JPH0697333B2 - Method for preventing photo-fading of organic coloring substances - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for preventing photobleaching of an organic coloring substance.

[Background of the Invention]

It is widely known that organic coloring substances generally have a tendency to fade with light. In the field of inks, dyes of fibers, or color photography, research has been conducted to prevent the photo-fading property of such organic coloring substances.

The present invention, for the purpose of preventing photofading of such organic coloring substances,
Used extremely advantageously.

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

Also, as used herein, the term light means an electromagnetic wave of from about 300 nm to about 800 nm or less, ultraviolet light of less than about 400 nm, visible light of about 400 nm to about 700 nm, and about 700 nm to about 800 nm.
Includes nm infrared.

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

In the field of silver halide color photographic light-sensitive materials, the dye image obtained from the coupler is exposed to light for a long time,
It is desirable that it does not discolor even when stored under high temperature and high humidity.

However, it is known that the fastness of these dye images, mainly to ultraviolet rays or visible rays, is not satisfactory, and that they are easily discolored when irradiated with these active rays. In order to eliminate such defects, conventionally,
A method of selecting and using various couplers with low fading property, using an ultraviolet absorber to protect the dye image from ultraviolet rays, or introducing a group imparting light resistance to the coupler has been proposed. ing.

However, for example, in order to give a satisfactory light resistance to a dye image using an ultraviolet absorber, a relatively large amount of the ultraviolet absorber is required, and in this case, the coloring of the ultraviolet absorber itself significantly contaminates the dye image. It was sometimes done. 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 improvement of light resistance by the ultraviolet absorber. Furthermore, a method of using a dye image anti-fading agent having a phenolic hydroxyl group or a group which is hydrolyzed to form a phenolic hydroxyl group is known, for example, JP-B-48-31256 and 48-31625.
51-30462, JP-A-49-134326 and JP-A-49-134327, phenol and bisphenols, U.S. Pat.
No. 262, pyrogallol, gallic acid and its esters, U.S. Pat.Nos. 2,360,290 and 4,015,990 include α-
Tocopherols and their acyl derivatives, JP-B-52-2
7534, JP-A-52-14751 and U.S. Pat.No. 2,735,765 include hydroquinone derivatives, U.S. Pat.
6-hydroxychromans in US 3,574,627, US patent
It is proposed to use a 5-hydroxychroman derivative in 3,573,050 and 6,6'-dihydroxy-2,2'-spirobichroman derivative in Japanese Patent Publication No. 49-20977. However, these compounds are not sufficient although they are effective as a discoloration preventing agent and a discoloration preventing agent for dyes.

Further, it is described in British Patent 1,451,000 to improve the light stability of an organic coloring compound by using an azomethine quenching compound whose absorption peak is bathochromic than the peak of the coloring compound. Since the azomethine quenching compound itself is colored, it greatly affects the hue of the coloring substance, which is disadvantageous. In addition, the use of metal complexes to prevent photo-deterioration of polymers is described in Journal of Polymer Science, Polymer Chemistry (J.Polym.Sci., Poly.
m.Chem.Ed.) Vol. 12, p. 993 (1974), Journal of Polymer Science, Polymer Letter (J.Polym.Sc)
i., Polym. Lett. Ed.), vol. 13, p. 71 (1975), and a method for stabilizing a dye with light by a metal complex is disclosed in JP-A-50-87649 and Research. Research Disclosure No.15162 (197
As described in 6), these complexes are not very effective in fading prevention itself and their solubility in organic solvents is not high, so it is not possible to add an amount sufficient to exert a fading prevention effect. Furthermore, since these complexes have a large coloring themselves, if added in a large amount, they adversely affect the hue and purity of the organic coloring substance, especially the dye.

Further, a method of photostabilizing a dye with various metal complexes is disclosed in JP-A-54-62826, JP-A-54-62987, JP-A-54-65185, and JP-A-54-695.
No. 80, No. 54-72780, No. 54-82384, No. 54-82385,
54-82386, 54-136581, 54-136582, 55-121
No. 29, No. 55-152750, No. 56-168652, No. 56-167138
No. 57-161744, Japanese Patent Publication No. 57-19770.

However, even by the above method, it is still insufficient to reduce the coloring of the complex itself.
In particular, it is not possible to eliminate the adverse effect on the hue and purity of the pigment or dye. Further, when these publicly known metal complexes are applied to a silver halide color photographic light-sensitive material (hereinafter referred to as a color photographic material), the uncolored portion of the developed color photographic material is likely to be contaminated. In particular, when the developed color photographic material is stored under the conditions of high temperature and high humidity, the generation of contamination remarkably increases.

[Object of the Invention]

It is an object of the present invention to provide a method of improving the stability of organic coloring substances to light.

Another object of the invention is to provide a method for improving the light stability of organic coloring substances, in particular dyes or dyes, without degrading the hue and the purity of these substances.

Yet another object of the present invention is to provide a method of improving the light stability of a color image forming a color photographic image without causing contamination of the undeveloped areas of the color photographic material.

[Structure of Invention]

The above object of the present invention is to provide an organic coloring substance and the following general formula [I].
It is achieved by coexisting with at least one kind of the compound represented by

General formula [I] In the formula, R represents a substituent, and n represents an integer of 0 to 6. n
When is 2 or more, plural Rs may be the same or different.

Hereinafter, the present invention will be described more specifically.

In the general formula [I], the substituent represented by R is not particularly limited, but typically, each of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Examples thereof include a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, hydroxyl, alkoxy, cycloalkoxy, aryloxy, heterocycleoxy, siloxy, and the like. Acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio Each group, and a spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

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

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

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

Examples of the sulfonamide group represented by 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 R include the alkyl group and aryl group represented by R above.

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

The cycloalkenyl group represented by R has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group. , An arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .; a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl group and the like; as the acyloxy group, an alkylcarbonyloxy group,
Arylcarbonyloxy group etc .; Carbamoyloxy group as alkylcarbamoyloxy group, arylcarbamoyloxy group etc .; Ureido group as alkylureido group, arylureido group etc .; Sulfamoylamino group as alkylsulfamoylamino group, aryl Sulfamoylamino group, etc .; The heterocyclic group is preferably a 5- to 7-membered one, specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc .; heterocyclic oxy group Is preferably a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-
2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2 , 4-Diphenoxy-1,3,5-triazole-
6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc .; As a spiro compound residue, spiro [3.3] heptane-1
-Yl etc .; as the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decane-
1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

In the general formula [I], when two Rs are adjacent to each other,
Two Rs may combine with each other to form a 5- to 7-membered ring. The present invention also includes the case where the carbon atom at the 2-position and / or the 4-position is a spiro carbon atom.

General formula [I] 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.

Methods for synthesizing these compounds of the present invention are known, for example, U.S. Patent No. 4,056,540, West German Published Patent Nos. 2,637,947, and 2,74.
It can be synthesized according to the method described in 9,279 and the like.

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 present invention.

Organic coloring substances used in the present invention, basic dyes, acid dyes, direct dyes, water-soluble dyes such as soluble vat dyes, mordant dyes, sulfur dyes, vat dyes, oil-soluble dyes, disperse dyes, azoic dyes, Insoluble dyes such as oxidation dyes, or dyes belonging to the class of dyeing properties such as reactive dyes are included. These organic coloring substances have at least one absorption maximum in methanol solution from 300 nm to 800 nm, preferably from 400 nm to 700 nm.

Among these dyes, the dyes preferably used in the present invention include quinone imine dyes (azine dyes, oxazine dyes, thiazine dyes, etc.), methine and polymethine dyes (cyanine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoamines and Indophenol dyes, indigoid dyes, carbonium dyes, formazan dyes, and other dyes belonging to the chemical structure classification are included.

The organic coloring substance used in the present invention is an image forming dye used in the field of photography, for example, a color coupler, a DRR compound, a DDR coupler, a dye formed from an amidrazone compound dye developing agent, a silver dye bleaching dye, etc. Include all.

Dyes preferably used as the organic coloring substance of the present invention, anthraquinone, quinone imine, azo, methine,
Examples 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.

In the above groups, the phenyl group represents an unsubstituted phenyl group or a substituted phenyl group, for example, an phenyl group substituted with an alkyl group, an alkoxy group, a halogen atom or an amino group.

Dye forming couplers suitable for use in the present invention include those of the yellow, magenta and cyan dye forming types. This coupler is a so-called 4 coupler as described, for example, in U.S. Pat. Nos. 3,277,155 and 3,458,315.
It may be an equivalent type or a two equivalent type in which the carbon atom at the coupling position is substituted with a substituent (split-off group) capable of leaving during the coupling reaction.

Preferred yellow dye image-forming couplers in the present invention include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type, imidazopyrazole type and pyrazolopyrazole. system,
There are pyrazolotetrazole type, pyrazolinobenzimidazole type and indazolone type couplers, and cyan dye image forming couplers include phenol type, naphthol type and pyrazoloquinazolone type couplers.

Specific examples of these yellow, magenta and cyan dye-forming couplers are known in the photographic art, and all known couplers are included in the present invention.

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

These yellow couplers are, for example, West German Published Patent No. 2,05
7,941, West German published patent 2,163,812, JP-A-47-26133
No. 48, No. 48-29432, No. 50-65321, No. 51-3631, No. 51-
50734, 51-102636, 48-66835, 48-94432
No. 49-1229, 49-10736, Japanese patent 51-33410,
The compounds described in JP-A No. 52-25733 and the like 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 given.

These magenta couplers are described, for example, in U.S. Pat.
4, British Patent 1,183,515, Japanese Patent Publication Nos. 40-6031, 40-60
35, 44-15754, 45-40757, 46-19032, JP-A-50-13041, 53-129035, 51-37646, 55-
62454, U.S. Patent 3,725,067, British Patent 1,252,418
No. 1,334,515, JP-A-59-171956, 59-162548.
No. 60-43659, No. 60-33552, Research Disclosure No.24626 (1984), Japanese Patent Application No. 59-243007, No. 5
9-243008, 59-243009, 59-243012, 60-701
No. 97, including compounds described in 60-70198,
And it can be synthesized according to the methods described therein.

The cyan coupler used in the present invention is not particularly limited, but a phenol cyan coupler is preferable.

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

These cyan couplers are described, for example, in U.S. Pat.
No. 2,801,171, JP-A-50-112038, 50-134644
No. 53, No. 53-109630, No. 54-55380, No. 56-65134, No. 5
6-80045, 57-155538, 57-204545, 58-9873
No. 1, 59-31953 and the like, and can be synthesized according to the methods described therein.

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

The above-mentioned developers include aminophenol and phenylenediamine, and these developers can be mixed and used.

Among the developers that can be combined with various couplers to form colored compounds according to the present invention, representative examples thereof are listed below.

[Exemplary developer] Examples of other dyes that can be used as the coloring compound in the invention include the followings.

Furthermore, other types of dyes preferably used in the present invention include USB351,673, U.S. Pat.Nos. 3,932,381, and 3,928,3.
No. 12, No. 3,931,144, No. 3,954,476, No. 3,929,760
No., No. 3,942,987, No. 3,932,380, No. 4,013,635,
4,013,633, JP-A-51-113624, 51-109928,
51-104343, 52-4819, 53-149328, Research Disclosure No. 15157 (1976), No. 130
24 (1975) and the like, and dyes formed by oxidation of DRR compounds can be mentioned.

Furthermore, other types of dyes used in the present invention include:
For example, British Patents 840,731, 904,364, 932,272
No. 1,014,725, 1,038,331, 1,066,352,
1,097,064, JP-A-51-133021, UST900,029 (US
Defensive Publication), U.S. Pat. No. 3,227,550, and the dyes released by the reaction of the DDR coupler with the oxidant of the color developing agent or the dye formed by the reaction with the oxidant of the color developing agent. it can.

Other types of dyes preferably used in the present invention include Japanese Patent Publications No. 35-182, No. 18332, No. 48-32130, and No. 46-
Examples thereof include dye developing agents described in Nos. 43950 and 49-2618.

Furthermore, other dyes used in the present invention include various dyes used in the silver dye bleaching method. Examples of yellow dyes that can be used for this purpose include direct fast yellow GC (CI29000), azo dyes such as glysophenin (CI24895), indigo golden yellow IGK (CI59101), and indigosol yellow 2G.
B (CI61726), Argosol Yellow GCA-CF (CI67
301), indanthrene yellow GF (CI68420), Mikeslen yellow GC (CI67300), indanthrene yellow 4GK (CI68405), and other benzoquinone dyes; anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes And so on. As a magenta dye,
Azo dyes such as Sumilite Sapra Rubinol B (CI29225) and Benzo Brilliant Keranin B (CI15080), Indigozol Brilliant Pink IR (CI7336
1), indigosol violet 15R (CI59321),
Indigo Zol Red Violet IRRL (CI5931
6), Indanthrene Red Violet RRK (CI6789
5), Mike Slen Brilliant Violet BBK (CI63
35) and other indigoid dyes; soluble vat dyes composed of benzoquinone and anthraquinone heteropolycyclic compounds, and other vat dyes.

As a cyan dye, Direct Sky Blue 6B (CI
24410), Direct Brilliant Blue 2B (CI2261
0), azo dyes such as Sumilite Supra Blue G (CI34200), Sumilite Supra Turkeys Blue G (CI74
180), Michelin Brilliant Blue 4G (CI74140)
Phthalocyanine dyes such as Indanthrene blues 5G (CI69845), Indanthrene blue GCD (C.
I.73066), indigosol 04G (CI73046), anthrazole green IB (CI59826) and the like.

The compounds of the present invention are generally oil-soluble and are commonly described in US patents.
2,322,027, 2,801,170, 2,801,171, 2,27
According to the method described in No. 2,191 and No. 2,304,940, in a high-boiling solvent, if necessary, dissolved in combination with a low-boiling solvent,
It is preferable to disperse and add to the hydrophilic colloid solution,
At this time, if necessary, a coupler, a hydroquinone derivative, an ultraviolet absorber or a known dye image fading preventing agent may be used in combination. At this time, there is no problem even if two or more compounds of the present invention are mixed and used. If the method for adding the compound of the present invention is further described in detail, one or more of the compounds may be added to a coupler, a hydroquinone derivative, an ultraviolet absorber or a known dye image antifading agent at the same time as an organic acid. Amides, carbamates, esters, ketones, hydrocarbons and urea derivatives, etc., especially dibutyl phthalate, tricresyl phosphate, di-i-octyl azelate, dibutyl sebacate, trihexyl phosphate, decalin, N, N -Diethylcaprylamide, N, N-diethyllaurylamide,
Dissolve in a high boiling solvent such as pentadecyl phenyl ether or fluoroparaffin, if necessary, in a low boiling solvent such as ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran (these high boiling solvents and low boiling solvents). The boiling point solvents may be used alone or in combination.) Anionic surfactants such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and / or nonionic interfaces such as sorbitan sesquioleate and sorbitan monolaurate It is mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing an activator, and the mixture is emulsified and dispersed using a high-speed rotary mixer, colloid mill or ultrasonic dispersion device, and the resulting dispersion is a hydrophilic colloid solution (eg silver halide emulsion). ) Added to , It can be used.

Both the colorant and the compounds of this invention can be present in any or some of the hydrocolloid layers in the photographic element. These materials may be present in the light-sensitive element and in non-light-sensitive elements such as dye image receivers used in photographic diffusion transfer film units. When colorants and compounds of the invention are included in such non-photosensitive image recording elements, they are preferably mordanted. Thus, for such use, the compounds of the invention will have a molecular form such that they can 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

In the photographic light-sensitive material used in the method of the present invention, the silver halide emulsion is generally a silver halide grain dispersed in a hydrophilic colloid, and as the silver halide, silver chloride, silver bromide, silver iodide, Silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof.

These silver halide emulsions can be optically sensitized with various sensitizing dyes in order to impart photosensitivity in a desired light-sensing 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 fog during the manufacturing process of light-sensitive materials, storage or photographic processing, and / or keeping photographic performance stable. A compound can be added.

In addition, various photographic additives such as hardeners, plasticizers, optical brighteners, antistatic agents, coating aids, etc. may be used individually or in combination.
A combination of two or more species can be added and used.

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.

The coupler-containing internal color photographic material is processed according to a conventional method to obtain a color image. The main steps in this case are color development, bleaching, and fixing, and steps such as washing with water and stabilization may be included if necessary. These steps can also be carried out in one bath for two or more steps such as bleach-fixing. Color development is usually performed in an alkaline solution containing an aromatic primary amine developing agent. Preferred specific examples of the aromatic primary amine developing agent are described above 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 color diffusion transfer film unit, the processing of the photographic material is automatically performed inside the light-sensitive material. In this case, the developing agent is contained in the 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-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 3-methoxy-N, N -Diethyl-
For example, p-phenylenediamine can be used.

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

[Examples] Hereinafter, the present invention will be described with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Magenta dye having the following structure (absorption maximum 583 nm in methanol solution) 0.5 g of trioctyl phosphate 4 ml and ethyl acetate 8
10 ml of 10% gelatin solution containing 2 ml of 0.5% sodium dodecylbenzenesulfonate aqueous solution.
Emulsified and dispersed.

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

When the above-mentioned emulsified dispersion liquid was prepared by the same method, the comparative compounds represented by the following structural formulas (a) and (b) were each added to the following formula:
Add 5 g and apply in the same manner as Sample No. 1 above to apply Sample No. 2
And No.3 were created.

Also, when making the emulsion dispersion by the method of the sample No. 1,
As shown in Table 1, 0.5 g each of the exemplary compounds of the present invention
Each of them was added and applied in the same manner as the above sample No. 1 to prepare 12 kinds of samples (No. 4 to 15).

Comparative compound (a) ... Metal complex described in JP-A-55-12129 Comparative compound (b) ... Same as above Each of the above samples was exposed to a xenon fade meter for 200 hours, and the light resistance of the dye image was examined. The results are shown in Table 1.
However, the light resistance of the dye image was determined by the dye residual ratio.

As is clear from Table 1, the samples using the anti-fading agent of the present invention (Nos. 4 to 15) have a better photo-fading prevention effect than the samples using the known metal complex (Nos. 2 and 3). In addition, a blackish brown discoloration was hardly observed.

Example 2 15 kinds of samples (No. 16 to No. 16) were prepared in the same manner as in Example 1 except that the magenta dye having the following structure was used instead of the magenta dye (absorption maximum in a methanol solution: 536 nm). 30) was created. The obtained sample was exposed to a xenon fade meter for 150 hours, and the light resistance of the dye image was examined. The results are shown in Table 2.

(Magenta dye) Also in Table 2, it can be seen that the sample using the anti-fading agent of the present invention has a superior photo-fading preventing effect to the sample using the known metal complex. Further, the sample according to the present invention showed almost no black-brown discoloration, and maintained a preferable hue even after the light resistance test.

Example 3 A solution prepared by dissolving 30 g of the exemplified coupler (M-8) as a magenta coupler in 30 ml of triphenyl phosphate and 100 ml of ethyl acetate was added to 500 ml of a 5% gelatin aqueous solution containing 2.5 g of sodium dodecylbenzenesulfonate, and then dispersed by a homogenizer. Then, the resulting dispersion was added to 1,000 ml of a green light-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion, and N, N ', N "-triacryloylhexahydro-s-triazine was used as a hardener. 10% of a 2% methanol solution of was added and dried on polyethylene-coated paper to obtain a sample of monochromatic color photographic material, which is designated as No. 31.

When the above emulsion dispersion was prepared by the same method, 24 g of each of the comparative compounds (c) and (d) having the following structures were added in the same manner to prepare Sample Nos. 32 and 33. .

Furthermore, as shown in Table 3, 20 g of each of the exemplified compounds of the present invention was added and coated in the same manner to prepare 7 types of samples (Nos. 34 to 40).

Comparative compound (c): Compound described in JP-A-54-48538 Comparative compound (d): Compound described in JP-A-56-159644 After exposing each of these samples, they were processed by the following processing solutions and processing steps.

[Developer]

Benzyl alcohol 12.0 ml Sodium hexametaphosphate 2.5 g Anhydrous sodium sulfite 1.9 g Sodium bromide 1.4 g Potassium bromide 0.5 g Sodium carbonate 30.0 g N-ethyl-N-β-methanesulfonamidoethyl-4
-Aminoalinine sulphate 5.0g Add water to make 1 and add sodium hydroxide to pH 1
Adjust to 0.30.

[Bleaching fixer]

Ethylenediaminetetraacetic acid ammonium ammonium 61.0 g Ethylenediaminetetraacetic acid diammonium 5.0 g Ammonium thiosulfate 124.5 g Ammonium metabisulfite 13.3 g Anhydrous sodium sulfite 2.7 g Water is added to adjust the pH to 1 using ammonia water.

[Treatment process] (30 ° C) Treatment time Current image 3 minutes 30 seconds Bleaching fixing 1 minute 30 seconds Water washing 3 minutes Drying Each sample on which a dye image was formed in this way, Kodak Latte, an ultraviolet cut filter, was used. Filter N
A fading test was carried out for 150 hours using a xenon fade meter with o.2A attached. The results are shown in Table 3.

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

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

Example 4 A solution of 35 g of the coupler (C-6) exemplified as a cyan coupler in 35 ml of dioctyl phthalate and 100 ml of ethyl acetate was dissolved in sodium dodecylbenzenesulfonate 2.
After adding to 500 ml of a 5% gelatin aqueous solution containing 5 g, the mixture was dispersed by a homogenizer, and the resulting dispersion was added to 1,000 ml of a red-sensitive silver chlorobromide (containing 30 mol% of silver chloride) emulsion to obtain N as a hardener. 10 ml of a 2% methanol solution of N, N ', N "-triacryloylhexahydro-s-triazine was added, and the mixture was coated on polyethylene-coated paper and dried to obtain a sample of a monochromatic color photographic material. .

When preparing the above-mentioned emulsion dispersion in the same manner as in Example 3, 15 g of each of the comparative compound (e) having the following structure and the exemplified compound of the present invention as shown in Table 4 was added to each of 9 kinds of samples (No. 42). ~ 50)
It was created.

Comparative compound (e): Compound described in JP-A-59-87456 After exposing each of these samples, a dye image obtained by treating in exactly the same manner as in Example 3 was attached with an ultraviolet ray cut filter (the same as that used in Example 3), and it was subjected to 250 hours with a Xekin fade meter. A fading test was performed. The results are shown in Table 4.

(The absorption maximum of the colored cyan dye in a methanol solution is 65
It was 2 nm. As is clear from Table 4, the anti-fading agent of the present invention has a large effect of preventing the photo-fading of the cyan coloring dye.

Example 5 Next, an example in which the present invention is applied to a photothermographic material is shown.

<Preparation of Photothermographic Element> The photothermographic element shown in Table 5 was prepared using the following materials.

Gelatin: 2: 1 of lime-processed gelatin for photography and phenylcarbamoylated gelatin (type 17819PC manufactured by Luslow)
Mixed by (weight ratio).

PVP ... Polyvinylpyrrolidone (K-30) Solid thermal solvent ... p-Butoxybenzamide Liquid thermal solvent ... 1,2,4-butanetriol Reducing agent ... The following reducing agents A and B are mixed in a 7: 3 (molar ratio) .

Organic silver salt ... 5-Methylbenzotriazole silver Photosensitive silver halide ... The same one as described in the examples of Japanese Patent Application No. 61-254257 was used.

Yellow dye donor (Y-CPM) Magenta dye donor (M-CPM) Cyan dye donor (C-CPM) <Preparation of heat-developable image-receiving element> On a photographic baryter paper (thickness 170 μm, weight 190 g / m ² ),
The following image-receiving layer coating solution was applied in a wet film thickness of 137.2 μm and dried to prepare a heat-developable image-receiving element (Sample No. 51).

(Image-receiving layer coating liquid) Polyvinyl chloride (manufactured by Wako Pure Chemical Industries, n = 1,100) 21.0 g Tetrahydrofuran 190 ml When preparing the above-mentioned image-receiving layer coating liquid by the same method, as shown in Table 6, a comparative compound and an ultraviolet absorber. Each of the exemplified compounds of the present invention was added in an amount of 0.8 g (0.4 g in the case of combined use) and coated in the same manner as in the above sample No. 51 to obtain 9 types of samples (No. 52-
60) was created.

The photothermographic element is exposed to a 4000 CMS tungsten light exposure through a step wedge and a green filter,
Apply the heat-developable image-receiving element and the coated surface to each other 10
After preheating at 0 ° C. for 4 seconds, pressure heating (heat development) at 150 ° C. for 90 seconds was performed. The pre-heating and the pressure-bonding heating used the heat developing apparatus shown in FIG. 2 of JP-A-61-153651.

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

(Evaluation of Photographic Properties) The maximum reflection density and the minimum reflection density of a magenta image were measured with a Sakura Densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) with green light.

(Evaluation of Light Stability) A sample having a magenta image was irradiated with light for 5 days and 10 days with a xenon fade meter (Suga Tester WE-6X-HC) to examine the residual ratio (%) of the dye concentration.

From Table 6, it can be seen that the anti-fading agent of the present invention exhibits an excellent anti-fading effect without deteriorating photographic characteristics even when used in a photothermographic material. Further, the combined use of the anti-fading agent of the present invention and the ultraviolet absorber further improves the anti-fading effect.

〔The invention's effect〕

By allowing the photobleaching inhibitor according to the present invention to be present together with an organic coloring substance, it is possible to remarkably reduce the discoloration due to light of the organic coloring substance, particularly a dye or dye used in a color photographic light-sensitive material.

Claims (1)

[Claims] 1. Photofading of an organic coloring substance, characterized in that the organic coloring substance and at least one compound represented by the following general formula [I] are allowed to coexist to prevent fading of the organic coloring substance to light. Prevention method. General formula [I] [In formula, R represents a substituent and n represents the integer of 0-6.
When n is 2 or more, plural Rs may be the same or different. ]