JPS63228150A - Method for preventing organic coloring material from light fading - Google Patents

Abstract

PURPOSE:To improve the stability of the organic coloring material against light by incorporating at least one kind of the org. coloring material together with at least one kind of a specific compd. in a photosensitive material. CONSTITUTION:At least one kind of the org. coloring material together with at least one kind of the compd. shown by formula I are incorporated in the photosensitive material. In formula I, R1 is hydrogen atom., alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl, a heterocyclic ring, acyl, sulfonyl, phosphonyl, carbamoyl, sulfamoyl or oxycarbonyl group, R2 and R3 are each a substituent group, (m) is an integer of 0-3, (n) is an integer of 0-4, X is an atomic group necessary for forming an isochromane ring or an isocoumarane ring. Thus, the discoloring and decoloring of the org. coloring material, especially, the coloring matter and the dye, etc., used for the color photographic sensitive material due to light is remarkably reduced.

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 photobleaching of organic coloring substances in the fields of inks, textile dyes, and color photography.

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

The organic coloring substance used in the present invention refers to a substance that appears colored to the human eye under sunlight,
Generally 300n-~800nm in methanol solution
1800n also means an organic substance having one absorption maximum.

Furthermore, in this specification, the term light refers to approximately 300n
It means electromagnetic waves of about 800nm or less from m, and about 400o
Includes less than ugly ultraviolet light, about 400 nm to about 0 on ugly visible light, and about 700 nm to about 800 nm infrared radiation.

There are many reports on methods for improving the light fastness of organic coloring substances, such as pigments or dyes. For example, US Pat. / By mixing organic compounds used in color photography, such as tin dyes, 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 helodenide color photographic materials, the dye image obtained from the coupler is exposed to light over a period 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 the dye image due to visible light, and there is a limit to the improvement of light resistance by the ultraviolet absorber. Furthermore, a method using a pigment III fading inhibitor having a 7-ethyl hydroxyl group or a group that can be hydrolyzed to produce a phenolic hydroxyl group is known; for example, Japanese Patent Publication No. 48-31256, No.
No.-31625, No. 51-30482, JP-A-49-
134326 and 49-134327, phenol and bisphenol neck, U.S. Pat.
No. 262 includes pyrogallol, gallic acid and its esters, U.S. Pat.
No. 5,990 describes α-tocopherols and their 7-sil derivatives, Japanese Patent Publication No. 52-27534, Japanese Patent Publication No. 52-1
No. 4751 and U.S. Pat. No. 2.735.765 contain hydroquinone derivatives; U.S. Pat. No. 3.432.300;
No. 3,574,627 describes 6-hydroxychromans, U.S. Pat. - It has been proposed to use spirobichromans and the like. However, although these compounds can be seen to some extent to be effective as dye fading and discoloration inhibitors, they are not sufficient.

Also, British Patent No. 1,451,000 describes the improvement of the light stability of organic colored compounds using a 7zomethine quenching compound whose absorption peak is more bathochromic than that of the colored compound. However, since the azomethine quenching compound itself is colored, the hue of the colored substance is greatly disadvantageous. *In addition, the use of metal complexes to prevent photodegradation of polymers has been proposed in the Journal of Polymer Science, Polymer Chemistry (ed. J, l'
olym, Sei, rPolyTa, CI+em, E
d,) Volume 12, 993K ((1974), Journal of Polymer Science, Polymer Letters 1!
(J, Polym, Sci, * Polym, Let
t, Ed, ) v tag, 71 Makoto (1975), etc., and a method for stabilizing dyes against light using a metal complex is described in JP-A-50-87649 and Research Disclosure.
Disclosure) No. 15162 (197
As described in 6), these complexes do not have a large anti-fading effect and do not have high solubility in organic solvents, so they cannot be added in an amount sufficient to exhibit an anti-fading effect. 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. 54-82388, No. 54-136581,
No. 54-136582, No. 55-12129, No. 5
No. 5-152750, No. 56-168652, No. 56
- No. 167138, No. 5 Fu No. 161744, Special Publication No. 5
No. 7-19770, etc.

However, even the above method is still insufficient to reduce the coloring of the complex itself. The negative influence on the hue and purity of colored substances, especially pigments or dyes, cannot be eliminated.

Furthermore, when these known metal complexes are applied to silver halide photosensitive materials (hereinafter referred to as color photographic materials), stains are likely to occur in the uncolored areas of the color photographic materials that have been developed. When processed color photographic materials are stored under conditions of high temperature and high humidity, the occurrence of contamination increases considerably.

[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 of improving the light stability of a color photographic image forming color photographic image without contaminating the uncolored portions of the color photographic material.

[Structure of the invention]

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

In the formula, R1 is a hydrogen atom, a furkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group,
represents an aryl group, a heterocyclic group, a 7-syl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulf-7 moyl group, or an oxycarbonyl group; R2 and R3 each represent a substituent; - or when n is 2 or more, multiple R2* or R
3 may be the same or different, and R'O and R2
are in adjacent positions, R'0 and R2 combine with each other to form 5
~7 may form a shell ring. Furthermore, when RIO and R3 or R2 and R3 are in a position where they can be closed to each other, R'O
and R3 or R2 and R3 may be bonded to each other to form a 5- to 7-shell ring, and X represents an atomic group necessary to form an inchroman or inkfuran ring.

The present invention will be explained in more detail below.

In the above general formula (1), the alkyl group represented by R' has 1 to 32 carbon atoms, the alkenyl group and alkynyl group have 2 to 32 carbon atoms, and the cycloalkyl group and cycloalkenyl group have 1 to 32 carbon atoms. Carbon number 3-1
2, particularly those of 5 to 7 are preferred, and the alkyl group, alkenyl group and alkynyl group may be linear or branched, and these groups may have a substituent, specifically,
Methyl, ethyl, t-butyl, pentadecyl, 1-hexylnonyl, 2-chloro-t-butyl, pencil, 2.
Examples include groups such as 4-not-aluminum-7enoxymethyl, 1-ethoxytridecyl, 7lyl, impropenyl, ethynyl, 2-flobinyl, cyclopentyl, cyclohexyl, and cyclohexenyl.

The aryl group represented by R1 is preferably a phenyl group or a naphthyl group, which may have a substituent.

R-i: phenyl, 4-nitrophenyl, 4
Examples thereof include groups such as -t-butylphenyl, 2,4-di-t-7mylphenyl, 3-hexadecyloxyphenyl, and α-su7tyl.

The heterocyclic group represented by R1 is preferably a 5 to 7 true heterocyclic group, which may be substituted (or may be fused,
i4: Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R1 include acetyl group,
Furkylcarbonyl groups such as phenyl 7cetyl group, dodeca/yl group, α-2,4-not-amyl 7enoxyptanoyl group, 7-arylcarbonyl group such as benzoyl group, 3-pentadecyloxybenzoylbenzoyl group, etc. Examples include groups.

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

The phosphonyl group represented by R1 includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, 7e7
aryloxyphosphonyl groups such as xyphosphonyl groups,
Examples include arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by R' may be substituted with a furkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, an N,N-butylcarbamoyl group, an N-( 2-bentadenruoctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl! ,,N-13-(2.4-di-t-7mil7
Examples thereof include (propyl)carbamoyl group and the like.

The sulfamoyl group represented by R' may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl group, N,N-butylcarbamoyl group, N- (2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-71nylsulfamoyl group, and the like.

The oxycarbonyl group represented by R' is preferably an alkoxycarbonyl group or an aryloquine carbonyl group. The alkoxycarbonyl group may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group, and the like. Moreover, the 7-aryloxycarbonyl group may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and a pentadecyloxyphenoxycarbonyl group.

The substituent represented by R2 and R3 is not particularly limited, but in addition to representing the same group as R1, it also includes a halogen atom, 7nily/, 7syl7mino, sulfone7mido, alkylthio, arylthio, sulfinyl, cyano, Alkoxy, aryloxy, heterocyclic oxy, heterocyclic thio, siloxy, acyloxy, carbamoyloxy, 7-mino, alkylamino, imide, ureido, sulfimoylamino, alkifukidicarbonyl 7-mino, aryloxycarbonylamino groups, Also included are Subia compound residues, endogenous hydrocarbon compound residues, and the like.

The 7syl7mi7 group represented by R2 and R3 includes alkylcarbonylamine7 group, arylcarbonylamine7 group,
Examples include groups.

Examples of the sulfonamide group represented by R2 and C/R' include an alkylsulfonylamino group and an arylsulfonylamino group.

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

Examples of sulfinyl group include furkylsulfinyl group, arylsulfinyl group, etc.; examples of 7-siloquine group include alkylsulfonyluoquine group,
Arylcarbonyloxy group ring; carbamoyloxy group such as furkylcarbamoyloxy group, 7lylcarbamoyloxy group; ureido group such as furkylureido group, arylureido group, etc.; group, arylsul7amoylamy7 group, etc.; As the heterocyclic oxy group, those having 5 to 7R heterocycles are preferable, such as 3,4,S,6-tetrahydropyranyl-2-oxy group, 1-7 22-tetrazole-5-
Oxy group ring: As the bicyclic thio group, a 5- to 7-shell heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-no7dinoxy-1,3, 5-) Riazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; Imide groups include succinimide group, 3-heptadecylsuccinimide group, 7-talimide group , glutarimide group, etc.; Spiro compound residues include spiro [3,3]hebutan-1-yl, etc.; bridged hydrocarbon compound residues include bicyclo [2゜2.
11 Hebutan-1-yl, tricyclo [3°3.1.
1'.7]decane-1-yl, 7.7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The compound represented by the general formula [I] according to the present invention is an isocoumaran compound represented by the following general formula CIa) or (
It is included in the inchroman compounds represented by Ib).

General formula (Ia) General formula (Ib) In general formulas (Im) and (Ib), R1, R2,
R3, ugly and n are R11 in the general formula (1)
R2, R3, plow and (synonymous with /n).

Furthermore, in general formula (It), when R'0 is at the 4th position and R3 is at the 3rd position, or when R'O is at the 7th position and R3 is at the 1st position, R'O and R3 are bonded to each other. may form a 5- to 7-membered ring. *In the general formula CI &), RI
When O is at the 5th position and R2 is at the 4th position, or when R'O is at the 8th position and R1 is at the 1st position, RIO and R3 can also be combined with each other to form a 5- to 7-membered ring. This means that in general formula (It) and general formula (Ib), RIo and R2
This also applies to cases where R2 and R are located at adjacent positions, or where R2 and R are located at positions where they can open the ring to each other.

Furthermore, the present invention also includes cases where the carbon atoms at the 1st and 3rd positions in the general formula (Ia) or the carbon atoms at the 1st, 3rd and 4th positions in the general formula (Ib) are spiro carbon atoms. In addition, two R3s at the 3rd and 4th positions of the general formula [:Ib]
may be combined with each other to form 5 to 7 shell rings.

In the present invention, R of the compound represented by general formula (I)
It is particularly preferred that ' is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.

Next, typical specific examples of the compound represented by the general formula [I] (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^-30 Synthesis methods for compounds are known, for example, Pharmaceutical Journal, 1974, Vol. 94 (6), pp. 774-776; Same Magazine, 1976, Vol. 96 (8), pp. 1031-103.
Page 5, US Patent 4. o21.451, JP-A-52-8
It can be synthesized according to the method described in No. 3846, No. 52-105174, 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, 7
It includes all dyes belonging to the classification of dyeing properties such as insoluble dyes such as Zoych dyes, oxidation dyes, and reactive dyes.

These organic coloring substances are mixed at 30°N in methanol solution.
- to 800am, 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 (anone dyes, oxazine dyes, thianone dyes, etc.), methine and polymethine dyes (cyanine dyes, azomethine dyes, etc.), azo dyes, and anthofquinone dyes. indoamine and indophenol dyes,
It includes dyes belonging to chemical structural classes such as 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 and indoamine and indoenol dyes, such as polymethine, indoamine, indo7er/- and formazan dyes. This dye includes metal compounds having the following groups.

Among the above groups, the phenyl group represents an unsubstituted 7enyl group or a substituted phenyl group, such as a phenyl group substituted with an alkyl group, an alkoxy group, a halogen atom, an amine 7 group, or the like.

Dye-forming couplers suitable for use in the present invention include yellow, magenta and yellow dye-forming types. This coupler is described in US Pat. No. 3,277.155, for example.
and 3,458,315, so-called 4-equivalent type, or substituted with a substituent (split-off group) that terminates when the carbon atom at the coupling position leaves during the coupling reaction. It may also be a 2-equivalent type.

Preferred examples of yellow dye image-forming couplers in the present invention include benzoylacetanilide type and pivaloylaceto 7ylide type couplers, and examples of maze/yellow dye image-forming couplers include 5-virazolone type, pyrazolotriazole type and imiguzolone type couplers. There are birazole-based, pyrazolopyrazole-based, pyrazolotetrazole-based, virazolinobenzimiguzole-based, and ingzolone-based couplers, and cyan dye image-forming couplers include phenol-based, naphthol-based,
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.

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

The following margin Y-1' I I l r〃 l ``ρ rσ These yellow couplers are used in
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. 51-102636, 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, typical examples of magenta couplers that can be used in the present invention will be listed.

Margin below −ノ′ C.I. C.I. CI1 2H5 C.I.

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. 1,252,418, British Patent No. 1,334.515, Japanese Patent Application Publication No. 171956/1983,
No. 59-162548, No. 60-43659, No. 6
No. 0-33552, Research Disclosure + -H
o. 24626 (1984), patent application No. 59-2430
No. 07, No. 59-243008, No. 59-24300
No. 9, No. 59-243012, No. 60-70197, No. 6G-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.

/ ゝTherefore. Lower remainder i CI CI e H These cyan couplers are disclosed in, for example, U.S. Pat.
．． No. 730, No. 2,801,171, Machiyami Sho 50-1
No. 12038, No. 50-134644, No. 53-10
No. 9630, No. 54-55380, No. 56-6513
4, No. 56-80045, No. 57-155538, No. 57-204545, No. 58-98731, No. 59-31953, etc., and methods described therein. It can be synthesized according to

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

The above developers include aminophenol and 7-ethylenediamine, and these developers can be used in combination.

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

[Example developer]

D-I D-2 D-3D-4 1; Js l; Js
ShiJs L;H2C;huHD-5D
-6 Examples of other dyes that can be used as coloring compounds in the present invention include the following.

H C Sushi 2H% NIISO2C111 Furthermore, other types of dyes preferably used in the present invention include U, S, +3351,673, U.S. Patent No. 3,93
2.381, 3,928.312, 3,931
, No. 144, No. 3,954,476, No. 3,929,
No. 760, No. 3,942,987, No. 3,932゜3
No. 80, No. 4,013,635, No. 4,013,63
No. 3, Special Ijlf No. 113624, No. 51-1, No. 51-1
No. 09928, No. 51-104343, No. 52-48
No. 19, No. 53-149328, Research Disclosure No. 15157 (1976), No.
, 13024' (1975), etc., 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 No. 840,731, British Patent No. 904,364, British Patent No. 932,272, British Patent No. 1,014,725, British Patent No. 1
, No. 038,331, No. 1,066.352, No. 1,
No. 097,064, JP-A-51-133021, US
T900,029 (U, S, Defensive P
publication), U.S. Patent 3,227,550
Dyes released by the reaction of the lk DDR coupler with the oxidized form of the color developing agent or dyes formed by the reaction with the oxidized form of the color developing agent can be mentioned.

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. Tributary dyes that can be used for this purpose include Direct 77 St Yellow CC (C.

1.29000), Glisophenin (C, 1,248
7zo dyes such as 95), Innogo Golden Yellow 1
niK (C, I.

59101), Ink Gozol Yellow 2 GB (C0
1,61726), Fluvosol Yellow QC^-CF
(C0I, 67301), F to Genthrene Yellow (C,!, 68420), Mikethrene Yellow GC
(C, 1,67300), Genthrene Yellow 4
Examples include benzoquinone dyes such as K (C, 1,88405); anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes.

As a magenta dye, Sumilite Sabralbinol B
(C0■, 29225), 7zo dyes such as Penzoprillant Galanin B (C, 1,15080), Indigosol Brilliant Pink IR (C01,73361)
), Indigosol Violet 15R (C, I, 59
321), Innovosol Red Violet IRRL
(C, I, 59316), Indanthrene Red Violet RRK (C1I, 67895), Mikethrene Brilliant Violet BBK (C, L6335)
and other innovoid dyes; soluble vat dyes made of benzoquinone-based and anthraquinone-based heteropolycyclic compounds; and other vat dyes.

As for cyan dye, Direct Sky Blue 6 B
(C, I, 24410), Direct Brilliant Blue 2 B (C, I, 22610), Azo dyes such as Sumilite Subrable-G (C01, 34200), Sumilite Sapra Turkey Blue C (C, 1, 7418)
0), Mikethren Brilliant Plue 4 G (C, 1
, 74140), Ingen Stremble Turkey Sprue 5G (C, 169845), Indan Stremblu-GCD (C, 1°73066)
, Indigosol 04G (C, 1,73046), Anthrazole Green 1B (C, I, 59826), and the like.

Compounds of the present invention are oil-soluble and are commonly used in U.S. Pat.
, 801゜171, No. 2,272,191 and No. 2,304.940, it is dissolved in a high boiling point solvent and, if necessary, a low boiling point solvent, and dispersed to make it hydrophilic. It is preferable to add it to the colloid m 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.Moreover, to explain the method of adding the compounds of the present invention in detail, one or more of the compounds may be added to the coupler as necessary. , hydroquinone derivatives, ultraviolet absorbers or known dye image fading inhibitors, etc., and organic acid amides, carbamates, esters, ketones, hydrocarbons, urea derivatives, etc., especially dibutyl heptatarate, tricresyl phosphate, etc. For high boiling point solvents such as di-octyl 7-gelate, butyl sepacate, trihexyl phosphate, decalin, H,H-noethylcapryl 7mide, N,N-diethyl laurylamide, pentadecyl phenyl ether or fluoroparaffin. If necessary, dissolve in a low boiling point solvent such as ethyl acetate, butyl acetate, butyl propionate, cyclohexyl, cyclohexane, or tetrahydrofuran.
(These 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. It is mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing a nonionic surfactant such as a monolauric acid ester, and emulsified and dispersed using a high-speed rotation mixer, colloid mill, or ultrasonic dispersion VCA, and the resulting dispersion is made hydrophilic. It can be used by adding it to a colloidal solution (for example) a silver lodenide emulsion).

Both the colorant and the compound of this invention can be present in any or several of the parent colloid layers in the photographic element. These substances include photosensitive elements and
The coloring substances which may be present in non-light sensitive elements such as dye image receptors used in photographic diffusion film units and the compounds of the present invention are included in such non-light sensitive image recording elements. If the dye is to be stabilized, it is preferred that they be mordanted; therefore, for such uses, the compounds of the present invention are preferably mordanted in order to prevent them from migrating away from the dye to be stabilized. It must have a molecular form that allows it to be retained in the body's mordant layer.

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 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 antifoggants 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 to maintain stable photographic performance. Compounds listed 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 containing a coupler in a developer. Processed according to the law 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. These steps can even be completed by performing two or more steps in one bath, such as bleach-fixing. 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-Methylamine/phenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-tmethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 3-methoxy-N,N -diethyl-p-phenylenecyamine, etc. can be used.

When the method of the present invention is applied to photographic materials, color positive film, color paper, color negative film, color reversal film, color expansion rI1. Examples include various color photographic materials such as photosensitive film units for photographic use and photosensitive materials for bleaching silver dyes.

〔Example〕

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

Example 1 0.5 g of magenta dye having the following structure (absorption maximum 583 nm in metal solution) I was dissolved in 4 liters of trioctyl phosphate and 8 ml of ethyl acetate, and this solution was dissolved in 0.5% dodecylbenzene. 10% sodium sulfonate aqueous solution containing 2 liters
The gelatin solution was emulsified and dispersed in 10 μm.

Next, this emulsified dispersion was mixed with 30 parts of a 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, the comparative compounds represented by the following supplementary formulas (,) and (b) were each added at 0%
．． 5g was added and coated in the same manner as Sample No. 1 above to prepare Samples No. 2 and No. 3.

Further, when preparing the emulsified dispersion liquid by the method of the above sample No. 1, as shown in Table 1, 0.5 tr of each of the exemplary compounds of the present invention was added and applied in the same manner as the above sample No. 1. Twelve 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 exposed to a xenon 7 ademeter for 200 hours, and the light resistance of the dye image was determined. I looked into gender. The results are shown in Table 1. However, the light resistance of the dye image was determined based on the dye residual rate.

Table 1 As is clear from Table 1, the samples using the anti-fading agent of the present invention (Nos. 4 to 15) had better photofading than the samples using the known gold III complexes (Nos. 2 and 3). It showed a preventive effect, and almost no dark brown discoloration, which tends to occur, 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).
15 types of samples (Nos. 16 to 30) were prepared in the same manner as in Example 1 except that the samples were changed to

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) Table 2 Table 2 also shows that the sample using the anti-fading agent of the present invention has a superior photo-fading preventing effect than the sample using the known metal 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 fastness test.

Example 3 Example coupler (M-8) 30g as magenta coupler
w) 30ml of 7-ethylphenylphosate and 11 ethyl acetate
5% gelatin aqueous solution containing 2.5 g of sodium dodecyl lebenzenesulfonate.
After adding to 0 affi, it was dispersed with a homogenizer, and the resulting dispersion was mixed with green photosensitive silver chlorobromide (silver chloride 30 mol%).
Contains) Emulsion 1,0OOa*l and N,N',N''-triacryloylhexahydro-5- as a hardening agent.
) 10 liters of a 2% methanol solution of Rhiannon was added, coated on polyethylene coated paper and dried to obtain a sample of a monochromatic color photographic material. This sample is designated as No. 31.

When preparing the above emulsified dispersion in the same manner, comparative compounds (c) and (d) having the following structures were added in an amount of 24 g each, and then applied in the same manner to prepare samples No. 32 and No.

33 was created.

Furthermore, as shown in Table 3, exemplified compounds of the present invention were each added to 20. 7 types of samples (No.

34-40) were created.

Comparative compound (c)... Compound OCJ+ described in JP-A No. 54-48538 Comparative compound (d)... Compound described in JP-A-56-159644 After exposing each of these samples, the following Nodokoro J! Ij solution and processing steps.

[Developer]

Benzyl alcohol 12.0s+/Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.9g Sodium bromide 1.4g Potassium bromide
0.5g sodium carbonate
30,0゜N-ethyl-N-β-7 tansulfone 7mi 1'ethyl-4-7mi/aniline sulfate 5
, 0g water is added to bring the volume to 11, and the pH is adjusted to 30 using sodium hydroxide.

[Bleach-fix solution] Ethylenediaminetetraacetic acid iron ammonium ei, og Ethylenediaminetetraacetic acid I! l! 2 Ammonium 5.0 g Ammonium thiosulfate 124.5° Ammonium metabisulfite 13.3 g Anhydrous sodium sulfite 2.7 g Add water to make 11, and adjust to pH 6.5 using aqueous ammonia.

[Processing process] (30℃) Processing time Development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Washing with water
Dry for 3 minutes. Each sample with a dye image formed in this way is coated with a Kodak Wratten Filter N, an ultraviolet cut filter.
A fading test was carried out for 150 hours in xenon 7°C 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 (Absorption size of colored magenta dye in methanol solution is 536n ring t'AraL-) As is clear from the results in Table 3, the anti-fading agent of the present invention is superior to the conventional organic anti-fading agent. It has better anti-fading effect than other agents.

Example 4 Exemplary coupler (C-6) 358 was used as a cyan coupler with dioctyl 7 tallate 35-1 and ethyl acetate 100m
After adding the solution dissolved in F to 500 liters of a 5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate, the dispersion was dispersed using a homogenizer, and the resulting dispersion was mixed with red-sensitive silver chlorobromide (silver chloride 30 g). (mol% content) Emulsion 1
．． Added to OOOmN, N, H', N'' as a hardening agent
-triacryloylhexahydro-S-triacin 2
% methanol solution was added, and the mixture was 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, a comparative compound (e) having the following structure and an exemplary compound of the present invention as shown in Table 4 were added to 15. 9 kinds of samples (No. 4
2-50) were created.

Comparative compound (e): Compound described in Machiya Sho 59-87456 After exposing each of these samples, the dye image obtained by processing in exactly the same manner as in Example 3 was filtered with an ultraviolet cut filter (
A fading test was carried out for 250 hours using a xenon 7 ademeter with the same material used in Example 3. The results are shown in Table 4.

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

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

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

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

PVP...Polyvinylpyrrolidone (K-30) solid heat solvent...p-IF dibenz7mid liquid heat solvent...
1.2.4-Butanetriol Reducing agent: The following reducing agents A and B are mixed in a 7:3 (molar ratio) daytime margin (A) (B) Organic silver salt: 5-methylbenzotriazole silver photosensitivity Silver halide: The same silver halide as described in the Examples of Japanese Patent Application No. 61-254257 was used.

Yellow dye-providing substance (Y-CPM) L x:y=80:20 (weight ratio) Margin below Magenta dye donor (M-CPH) H3 Cyan dye donating substance (C-CPM) CI(.

N x:y=60:40 (weight ratio) The following margins are shown in silver equivalent values) Preparation of thermal development image-receiving element> Photographic baryta paper (thickness 170 μl 1 weight 190 g/z
2) Apply the following image-receiving M coating solution on top to a wet film thickness of 137.2 μm.
A heat-developable image-receiving element was prepared by coating and drying (Sample No. 51).

(Image-receiving layer coating liquid) Polyvinyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., n = 1,100) 21
．． 0g Tetrahydro 7ran 190zi' When preparing the above image-receiving layer coating solution in the same manner, add 0.8g each of the comparative compound, ultraviolet absorber, and exemplified compound of the present invention as shown in Table 6. 0.4 g each) and applied in the same manner as Sample No. 51 above to create nine types of samples (No. 52 to 60).

In the heat-developable photosensitive element, the element was exposed to 4000 cm S of tungsten light through a step wedge and a green filter.
Pressure heating (thermal development) was performed at 50° C. for 90 seconds. Preheating and compression heating are performed according to Japanese Patent Application Laid-open No. 61-15365.
The thermal development loading amount shown in Figure 2 of No. 1 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 Properties) The maximum reflection density and minimum reflection density of the magenta image were measured using Sakura Densitometer PD^-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-Test Instrument-E-6X-IC), and the dye concentration residual rate (%) was examined. Ta.

Margin below Table 6 This ultraviolet absorber (UV-1) This 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 the ultraviolet light absorbing agent in combination, the anti-fading effect is further improved.

〔Effect of the invention〕

By allowing the photofading inhibitor according to the present invention to exist with an organic coloring substance, it is possible to significantly reduce the fading caused by light of organic coloring substances, such as pigments and dyes 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, or an oxycarbonyl group, and R^2 and R^3 each represent a substituent. m represents an integer from 0 to 3, and n represents an integer from 0 to 3.
Represents an integer of 4. When m or n is 2 or more, multiple R^2 or R^3 may be the same or different, and R^1O and R^2
When R^1O and R^2 are located at adjacent positions, R^1O and R^2 may be bonded to each other to form a 5- to 7-membered ring. Furthermore, R^1O and R^
3 or R^2 and R^3 are in a position where they can be ring-closed with each other, R^1O and R^3 or R^2 and R^3 may be combined with each other to form a 5- to 7-membered ring. . X represents an atomic group necessary to form an isochroman or isocoumaran ring. ]