JPS63259566A - Method for preventing fading of organic coloring substance due to light - Google Patents

Abstract

PURPOSE:To improve the stability of an org. coloring substance against light by allowing the substance to coexist with a specified compd. so as to prevent the fading of the substance due to light. CONSTITUTION:An org. coloring substance is allowed to coexist with at least one kind of compd. represented by formula I or II. In formulae I, II, R<1> is H, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryloxycarbonyl or the like, R<2> is a substituent, n is an integer of 0-6, in case of n>=2, plural substituents R<2> may be the same or different from each other, X is O or =N-R<3> and R<3> is R<1>. Thus, the discoloring and fading of the org. coloring substance, especially a dye or coloring matter used in a color photographic sensitive material due to light can be remarkably suppressed.

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 has been conducted to prevent such interchromaticity of organic coloring substances in fields such as inks, textile dyes, or color photography.

The present invention has the purpose of preventing optical coloring 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
+o means electromagnetic waves of approximately 800 nm or less, approximately 400 nm
Includes less than 1 ultraviolet light, visible light from about 400 nm to about 700 nm, and infrared light from about 70 Or+m to about 800 nm.

There are many reports on methods for improving the light emitting properties of organic coloring substances, such as pigments or dyes.For example, US Pat. By mixing organic compounds used in color photography with 7-enol 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 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, methods using dye image fading inhibitors having a phenolic 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, phenol and bis-7 ethers, U.S. Patent 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.
No. 51 and U.S. Pat. No. 2,735.765 contain hydroquinone derivatives; U.S. Pat.
, 574,627, 5-hydroxychroman derivatives in U.S. Pat. No. 3,573,050, and 6°6' in Japanese Patent Publication No. 49-20977
It has been proposed to use -dihydroxy-2,2'-spirobichroman MW. 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, Polymer Chemistry II (J, P
olym, Sci.

Polym, Che16. Ed, ) vol. 12, p. 993 (1974), Journal of Polymer Science, Polymer Letters II (J, Polym, Sei,
* Polym, Lett, Ed, ), 13 volumes,
71 (1975), etc., and methods for stabilizing dyes against light using metal complexes are described in JP-A-50-87649 and Research Disclosure No.
, 15162 (197B), but these complexes do not have a great anti-fading effect, and
Since the solubility in organic solvents is not high, do not add an amount large enough to exert the anti-fading effect.Furthermore, these complexes are highly colored by themselves, so if added in large amounts, , have a negative effect on the hue and purity of organic coloring substances, especially pigments.

Furthermore, methods for photostabilizing dyes using various metal complexes are described in JP-A-54-62826, JP-A-54-82987, 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
-187138, No. 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 7) silver lodenide 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 polychromatic materials.

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 [1]
This is achieved by coexisting with at least one compound selected from the compounds represented by the general formula [■].

General formula [f] General formula [II] 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 sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R2 represents a substituent. n represents an integer from 0 to 6,
When n is 2 or more, a plurality of R2s may be the same or different.

X represents an oxygen atom or a =N-R3 group, and R represents a group similar to the group represented by R1.

The present invention will be explained in more detail below.

In the above general formulas (1) and (If), the alkyl group represented by R1 and R3 has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 carbon atoms.
-32, cycloalkyl groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups and alkynyl groups may be linear or branched. Moreover, these groups may have a substituent.

Specifically, methyl, ethyl, t-butyl, pentadecyl, 1-hexyl/nyl, 2-chloro-t-butyl, benol, 2,4-di-t-aluminum 7e/xymethyl, 1
-Ditoxytridecyl, allyl, impropenyl, ethynyl, 2-7'' robinyl, cyclopentyl, cyclohexyl, cyclohexenyl and the like groups.

The aryl group represented by R1 and 3 is preferably a 7enyl group or a naphthyl group, even if it has a substituent. Examples of tetramers include phenyl, 4-nitro7enyl, 4-t-butylphenyl, 2,4-not-7mil7enyl, 3-hexadecyloxyphenyl, σ-7tyl, etc. The following groups are mentioned.

The heterocyclic groups represented by R1 and R3 preferably have 5 to 7 rings, and may be substituted or fused. Specific examples include 2-7'-lyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R1 and R3 include acetyl group, phenylacetyl group, dodecanoyl group, α-
Furkylcarbonyl group such as 2,4-not-t-amylphenoxybutafyl group, benzoyl group, 3-pentadecyloxybenzoyl group%11-907 such as rubenzoyl group
Examples include lyl carbonyl group.

Examples of the sulfonyl group represented by R1 and R3 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 R3 includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a 7ヱ7xyphosphonyl group, and a phenylphosphonyl group. Examples include arylphosphonyl groups such as nyl groups.

The carbamoyl group represented by R1 and R3 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, N,N
-dipylcarbamoyl group, N=(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4-not-7
Examples include mil7eth/xy)propyl)carbamoyl group and the like.

The sulfamoyl group represented by R1 and R3 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl group, N
, N-noethylsul7amoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N
-dodecylsulfamoyl group, N-phenylsulfamoyl group, etc.

The oxycarbonyl group represented by R1 and R3 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 benoloxycarbonyl group, etc. . Further, the aryloxycarbonyl group may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and a gu-pentadecyloxyphenoxycarbonyl group.

There are no particular restrictions on the substituent represented by R2, but R1
In addition to representing the same groups as R3, halogen atoms and anilino, acylamino, sulfonamide, alkylthio, arylthio, sulfinyl, cyan, alkoxy, aryloxy, heterocyclicoxy, heterocyclicthio1, siloxy, acyloxy, carbamoyloxy, amino , alkylamino, imide, ureido, sulfamoylamino, alkoxyluponylamino, and aryloxycarbonylamino groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

Examples of the acylamino group represented by R2 include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R2 include an alkylsulfonyl 7mino group and an arylsulfonylamino group.

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

Sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; 7-syloxy groups include alkylcarbonyloxy groups,
Arylcarbonyloxy group ring; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; examples of sul-7 amoylami I groups include alkylsul-7 amoylami-7 groups, arylsul-7 amoylami groups; 77 moyl 7 mi 7 group, etc. The heterocyclic oxy group preferably has 5 to 7 heterocycles, such as 3,4,5.6-tetrahuman σ pyranyl-2-oxy group, 1-7 enyltetrazole- 5-
Oxy group ring: As the heterocyclic thio group, a 5 to 7 true polycyclic thio group is preferable, such as a 2-bilinorthio group, a 2-benzothiazolylthio group, a 2,4-cy7-functional/xy-1, 3,5-triazole-6 monothio group, etc.; siloxy groups include trimethylsiloquine group, triethylsiloxy group, trimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-heptadecylsuccinimide group, 7-thalimide group, glutarimide group, etc.; Spiro compound residues include spiro [3,3]hebutan-1-yl; bridged hydrocarbon compound residues include bicyclo [2゜2.
11 Hebutan-1-yl, tricyclo [3°3.1.
Examples include 13.71decane-1-yl, 7,7-nomethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

In general formulas CI) and (II), when two R3s are located at adjacent positions, the two R3s may be bonded to each other to form a 5- to 7-membered ring.

The compound represented by the general formula [Ia] according to the present invention is a 4-piperidone compound represented by the following general formula (Ia) or a 4-iminopiperidine compound represented by C1b), or a 4-iminopiperidine compound represented by the general formula [11a)] It is a 3-piperidone-based compound represented by the following formula or a 3-iminopiperidine-based compound represented by (llb).

General formula CI&) General formula [:Ib'
General formula (Ha:II General formula Cl
Ib: 1 In general formulas (Ia) to Cab), R', R
2, R3 and n are represented by the general formula [R, ', R in Ia
, 2, R3 and n, respectively, and carbon atoms at the 2-, 3-, 5-, and 6-positions of general formulas CI &) and (Ib), 2 of general formulas CIIa) and [:IIb']
It also includes cases where the carbon atoms at the 4th, 5th, and 6th positions are each spiro carbon atoms.

Next, typical examples of the anti-fading agent represented by the general formula (1) (hereinafter referred to as the compound of the present invention) used in the present invention will be shown, but the present invention is not limited thereto.

A-24 A-26A-27 A-29A-30 These methods of synthesizing the compounds of the present invention are known, for example, as described in JP-A-54-98771, JP-A-54-98772, and JP-A-54-98772.
No. 4-112873, West German Published Patent No. 2,753,278
It can be synthesized according to the method described in No.

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 800r+a+, preferably 400nm to 70
It has at least one absorption maximum in Onso.

Among these dyes, preferred dyes for the present invention include quinone imine dyes (anone dyes, oxazine 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 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,
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 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, 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 of radish.

Preferred examples of yellow dye image-forming couplers in the present invention include benzoylacetanilide type and pivaloylacetanilide type couplers, and examples of magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type, imigzopyrazole type and pyrazolone type couplers. Zolopyrazole series,
There are pyrazolotetrazole-based, pyrazoli/benraimigzole-based, and indasilone-based couplers, and cyan dye image-forming couplers include phenol-based, cabtol-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. 1.1-11, Y margin rσ rρ rσ rσ rσ Y-7 rσ These yellow couplers are, for example,
No. 057,941, West German Publication 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. 51-102838, 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, typical examples of magenta couplers that can be used in the present invention will be listed.

, ＼ Margin below I f I C, H5 CH.

+21125 These magenta couplers are described, for example, in U.S. Pat.
No. 4,514, British Patent No. 1,183,515, Japanese Patent Publication No. 40-6031, No. 40-6035, No. 44-15
No. 754, No. 45-40757, No. 46-19032
No., JP-A-50-13041, JP-A No. 53-129035
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. 1958, No. 59-162548, No. 60-436
No. 59, No. 60-33552, Research Disclosure + -No. 24626 (1984), Patent Application No. 5
No. 9-243007, No. 59-243008, No. 59
-243009, 59-243012, 60-
No. 70197, No. 60-70198, etc., and can be synthesized according to the methods described therein.

Although there are no particular limitations on the cyan coupler used in the present invention, a 7-er/-based cyan coupler is preferred.

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

Margin below I I H C2H.

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-mentioned developers include ami/7er/-el 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 F! Agent]

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

il 01;2H1 (1++ 7) NISO2CH3 Furthermore, other types of dyes preferably used in the present invention and L
Te Ji, U.S., B551.673, U.S. Patent No. 3,932,381, Patent No. 3,928,312, Patent No. 3
, No. 931,144, No. 3,954,476, No. 3,
No. 929,760, No. 3,942,987, No. 3,
932.

No. 380, No. 4,013,835, No. 4,013,8
No. 33, JP-A-51-113624, JP-A No. 51-109
No. 928, No. 51-104343, No. 52-4819
No. 53-149328, Research Discrow) + - No. 15157 (1976), No.
13024 (1975) and the like, which are formed by oxidation of DRR compounds.

Furthermore, other types of dyes that may be used in the present invention include:
For example, British Patent Nos. 840,731, 904, 364
No. 932,272, No. 1,014,725, No. 1,038,331, No. 1,068,352, No. 1
, No. 097,064, JP-A-51-1330-1, υ
5T900y029 (U, S, Defensive,
Publication)-.

DD as described in U.S. Pat. No. 3,227,550
Mention may be made of dyes released by the reaction of the R coupler with the oxidized product of the color developing agent or dyes formed by the reaction of the R coupler with the oxidized product of the color developing agent.

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 7 Asto Yellow GC (C.

1.29000), Glisophenin (C, [2489
5) Azo dyes such as Insigo Golden Yellow IG
K (C,1゜59101), Indigosol Yellow 2 GB (C,1,61726), Arbosol Yellow CC^-CF (C,I, 67301), Ingenthrene Yellow GF (C,I, 68420), Mike Benzoquinone dyes such as C (C, I, 67300) and Stren Yellow 4 GK (C, 1, 68405); Antoquinone dyes, polycyclic soluble vat dyes, and other vat dyes etc. can be mentioned.

As a magenta dye, Sumilite Sabralbinol B
(C01,29225), azo dyes such as Penzoprilliant Keranin B (C,1,15080), Innovosole Brilliant Pink Il't (C,1,73
361), indigosol violet 15R (C,I
, 59321), Indigosol Red Violet I
RRL (C,I, 59318), Indanthrene Red Violet RRK (C,I, 67895), Mikethrene Brilliant Violet BBK (C,I.

Examples include indigoid dyes such as 6335); soluble vat dyes composed of benzoquinone-based and anthoquinone-based heteropolycyclic compounds; and other vat dyes.

As a cyan dye, Direct Sky Blue 68 (
C,1,2441,0), Direct Brilliant Blue 2 B (C,1,22610), Azo dyes such as Sumilight Subrable-G (C01,34200), Sumilight Sapra Turkey Blue G (C,I, 741
80), Mikethren Brilliant Blue 4 G (C,
7 talocyanine dyes such as I, 74140), indanslentarkey sprue 5 (: (C, 1,69845)
), indanstrable-GCD (C,I.

7306-6), Indigosol 04G (C, I, 7
3046), Anthrazole Green 18 (C,1,
59826).

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 at this time, if necessary, a coupler, a hydroquinone derivative, an ultraviolet absorber, a known dye image fading 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 are added with an organic acid, if necessary, a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor. amides, carbame)! , esters, ketones, hydrocarbons and urea derivatives, especially dibutyl heptatarate, triphrenol phosphate, di-
Acetic acid is added 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. Dissolves in low boiling point solvents such as ethyl, butyl acetate, butyl propionate, cyclohexyl, cyclohexane, tetrahydrofuran, etc.
(These high-boiling, α- and low-boiling solvents can be used alone.
1 or a mixture of them may be used. ) An aqueous solution containing an anionic surfactant such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and/or a hydrophilic surfactant such as gelatin containing a nonionic surfactant such as sorbitan sesquioleate and sorbitan moalaurate. Mix and emulsify and disperse using a high-speed rotating mixer, colloid mill or ultrasonic dispersion device,
The resulting dispersion can be added to a hydrophilic colloid solution (for example, a silver lodenide emulsion) and used.

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 and non-light-sensitive elements such as dye image receptors used in photographic diffusion transfer film units. When included in a photosensitive image recording element, 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 anticapri agents or stabilizers in the photographic industry for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or keeping photographic performance stable. 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 an internal color photographic material containing a coupler or an external color photographic material in which a coupler is contained in a developer. A color image is obtained. 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-pyrazolidone, 1-phenyl-4,4-tmethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 3-methoxy-N,N -Noethyl-p-7x herring diamine, etc. can be used.

When the method of the present invention is applied to photographic light-sensitive materials, color positive films, color papers, color negative films, color anti-pine films, film units for color diffusion transfer, light-sensitive materials for silver dye bleaching, color light-sensitive materials for heat development, etc. Examples include various color photographic and photosensitive materials.

[Example] The present invention will be described below with reference to Examples, but the manner in which the present invention can be carried out is not limited to these.

Example 1 Magenta dye having the following structure (absorption maximum 583 nm in methanol solution) C! 0.5 g was dissolved in 4 mf of Cuptil 7 Tare) and 8 ml of ethyl acetate, and this solution was emulsified and dispersed in 10 mA' of a 10% gelatin solution containing 0.5% sodium dodecylbenzenesulfonate aqueous solution wX2 mf.

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 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 V No. 3 were prepared by adding 50xg of the sample and applying the same method 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 zg of each of the exemplary compounds of the present invention was 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.

5 Tea 4) J Composition Table 1 As is clear from Table 1, the samples using the anti-fading agent of the present invention (Nos. 4 to 15) are different from the samples using known metal complexes (Nos. 2 to 15). and 13) showed a superior effect of preventing color change during light, 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 of 536 nm in methanol solution).
) Samples 15a (No. 15a, L, S-30) were prepared in the same manner as in Example 1 except that

The obtained sample was exposed to a xenon 7-ade meter for 150 hours to examine the light resistance of the dye image. The results are shown in Table 2.

(Magenta dye) Margin below 1 --' Table 2 Table 2 also shows that the sample using the anti-fading agent of the present invention has a better effect of preventing light fading than the sample using the known gold R complex. It can be seen that 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 25 g of exemplified coupler (M-8) as magenta coupler
A solution of 25mf of tricresylphos 7A) and 100n of ethyl acetate was added to a 5% aqueous gelatin solution containing 2.5g of sodium dodecylbenzenesulfonate.
00n+f, dispersed with a homogenizer, and the resulting dispersion was mixed with green photosensitive silver chlorobromide (silver chloride 30 mol%).
Contains) added to 1,000 ml of emulsion, N as a hardening agent,
10 mN of a 2% methanol solution of N',N"-)lyacryloylhexahydro-s)rianone was added, coated on polyethylene coated paper and dried 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, 25 g of comparative compounds (c) and (d) each having the following structure were added and applied in the same manner to prepare samples No. 32 and No.

33 was created.

Furthermore, as shown in Table 3, 20g of each of the exemplary compounds of the present invention were added and applied in the same manner to seven types of samples (No.

34-40) were created.

Comparative compound (c)... Compound described in JP-A No. 54-48538 Comparative compound (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]

Bennol alcohol 12.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.9g Sodium bromide 1.4g Potassium bromide
0.5g sodium carbonate
30.0gN-ethyl-N-β-methanesulfonamidoethyl-4-7mino7niline sulfate 5
．． Add 0g of water to bring the mixture to 1N, and adjust the pH to 10.30 using sodium hydroxide (1111g).

[Bleach-fix solution]

Iron ammonium ethylenediaminetetraacetate 61.0° Ethylenediaminetetraacetic acid diammonium 5.0g Ammonium 100osulfate 124.5g Ammonium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g Add water to make IIl, and use aqueous ammonia. Adjust the pH to 6.5.

[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 Kodak Laughten Filter N, an ultraviolet edge cut filter, to each sample with a dye image formed in this way.
A fading test was conducted for 150 hours 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.

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

Example 4 As a cyan coupler, 35 g of the exemplary coupler (C-6) was mixed with 35 ml of octyl (7 tales) and 100 ml of ethyl acetate.
ml of a 5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate.
After adding to t', it is dispersed using a homonizer, and the resulting dispersion is converted into red-sensitive silver chlorobromide (containing 30 mol% silver chloride).
Added to 1,000 ml of emulsion and added N and N' as hardeners.
, N"-) 2% methanol solution of acryloylhexahydro-S-trianone (10+nN) 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, 12g of each of the comparative compound (e) having the following structure and the exemplified compound of the present invention as shown in Table 4 were added to prepare sample l'1 (No.
42-50) 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 treated with an ultraviolet light car/) filter. A 250 hour fading test was carried out using a xenon fade meter (same as that used in Example 3). The results are shown in Table 4.

Table 4 (Absorption of colored cyan dye in methanol solution [maximum is 6
It was 52n. ) As is clear from Table 4, the anti-fading agent of the present invention also has a large effect of preventing cyan coloring pigments from changing color.

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-butane) l) All reducing agent...The following reducing agents A and B are 7=3 (molar ratio) or less (A>(B) Organic silver salt...5-methylbenzotriazole silver Photosensitive silver halide: The same one described in the Examples of Japanese Patent Application No. 61-254257 was used.

Yellow dye-providing substance (Y-CPM) CH.

x:y=80:20 (weight ratio) Margin below Magenta dye-providing substance (M-CPM) CH.

Cyan dye donor material (C-CPM) Listen x:y=60:40 (weight ratio) Below is the margin, ゛.

ζ.

Preparation of heat-developable image-receiving element> Photographic baryta paper (thickness 170μ11 weight 190y/z
2) Apply the following image-receiving layer coating solution on top to a wet film thickness of 137.2 μm.
It was coated on the shoulder and dried to prepare a heat-developable image-receiving element (Sample No. 51).

(Image-receiving layer coating liquid) Polyvinyl chloride (Wako Tsumugi Co., Ltd., n = 1,100) 21
．． 0g Tetrahydrofuran 190z1 When preparing the above image-receiving layer coating solution in the same manner, as shown in Table 6, add 0.8g each of the comparative compound, ultraviolet absorber, and exemplary compound of the present invention (if used together, add 0.8g each). .4 g each) and applied in the same manner as Sample No. 51 above to create nine types of samples (No. 52 to 60).

The heat-developable photosensitive element was exposed to 4,000 CMS of tungsten light through a step wedge and a green filter, and the coated surfaces of the heat-developable image-receiving element were overlapped with each other and preheated at 100° C. for 4 seconds. 15
Pressure heating (thermal development) was performed at 0° C. for 90 seconds. In addition, the preheating and 1st compression heating are described in Japanese Patent Application Laid-Open No. 153651/1986.
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 Sakura Densitometer PO^-65 (manufactured by Konishiroku Photo Industry) using green light.

(Evaluation of light resistance stability) A sample with a magenta image was irradiated with light for 5 and 10 days using a xenon fade meter (S tester HE-OX-IC), and the dye concentration residual rate (%) was examined. .

Margin below Table 6 *Ultraviolet absorber (UV-t) *Comparative compound (c) 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〕

Contains the photochromic color inhibitor according to the present invention! By being present with a coloring substance, it is possible to significantly reduce the discoloration caused by light of organic coloring substances, especially pigments, dyes, etc. used in color photographic materials.

Claims (1)

[Claims] Organic coloring substance and the following general formula [I] and general formula [II]
A method for preventing photofading of an organic coloring substance, which comprises preventing the organic coloring substance from fading due to light by coexisting with at least one compound selected from the compounds represented by the following. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group , cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, 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 6, and when n is 2 or more, multiple R^
2 may be the same or different. X represents an oxygen atom or a =N-R^3 group, and R^3 represents a group similar to the group represented by R^1. ]