic materials. In particular, when developed color photographic materials are stored under conditions of high temperature and high humidity, the occurrence of contamination increases significantly.

[Purpose of the invention]

The object of the present invention is to provide a method for overall 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 invention is to form color photographic images without contaminating the uncolored parts of the color photographic material.
, t' to improve the light stability of color images.

[Structure of the invention]

The object of the present invention is to combine an organic coloring substance with the following general formula CI
) This is achieved by coexisting at least one of the compounds shown in (a).

General formula (I) where R1 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group,
It represents 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 R2 represents a substituent. n is O~
・Represents the integer 3.

Each of the plurality of R3s and R3s may be the same or different. Also, if R, O and R2 are in adjacent positions, R, 0 and R
3 may be bonded to each other to form a 5- to 7-membered ring.

Hereinafter, the present invention will be explained in more detail.

In the general formula CI), the alkyl group represented by Ro has 1 to 32 carbon atoms, the alkyl group and alkynyl group have 2 to 32 carbon atoms, and the cycloargyl group and cycloalkenyl group have 1 to 32 carbon atoms. Numbers 3 to 12
In particular, those having 5 to 7 atoms are preferable, and the alkyl group, alkenyl group and arginyl group may be linear or branched. Also,
These groups may have substituents. Specifically, methyl, ethyl, t-butyl, pentadecyl, l-hexylnonyl, 2-chloro-t-butyl, benzyl, 2.4-
Groups such as di-L-alumiphenoxymethyl, 1-ethoxytridecyl, allyl, isopropenyl, ethynyl, 2-propynyl, ncrobentyl, cyclohexyl, and cyclohexenyl are mentioned.

The aryl group represented by R3 is preferably a phenyl group or a naphthyl group, which may have a substituent.

A-isomers include phenyl, 4-nitrophenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 3
Examples include groups such as -hexadecyloxyphenyl and α-naphthyl.

The heterocyclic group represented by R1 is preferably a 5- to 7-membered one, and may be substituted or fused.

Specific examples include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R1 include acetyl group,
Alkylcarbonyl groups such as phenylacetyl group, dodecanoyl group, α-2,4-di-monoamylphenoxybutanoyl group, arylcarbonyl group such as benzoyl group, 3-pentadecyloxybenzoyl group, p-chlorobenzoyl group, etc. Can be mentioned.

Examples of the sulfonyl group represented by R include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, and an arylsulfonyl group such as a benzenesulfonyl group.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a pudylocdylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group,
Examples include arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by R 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)carbamoyl group, N-ethyl-N~
dodecylcarbamoyl group, Ni3- (2,4-di-L
-amylphenoxy)propyl)carbamoyl group, etc.

The sulfamoyl group represented by R may be substituted with an argyl group, an aryl group (preferably a phenyl group), etc., such as N-globylsulfamoyl group, N,N-diethylsulfamoyl M, N -(2-pentadecyloxyethyl)sulfamoyl group, N-ethylN-F7'silsulfamoyl group, N-7enylsulfamoyl group, and the like.

The oxycarbonyl group represented by R□ 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 ethoxymethoxycarbonyloxycarbonyl group, and the like. Further, the aryloxycarbonyl group may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoxycarbonylsifenoxycarbonyl group, and the like.

There are no particular restrictions on the substituent represented by R2, but R.
In addition to representing the same groups as halogen atoms and anilino, acylamino, sulfonamide, argyldis, arylthi, sulfinyl, cyano, alkoxy, aryloxy, heterocyclic oxy, heterocyclic thio, siloxy, acyloxy, carbamoyloxy, amino, alkylamino,
Examples include imide, ureido, sulfimoylamino, alkoxycarbonylamino, and aryloxycarbonylamino groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamido group represented by R include an argylsulfonylamino group and an arylsulfonylamino group.

The argyl component and aryl component in the alkylthio group and arylthio group represented by R are the above R.

Examples include alkyl groups and aryl groups represented by the following.

Sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; acyloxy groups include alkylcarbonyloxy groups,
Arylcarbonyloxy groups, etc.: Carbamoyloxy groups include argylcarbamoyloxy groups, argylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; sulfamoylamino groups include alkylsulfamoylamino groups. , arylsulfamoylamino group, etc. The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3.4,5.6-titrahydrobilanyl to 2-oxy group, l-phenyltetrazole -5-
Oxy group, etc.: The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-penzothiazolyldio group, 2,4-diphenoxy-1. 3.5 triazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-hebutadenesuccinimide group, phthalimide group, glutarium Imide group, etc.; spiro compound residues include spiro [3.31hebutan-■-yl, etc.; bridged hydrocarbon compound residues include bicyclo [2.

2.11 heptan-1-yl, tricyclo [3.3.
1.13.1] Decane-l-yl, 7,7-dimethylrubicyclo [2.2. ! ] In the present invention - Sailor [I
In the compound represented by ], %R1 is preferably a hydrogen atom, an alkyl group, or an alkenyl group, and m is preferably 0 or 1.

Furthermore, a symmetrical type is preferred.

Next, typical examples of the compounds represented by the above-mentioned -Funenin CI) used in the present invention (hereinafter referred to as compounds of the present invention) will be shown, but the present invention is limited thereto, and the synthesis of these compounds of the present invention is not limited to these. The methods are known, for example Magyar K'e
m Lapia, 4, 708 (1949), An
n.

Chem, 468.162-201 (1929
) etc. can be synthesized according to the method described in .

Synthesis examples of exemplary compounds of the present invention are shown below.

Synthesis example (synthesis of exemplified compound 1) 8 g of 3.4-dimethoxyphenylsulfonyl chloride
, heat 5 m12 of water and 7.5 g of zinc, and
*24 mQ of Lum was added and refluxed for 3 hours. After removing the mercaptan by steam distillation, toluene was added, washed with water, and the desired product 1. was obtained by column chromatography.
Obtained 0g. Melting point: 175-176°C (benzene recrystallized product).

Identification was performed by NMR% Mass spectrum and elemental analysis, and it was confirmed to be Exemplary Compound 1.

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, azomethine 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 800nm, preferably 400nm to 700n
has 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 (cyanine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoamine dyes, and It includes dyes belonging to chemical structural classes such as indophenol dyes, indigoid dyes, carbonium dyes, and formazan dyes.

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

Preferred dyes for use as organic colorants in the present invention include ani-laquinone, quinone imine, azo, methine, polymethine, indoamine, 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 those of the 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 removed during the coupling reaction (tin-off group). A 2-equivalent type may also be used.

In the present invention, preferred yellow dye image-forming couplers include benzoylace]anilide type and pivaloylacetanilide type couplers, and magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type, imidazopyrazole type couplers, There are pyrazolo pyrazole, pyrazolotetrazole, pyrazolinobenzimidazole, and indacilone couplers, and cyan dye image-forming couplers include phenol, naphthol, and
There are pyrazoloquinazolone 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.

Second, the yellow coupler Y-7 that can be used in the present invention is disclosed in, for example, West German Published Patent Application No. 2,
No. 057.941, West German Published Patent No. 2,163,812, Japanese Patent Application Publication No. 47-26133, Japanese Patent Publication No. 48-29432,
No. 50-65321, No. 51-3631, No. 51-
No. 50734, No. 5N-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, magenta turnip Q that can be used in the present invention C,H.

i0 C,H.

M-12 The magenta coupler of Jl et al.
No. 84,514, British time ¥'f 1.183.515, Special Publication No. 40-6031, No. 40-6035, No. 4
No. 4-15754, No. 45-40757, No. 46-1
No. 9032, JP-A-50-13041, JP-A No. 53-12
No. 9035, No. 51-37646, No. 55-6245
No. 4, US Patent No. 3゜725.067, British Patent No. 1, 2
No. 52.418, No. 1,334.515, JP-A-59
-171956, 59-162548, 60-
43659, 60-33552, Research Disclosure No. 24626 (1984), Japanese Patent Application No. 59-243007, 59-243008, 59-243009, 59-243012, 6
All of the compounds described in No. 0-70197, No. 60-70198, etc. can be synthesized according to the methods described therein.

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

Next, cyan couplers C and H can be used in the present invention.

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, 54-55380Ji3-1 56-6
No. 5134, No. 56-80045, No. 57-1555
No. 38, No. 57-204545, No. 58-98731
No. 59-31953, etc., and can be synthesized according to the methods described therein.

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.

Examples of other dyes that can be used as coloring compounds in the present invention include the following.

(F ■) (F H 2Hs C! H.

C,H.

11,01l to H's (F (F (F (F QCxH.

NHSO*CHs Further, other types of dyes preferably used in the present invention include U, S, No. 8351.673, U.S. Pat.
, 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), No. 1
Examples include dyes formed by oxidation of DRR compounds described in, for example, 3024 (1975).

Furthermore, other types of dyes that may be used in the present invention include:
For example, British Patent Nos. 840.731, 904.364, 932,272, 1,014,725-1, 1,038,331, 1,066.352, 1
, No. 097.064, JP-A-51-133021, I
JST900.029 (U, S, Defensive
Puh eat 1on), U.S. Patent 3, 227
Mention may be made of dyes released by the reaction of DI)R couplers with oxidized forms of color developing agents or dyes formed by the reaction of DI)R couplers with oxidized forms of color developing agents, such as those described in US Pat.

Other types of dyes preferably used in the present invention include Japanese Patent Publications No. 35-182, No. 18332, No. 48-
No. 32130, No. 4er 43950, No. 49-261
Examples include the dye developers described in No. 8 and the like.

Furthermore, other dyes used in the present invention and 1. Here, various dyes used in the silver dye bleaching method can be mentioned. Yellow dyes that can be used for this purpose include Direct Fast Yellow GC (c, 1.29000
), azo dyes such as Grisov J Nin (c, 1.24895), indigo golden yellow IGK (C, 1
゜59101), B (C,
1,61726), Arbosol Yellow GCA-CF
(C, 1, 67301), Indanthrene Yellow GF
(c, +, 68420), Mikasu 1/N Yellow GC (
C, 1,67300), indanthrene yellow 4
Benzoquinone dyes such as K (C, 1,68405): Examples include anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes. As a magenta dye, Sumilite Zapra Rubinol B (C, I, 2
9225), benzobryrif'yt'r 5-=, 7
Azo dyes such as B (c, r, 15080), indigosol brilliant pink IR (C, 1,733
61), Indigosol Violet 15R (C,1,
59321), indigocynyllet violet I
RRL (C, 1, 59316), Indanthrene Yellow 4 * Let RRK (C, 1, 67895), Indanthrene Brilliant Violet BBX (C 1, 6
335) Nato's indigoid dye; benzoquinone, An! - Soluble vat dyes made of cuquinone-based heteropolycyclic compounds and other vat dyes can be mentioned.

As a cyan dye, dye 1/kuto sky blue 6
Azo dyes such as B (c, +, 24410), Direct Brilliant Blue 2 B (C, J, 22610), Sumilight Subra Blue-G (C, 1, 34200), Sumilight Subra Turkey Blue c (e, 1.7
4180), Migasuren Brilliant Blue 4G (C,
I. Phthalocyanine dyes such as Indance Lenkey Sprue 5 G (C, 1,69845)
), indanstrable-GCD (C, 1,73066
), Indigosol 04G (C, 1,73046),
Anthrazole Green IB (C, 1, 59826)
etc. can be mentioned.

The compounds of the present invention are generally oil-soluble and are typically used in U.S. Pat.
, 801゜171, No. 2,272.191 and No. 2,304,940 by dissolving and dispersing in a high boiling point solvent, optionally using a low boiling point solvent. It is preferable to add it to a hydrophilic colloid solution.
At this time, if necessary, a coupler, a hydroquinone derivative, an ultraviolet absorber, a known dye image scarlet inhibitor, etc. may be used in combination 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 may be added to an organic acid amide at the same time as a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor. carbamates,
Esters, ketones, hydrocarbons, urea derivatives, etc., especially dibutyl phthalate, tricresyl phosphate, Jimmy octyl azelate, dibutyl sebaque-h,
t=lihexylphos 7ate, decalin, N,N-diethylcaprylamide, N,N-diethyllauramide, pentadecyl phenyl ether or fluoroparaffin, and optionally ethyl acetate, butyl acetate, propionic acid. butyl, cyclohexanol,
These high boiling point solvents and low boiling point solvents which are soluble in low boiling point solvents such as cyclohexane and tetrahydrofuran may be used alone or in combination. ) mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate; , a high-speed rotating mixer, a colloid mill, an ultrasonic dispersion device, or the like, and the resulting dispersion can be added to a hydrophilic colloid solution (for example, a silver halide emulsion) for use.

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 coupler-containing internal color photographic material or an external color photographic material containing a coupler in a developer.

The above-mentioned coupler-containing internal color photographic material is processed in a conventional manner 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, l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 3-methoxy-N,N -diethyl-p-7 22-diamine, etc. can be used.

When the method of the present invention is applied to photographic materials, various color photographic materials can be used, such as color positive film, color paper, color negative film, color reversal film, color diffusion transfer film unit, and silver dye bleaching material. .

〔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 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and sample 1 was obtained. (In the following examples, the amount added is shown as the amount per 100 cm of light-sensitive material.) First layer: "flr-sensitive silver halide emulsion layer" α-pivaloyl-α-(2°4
-dioxo-1-benzylimidazolidin-3-yl)
~6.8 mg of 2-chloro5-[γ-(2,4-di-t-amylphenoxy)butyramide 1 acetanilide
, 3.2 mg of blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) in terms of silver, and 3.5 m of dibutyl phthalate-1.
g and a layer containing 13.5 mg of gelatin.

2nd layer: middle layer 2.5-di-t-octylhydroquinone 0.5+n
g, a layer containing 0.5 mg of dibutyl phthalate and 9.0 mg of gelatin.

Third layer: Green-sensitive silver halide emulsion layer 3.5 mg of the magenta color (M-13), 2.5 mg of green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver, A layer containing 3.0 mg of dibutyl phthalate and 120...g of gelatin.

4th layer: intermediate layer UV absorber 2-(2-hydroxy-3,5-di-t)
-butylphenyl)benzotriazole 0.7+ng
, dibutylphta l/-) 6.0+ng, 2.5
- 0.5+++ g of di-t-octylhydroquinone and 12 g of gelatin. Layer containing Onig.

5th layer: Red-sensitive silver halide emulsion layer 4-2 mg of 2-[α-(2,4-di[-pentylphenoxy)butanamyl')-4,6-cyclo-5-ethylphenol] as a cyan coupler5Red-sensitive 3. Silver chlorobromide emulsion (containing 80 mol% silver bromide) is converted to silver.
0 mg, 3.5 mg of tricresyl phosphate and 11.5 o+g of gelatin.

No. 611j: Protective layer 8. Gelatin. Layer containing Onig.

In Sample 1, the compounds of the present invention were added to the third layer in the combinations shown in Table 1 at a ratio of 100 mol % to the coupler to create Multilayer Samples 2 to 12.

After exposing the sample obtained above through an optical wedge according to a conventional method,
Processed in the next step.

Processing process Processing temperature Processing time Color development
Bleach and fix at 33°C for 3 minutes and 30 seconds Water at 33°C for 1 minute and 30 seconds
Washing 33°C3 revolution Drying 50-80°C 2 minutes The components of the treatment solution are as follows.

Color developer Benzyl alcohol 12.0mQ diethylene glycol 10.0mR Potassium carbonate 25.0g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-ethyl-N-β-methanesulfonamidoethyl-3- Methyl-4-aminoaniline sulfate 4.5g Add water to make IQ, and adjust to pH 10.2 with sodium hydroxide.
Adjust to.

Bleach-fix solution Ammonium dioate 120.0g Sodium metabisulfite 15.0g Anhydrous sodium sulfite 3. OgEDTA ferric ammonium salt 65.0g Add water to make 2 and adjust pH to 6.7-6.81.

The concentration of sample 1-12 treated above was measured using a densitometer (model KD-7R manufactured by Konica Corporation) under the following conditions.

Each of the above-mentioned processed samples was exposed to a xenon fade meter for 16 days to examine the light fastness of the dye image.

Comparative compound 1 (compound described in JP-A-54-48538) Comparative compound 2 (compound described in JP-B-45-14034) Comparative compound 3 (compound described in U.S. Pat. No. 3,573,050) Comparative compound 4 CH3 CH .

From the results in Table 1, the use of the compound of the present invention was effective in stabilizing magenta dye images formed from magenta couplers, and Y stain in unexposed areas was also improved.

Example 2 A silver chlorobromide emulsion containing 99.5 mol % of silver chloride was used in place of each silver halide emulsion used in Example 1, and the magenta coupler and dye image stabilizer in the third layer are shown in Table 2. A sample similar to Sample 1 of Example 1 except that it was changed as follows (Sample 13
-28) were created.

Samples 13 to 28 were subjected to photoexposure according to a conventional method and then subjected to the following treatments.

Processing process Processing temperature Processing time Color development 34.7±0.3°0 45 seconds Bleach fixing 34.7±0.5°0 45 seconds Stabilization 3
Dry at 0-34℃ for 90 seconds Color developer Pure water at 60-80℃ for 60 seconds
800+n12 triethanolamine
8g N,N-diethylhydroxylamine potassium chloride N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate sodium tetrapolyphosphate Potassium carbonate Potassium sulfite Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) Add pure water to bring the total volume to 1Q.

bleach-fix solution Ferric ethylenediaminetetraacetic acid ammonium dihydrate Ethylenediaminetetraacetic acid Ammonium thiosulfate (70% solution) Sub-mM ammonium (40% solution) Add water to bring the total volume to 1Q, and make potassium carbonate. Adjust the pH to 5.7 with glacial acetic acid.

Adjust to pH 10.2g g g g 0g 0.2g g 0g g 00m12 27.5Q Rum or stabilized□ 5-chloro-2-methyl-4-isothiazolin-3-one 1g1-hydroxyethylidene-1,1 diphosphonic acid Add 2g of water to make 1Q, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.
Adjust to.

The light resistance of each sample after treatment was evaluated in the same manner as in Example 1.

When the dye image stabilizer of the present invention was added to the yellow coupler and cyan coupler of the present invention in the same manner as the magenta coupler of Table Example 2, good light fastness of the color image was exhibited. In addition, good color images were obtained.

〔Effect of the invention〕

By using the dye image stabilizer of the present invention as a stabilizer for a dye capable of forming an image, a photographic image obtained from a silver halide photographic light-sensitive material has an excellent fading prevention effect. The Y-stin has also been improved.

Claims (1)

[Scope of Claims] A method for preventing photofading of an organic coloring substance, which comprises coexisting the organic coloring substance and at least one compound represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. , sulfonyl group,
It represents a phosphonyl group, a carbamoyl group, a sulfamoyl group, or an oxycarbonyl group, and R_2 represents a substituent. n
represents an integer from 0 to 3. Each of the plurality of R_1 and R_2 may be the same or different. Also, R_1O and R_2
When R_1O and R_2 are in adjacent positions, R_1O and R_2 may be bonded to each other to form a 5- to 7-membered ring. ]