JPS63208837A - Method for preventing fading of organic coloring material to light - Google Patents

Abstract

PURPOSE:To prevent fading of an org. coloring material to light by allowing the org. coloring material and at least one kind of specific compd. to co-exist. CONSTITUTION:The org. coloring material and at least one kind of the compd. expressed by the formula are made to co-exist. In the formula, R<1> denotes a hydrogen atom., alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkinyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, phosphonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group or aryl oxycarbonyl group; R<2> denotes a substituent. (n) Denotes 0-6 integers; X denotes an oxygen atom or sulfur atom.; Y denotes a methylene group or ethylene group. The decoloration and fading of the org. coloring material, more particularly, coloring matter, dyes, etc., to be used for a color photographic sensitive material by light are thereby considerably decreased.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for preventing photofading of organic colored 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, a-fiber dyes, color photography, and the like.

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

8! used in the present invention! Colored substances refer to substances that appear colored to the human eye under sunlight, and generally have a diameter of 300 nm to 800 nm in methanol solution.
means an organic substance having at least one absorption maximum in m.

Furthermore, in this specification, the term light refers to approximately 300n
It means electromagnetic waves from m to about 800 na+ or less, about 400
Includes ultraviolet light below rH, visible light from about 400 nm to about 700 nm, and infrared light from about 700 nm to about 800 nm.

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 indo7er/-, indoaniline, and azo azomethine dyes, are combined with 71/-type compounds having a fused heterocyclic ring system. By mixing with
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 deficiencies, 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 undesirable due to the coloring 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, a method is known in which a dye image fading inhibitor having a 7-ethyl hydroxyl group or a group that can be hydrolyzed to produce a ferro-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. 134327 describes 7-er/7-el and bis-7-er7-ols, U.S. Pat. No. 3,069,262 describes pyrogallol, gallic acid and its esters, and U.S. Pat.
No. 90 and No. 4,015,990, α-toph7erols and their acyl derivatives, Japanese Patent Publication No. 52-275
No. 34, JP-A No. 52-14751 and U.S. Patent No. 2,
No. 735,765 describes hydroquinone derivatives; U.S. Pat. No. 3,432,300 describes 6-hydroxychromans, U.S. Pat.
No. 50 proposes the use of 5-hydroxychroman derivatives, and Japanese Patent Publication No. 49-20977 proposes the use of 6,6'-dihydroxy-2゜2゛-spirobichromans. 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 has a large effect on the hue of the colored substance, which is considered a disadvantage. In addition, the use of metal complexes to prevent photodegradation of polymers has been proposed by J.P. Guillory, R Journal of Polymer Science, Polymer Chemistry ai (J, Poly
m, Sci, , Polym, Chem, Ed, )1
Volume 2, page 993 (1974), R.P.R.
Ranaweera, G-Fist Sco7to (R, P, R, Rana
weera, G, 5cotL), Journal of Polymer Science, Polymer Letters HA (J, Pol
ym, Sci, +Po1yI1. LetL, Ed,
).

13, p. 71 (1975), etc., and methods for stabilizing dyes against light using metal complexes are described in JP-A No. 50-87649 and Research Disclosure + - (Research Disclosure).
> No. 15162 (1976), these complexes do not have a large anti-fading effect and are not highly soluble in organic solvents, so they must be used in an amount sufficient to exhibit the anti-fading effect. cannot be added. Furthermore, these complexes themselves are highly colored;
If added in large amounts, it will have a negative effect on the hue and purity of the if-colored substances, especially the 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.
-651, 54-82385, 54-8238
No. 6, No. 54-136581, No. 54-136582
No. 55-12129, No. 55-152750,
It is described in No. 56-168652, No. 56-167138, No. 57-161744, Japanese Patent Publication No. 57-19770, 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 color photographic materials that have been developed are 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 objects of the present invention are achieved! Colored substances and the following general formula [1
This is achieved by coexisting at least in of the compound represented by ].

General formula [1] In the formula, R1 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group,
It represents an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and R2 represents a substituent. n represents an integer from θ to 6,
When n represents an integer of 2 or more, a plurality of R2's may be the same or different. X represents an oxygen atom or a sulfur ff atom,
Y represents a methylene group or an ethylene group.

The present invention will be explained in more detail below.

Examples of the alkyl group represented by R1 in the above general formula [■] include groups such as methyl, ethyl, [-butyl, octyl, dodecyl, and hexadecyl; examples of the cycloalkyl group include groups such as cyclopentyl and cyclohexyl; Examples of alkenyl groups include 7lyl, hexenyl,
Groups such as oleyl, cycloalkenyl groups such as cyclohexenyl and cyclooctenyl, alkynyl groups such as propynyl, butynyl and octenyl, and aryl groups such as 72nyl and ρ-
Groups such as butylphenyl and naphthyl; examples of heterocyclic groups include groups such as chenyl, tetrahydrofuryl, and pyrinol; examples of acyl groups include groups such as acetyl, myristoyl, stearoyl, and benzoyl; examples of sulfonyl groups include, for example, Groups such as methylsulfonyl and p-methoxyphenylsulfonyl; examples of the phosphonyl group include groups such as butylphosphonyl and non-7enylphosphonyl; examples of the carbamoyl group include groups such as methylcarbamoyl, quethylcarbamoyl, and phenylcarbamoyl; Examples of the 77 moyl group include ethylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc., alkoxycarbonyl groups include ethoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc., and aryloxycarbonyl groups include ,
For example, specific examples include phenoxycarbonyl, pt-butyl 7eth/oxycarbonyl, and the like.

The substituent represented by R2 is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkenyl, cycloalkyl, etc. In addition, halogen atoms and cycloalkyl , alkynyl, heterocycle, sulfonyl, sulfinyl,
phosphonyl, acyl, carbamoyl, sulfamoyl,
Schiff/, alkoxy, aryloxy, heterocyclic oxy,
Acyloxy, carbamoyloxy, ami/, flukylamino, imide, ureido, sul7amoyl7mi/, alkoxycarbonylamino, aryloxycarbonylamino, furkylcarbonyl group 7lyloxycarbonyl groups, as well as spiro compound residues, bridged Also included are hydrocarbon compound residues and the like.

The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R2 is preferably a phenyl group.

Examples of the 7 acyl amide groups represented by R2 include 7 alkyl carbonyl amide groups, 7 aryl carbonyl amide groups, and the like.

Examples of the sulfonamide group represented by R2 include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkenyl group represented by R2 has 2 to 32 carbon atoms.
The cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R2 has 3 carbon atoms.
-12, especially 5-7 are preferred.

Sulfonyl groups represented by R2 include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. group, arylphonyl group, etc.; 7-syl group includes furkylcarbonyl group, arylcarbonyl group, etc.; carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc. Nisulfamoyl group includes alkylsulfamoyl group,
Arylsulfamoyl group ring; As an acyloxy group, an alkylcarbonyloxy group, a 7lylcarponyloxy group, etc.; As a carbamoyloxy group, an alkylcarbamoyloxy group, a 7lylcarpamoyloxy group, etc.; As a ureido group, an alkyl Ureido group, aryl ureido group, etc.; Examples of the sul 7 amoylamino group include an alkyl sul 7 amoylamino group, arylsul 7 amoylamino 7 group, etc.; as the heterocyclic group, those with 5 to 7 shells are preferable, specifically 2-furyl group , 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group; As the heterocyclic oxy group, those having a bicyclic ring of 5 and -7 shells are preferable, for example, 3
．． 4,5.6-tetrahydropyranyl-2-oxy group,
1-7 enyltetrazole-5-oxy group, etc.; Imide groups include succinimide group, 3-heptadecylsuccinimide group, 7talimide group, glutarimide group, etc.; spiro compound residues include spiro [3,3 ] Heptan-1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo [2゜2.
11 Hebutan-1-yl, tricyclo [3°3.1.
Examples include 1'.71decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]heptane-1-yl, and the like.

The methylene or ethylene group represented by Y may be substituted with an alkyl or aryl group.

The compound represented by the general formula [I] of the present invention is included in any of the following general formulas (Ia) to (Id).

General formula [1a] General formula (Ibl General formula [IC] General formula [1d] General formula (Ia)-" ([In dl, R', R2t;
and n are R1. in the general formula [1]. R2 and n
are synonymous with each other. Among the compounds represented by the general formula [1), R' is particularly preferably an alkyl, cycloalkyl, aryl, or heterocyclic group.

Next, typical examples of the compound represented by the general formula [I] (hereinafter referred to as the photofading inhibitor of the present invention) used in the present invention will be given, but the present invention is not limited thereto.

Methods for synthesizing these compounds of the present invention are known, for example, as described in Bei!, Vol. 27, p. 460;
Kimi-7 Butyrotychlichesky Soedinei (K
Him, Geterotsikl, 5oedin)
* 1971, Vol. 7 (1), pp. 25-28, Tetrahedron Lett.
+ 1971, Vol. 26, pp. 2421-2424, Journal of the Chemical Society, Perkin Transaxia:/I(J, CheIII,
Soc, PerkinTrans, I),
1975, pp. 88.772-774, Journal of Heterocycology 17th Chemistry (J, He
terocycle, Chew, ), 1975,
It can be synthesized according to the method described in Vol. 12 (12), pages 409-411, 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 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, oxanone 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.
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,
The dyes most preferably used in the present invention are methine and polymethine dyes, such as polymethine, indoamine, indophenol and formazan dyes; This dye includes compounds having the following groups.

Among the above groups, the phenyl group represents an unsubstituted phenyl group or a 1n-substituted phenyl group, such as a phenyl group substituted with an alkyl group, an alkoxy group, a halogen atom, an amide 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.
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.

Preferred examples of yellow dye image-forming couplers in the present invention include benzoyl 7cetanilide type and pivaloylacetanilide type couplers, and examples of magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type and imigzovirazole type couplers. , pyrazolo pyrazole series,
There are birazolotetrazole-based, pyrazolinobenzimidazole-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, typical examples of yellow couplers that can be used in the present invention are listed.

1\ -I Y-5 Y-Nire's yellow coupler is, for example, West German Published Patent Application No. 2.0.
No. 570941, West German Published Patent No. 2,163,812,
JP 47-26133, JP 48-29432, JP 50-65321, JP 51-3631, JP 51-5
No. 0734, No. 51-102636, No. 48-668
No. 35, No. 4g-94432, No. 49-1229,
Including compounds described in Japanese Patent Publication No. 49-10736, Japanese Patent Publication No. 51-33410, Japanese Patent Publication No. 52-25733, etc.
and can be synthesized according to the methods described therein.

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

Shishishi M-9 M-10 These magenta couplers are disclosed in, for example, 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, 'Ao-a i'r S No. 2 Research Disclosure No. 24626 (198
4), Patent Application No. 59-243007, No. 59-2430
No. 08, No. 59-24 to No. 09, No. 59-243
No. 012, No. 60-70197, No. 60-70198
It 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 are listed.

■ C・-4 1;, H, L; ν These cyan couplers are disclosed in, for example, U.S. Pat.
．． No. 730, No. 2,801,171, Japanese Unexamined Patent Publication No. 1973-1
No. 12038, No. 5G-134644, No. 53-10
No. 9630, No. 54-55380, No. 56-6513
No. 4, No. 56-80045, No. 57-155538, No. 57-204545, No. 5g-98731, No. 59-3195a, 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 developer includes aminophenol and phenylenediamine, and these developer networks 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.

(+-1) (+-7) (1-,8) Further, as other types of dyes preferably used in the present invention, U, S, B 351,673, U.S. Pat. No. 3,932゜381 , No. 3,928,312, No. 3
, No. 931, 144, No. 3,954゜476, No. 3,
No. 929,760, No. 3,942,987, No. 3,9
32゜380, 4.01: (, 635, 4.01)
No. 013,635, No. 4,013.633, Japanese Unexamined Patent Publication No. 1973
No. 1-113624, No. 51-109928, No. 51
-104343, 52-4819, patent application 1972-
No. 64533, Research Disclosure + -No.
15157 (1976), same magazine No. 13024 (19
75) etc. I) Dyes formed by oxidation of RIt compounds can be mentioned.

Furthermore, other types of dyes that may be used in the present invention include:
For example, British Patent No. 840.731, British Patent No. 904364,
932.272, 1,014,725, 1,
No. 038,331, No. 1.066.352, No. 1.0
No. 97,064, JP 51-133021, U.S.
T 900s029 (U, S, Defensi
ve PublicnLion), U.S. Patent 3,2
Mention may be made of dyes released by reaction of DDR couplers 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. 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 azo dyes such as Direct 7 Asto Yellow GC (CI 29000), Glisophenine (CI 24895), Indigo Golden Yellow IGK (CI 59101),
Ink Gosol Yellow 2GB (CI61726), Arbosol Yellow 0CA-CF (CI67301),
Indanthrene yellow GF (CI 68420)
, Mikethrene Yellow G C (CI 67300), Indanthrene Yellow 4 G K (CI 68405)
), anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes. Magenta dyes include azo dyes such as Sumilite Sublarbinol B (CI 29225), Penzopriant Keranin B (CI 15080), indigosol brilliant pink I R (CI
73361), Indigosol Violet 15R (
CI 59321), Indigosol Red Violet IRRL (CI 59316), Indanthrene Red Violet) RRK (CI 67895), Mikethrene Prilliand Violet B B K (CI 6)
Indigoid dyes such as 335); benzoquinone dyes,
Examples include soluble vat dyes made of anthraquinone heteropolycyclic compounds and other vat dyes.

Direct Sky Blue 68 is a cyan dye.
(CI 24410), Direct Brilliant Blue 28 (CI 22610), Sumilight Sub Blue-
Azo dyes such as G (CI 3420G), Sumilite Sabra Turkey Blue (CI 74180), Mikeslen Prilliant Blue 4 G (CI 741)
7-talocy7ine dyes such as Indanthrene Turkey Sprue 5 G (CI 69845), Indanthrenblue-GCD (CI 73066), Indigosol 04-G (CI 73046), Anthrazol Green I B (CI 59826).

As mentioned above, the compounds of the present invention stabilize organic coloring substances. These compounds of the present invention may be present in any or all of the emulsion layers of the color photographic material.The compounds of the present invention may be present in any of the layers contained in the non-light-sensitive portions of the color transfer material. You can also do that. The methods effective for dispersing these compounds of this invention are the same as those used for dispersing couplers.

The compounds of the present invention are generally oil-soluble and are typically used in U.S. Pat.
, No. 801゜171, No. 2,272.191 and No. 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 the compound of the present invention to a hydrophilic colloid solution, and if necessary, there is no problem in adding a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor, etc. 2
There is no problem in using a mixture of two or more kinds of compounds.Moreover, to explain in detail the method of adding the compounds of the present invention, one or more kinds of the compounds can be added as necessary to couplers, hydroquinone derivatives, ultraviolet absorbers, or Known dye image fading inhibitors, etc. can be added at the same time to organic acid amides, carbamates, esters, ketones, hydrocarbons, urea derivatives, etc., especially diptyl heptatarate, tricresyl phosphate, normal octyl azelate, dibutyl sepamate. cate, trihexylphos 7ate, decalin, N,N-ethylcaprylamide, N,N-quethyl? "7') A
If necessary, dissolve in a high boiling point solvent such as t 7 mito, pentadecyl phenyl ether or fluoroparaffin, and in a low boiling point solvent such as ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydro 7 run, etc. High boiling point solvents and low boiling point solvents may be used alone or in combination.) Anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquioleate and sorbitan monolauric acid. It is mixed with an aqueous solution containing a hydrophilic pigment such as gelatin containing a nonionic surfactant such as an ester, and emulsified and dispersed using a high-speed rotation mixer, colloid mill, footsteps liquid dispersion device, etc., and the resulting dispersion is converted into 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 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 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.

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 as 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 3,594.185 and Belly Patent 757,9
No. 59 and No. 757,960.

The coloring substances used in the present invention and the compounds of the present invention are listed in the Product Licensing Index (Product Licensing Index).
uct L 1censiB Index), 92
Volume (December 1971 L 9232, 107-110
It is possible to weep according to the method with the materials as described in i. Regarding this point, see ff11 of the above-mentioned document. n.

III, IV, V, ■, ■, ff, X, XI, ff
, X1. XIV, XV.

Sections XVI, X■, xvi, and XX■ are applicable.

Any type of compound of the invention should provide the improvements of the invention, and there is theoretically no upper limit to the amount that may be used.

When the present invention is applied to photographic light-sensitive materials, it is preferred that the compound of the present invention is present in an amount of at least 1 micromole per 2 of the light-sensitive material, and about 10 to 1 xio per 1z2 of the light-sensitive material.
'It is further preferred if micromoles of the compound of the invention are present.

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 an amount ranging from about 10 to 104 micromoles per square meter of light-sensitive material. More preferably, it is present in an amount ranging from about 100 to about 600 micromoles per shoulder 2 of the photosensitive material.

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

What is the maximum wavelength absorption peak of this base material?

It is preferably in the range of 300 to 800 im, most preferably in the range of 400 to 700 im in methanol solution.

In the photographic material used in the method of the present invention, the silver halide emulsion is generally one in which silver helodenide grains are dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, and 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 can be used alone or in combination of two or more.

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 in which a coupler is contained in a developer. It is processed according to 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 the aromatic wS primary amine developing agents were previously described as exemplary developers D-1 to D-6.

When the color photographic material to which the method of the present invention is applied is a film unit for color diffusion transfer, processing of the photographic material is automatically carried out inside 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-methylami/phenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 3-methoxy-N,N -noethyl-p-7 22-diamine, 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 above-mentioned dye-forming color coupler and an oxidized form of a p7z nylene diamine-based color developing agent, a dye development method, etc. Method using drugs, method using oxidative burst reaction of DRR compound, DDI? Any known method can be used, such as a method using a dye separation reaction due to a coupling reaction of a coupler, a method using a dye forming reaction due to a coupling reaction of a DDR coupler, or a method using a silver dye bleaching method.

Therefore, when applying the method of the present invention to photographic light-sensitive materials, various color photographic light-sensitive materials such as color positive film, color paper, color negative film, color reversal film, color diffusion transfer film unit, light-sensitive material for silver dye bleaching, etc. can be mentioned.

〔Example〕

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

Example I A magenta dye having the following structure (absorption maximum 53gno+ in methanol solution) was dissolved in tricresyl phosphate) 4t*Q and methyl acetate 8111Q, and this solution was dissolved in 0.5 %
Sodium dodecylbenzenesulfonate aqueous solution 2mff
was emulsified and dispersed in 12 mQ of IO% gelatin solution containing

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

When preparing the above emulsified dispersion in the same manner, 0.4 g of each of the comparative compounds represented by the following structural formulas (a) and (I)) was added and applied in the same manner as in Sample No. 1. Samples No. 2 and No. 3 were prepared in this manner.

Further, when preparing the emulsified dispersion liquid by the method of the above sample No. 1, 0.4 g of each of the exemplary compounds of the present invention was added as shown in Table 1 and applied in the same manner as the above sample No. 1. 12 types of samples (No. 4 to 15) were created.

Comparative compound (a)...Metal complex comparative compound (b) described in JP-A-55-12129...Same as above Each of the above samples was measured with a xenon fade meter for 7 days.
The light fastness of the dye image was determined by J.q. The results are shown in Table 1. However, the light resistance of the dye image was determined based on the dye residual rate.

The samples using the agent (Nos. 4 to 15) showed better anti-fading effects than the samples using the known metal complexes (Nos. 2 and S'), and almost no black-brown discoloration occurred. I was not able to admit.

Example 2 In Example 1, the magenta dye was used as a magenta dye having the following structure (maximum absorption of 536 ni 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 IQ light for 5 days using a xenon fade meter to examine the light resistance of the dye image. The results are shown in Table 2 (magenta dye). It can be seen that this sample has a better photofading prevention effect than the sample using the Iji complex.

In addition, the sample according to the present invention showed almost no blackish-brown discoloration and maintained a favorable hue even after the light exposure test.

Example 3 28g of exemplified coupler (M-8) as magenta coupler
dibutyl phthalate) 35aQ and ethyl acetate 100
- 500ml of 5% aqueous gelatin solution containing 2.5g of sodium dodecylbenzenesulfonate (
The resulting dispersion was added to green-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion 1000100O, and N was added as a hardener.

Add 10n+Q of a 2% methanol solution of N',N''-triacryloylhekizahydro-s-triazine, apply on polyethylene coated paper and dry to obtain a sample of a monochromatic color photographic material.This sample will be designated as No. 31. .

When preparing the above emulsified dispersion in the same manner, 15 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, the book 9.0! The exemplified compound of I is
Seven samples (No.
.

34-40) 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]

"Add benzyl alcohol 12.0at water to make IQ, and use sodium hydroxide to adjust pH to 10.
,30.

[Bleach-fix solution]

Add water to make 1e, and use ammonia water to pH 6.5.
Adjust to.

[Processing process] (30℃) Processing time Development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Washing with water 3 minutes L drying Each sample with a dye image formed in this way was coated with a Kodak ultraviolet cut filter.・Wratten filter N
A 7-day color test was conducted using a xenon fade 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.

(The absorption maximum of the colored magenta dye in methanol solution was 536 na+.)
&, 1.1-1-1-alln, the color inhibitor has a photofading prevention effect superior to that of conventional organic antifading agents.

Example 4 Exemplary coupler (C-6) 359 was used as a cyan coupler with dioquidyl phthalate') 35sQ and ethyl acetate 1
00mg of a 5% aqueous gelatin solution containing 2.5g of sodium dodecylbenzenesulfonate.
-, then dispersed with a homogenizer, and the resulting dispersion was added to red-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion 100011 (2), and N was added as a hardener.

10 si2 of a 2% methanol solution of N', N", -) acryloylhexahydro-S-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. 41.

When preparing the emulsified dispersion liquid in the same manner as in Example 3, 159 of each of the comparative compound (e) having the structure below and the exemplary compound of the present invention as shown in Table 4 were added to prepare 9 samples (No. 4, No. 4).
2-50) were created.

Comparative compound (e): Compound described in JP-A-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 10-day fading test was carried out using a xenon fade meter with the same material used in Example 3). The results are shown in Table 4.

The large one was 652 tua. ) As is clear from Table 4, the photofading inhibitor of the present invention also has a large effect of preventing cyan coloring dye from photofading.

〔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, especially the pigments, dyes, etc. used in color photographic light-sensitive 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. Acyl group, sulfonyl group,
It represents a phosphonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R^2 represents a substituent. n represents an integer of 0 to 6, and when n represents an integer of 2 or more, a plurality of R^2 may be the same or different. X represents an oxygen atom or a sulfur atom, and Y represents a methylene group or an ethylene group. ]