JPS63285547A - Method for preventing photofading of organic coloring material - Google Patents

Abstract

PURPOSE:To prevent fading by light of an org. coloring material by allowing the org. coloring material and specific fading preventive agent to co-exist. CONSTITUTION:The org. coloring material and the fading preventive compd. expressed by the formula are allowed to co-exist. In the formula, R<1> denotes a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkinyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, carbamoyl group, phosphonyl group, sulfamoyl group, oxycarbonyl group; R<2> denotes a group which can be substd.; m denotes 0, 1-6. Dyes for forming photographic images, for example, anthraquinone dye, general dyes, etc., in addition to colored couplers, etc., are used for the org. coloring agent. Since the photofading preventive agent and the org. coloring material are allowed to co-exist, the photofading of the org. coloring material, more particularly, the coloring matter and dye of a color photographic sensitive material is decreased.

Description

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

[Background of the invention]

It is generally known that organic coloring substances tend to fade due to light. ink, fiber.

Research is being conducted to prevent such photofading of organic coloring substances in the fields of 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 300nm-800n+ in methanol solution
s means an organic substance that has one absorption maximum.

Furthermore, in this specification, the term light refers to approximately 30 On
- means electromagnetic waves of approximately 800 nm or less, approximately 40 On
UV light from about 400 nm to about 70 nm and infrared from about 70 nm to about 800 nm.

There are many reports on methods for improving the light fastness of organic coloring substances, such as pigments or dyes. For example, U.S. Pat. By mixing organic compounds used in color photography, such as dyes, with phenolic-type compounds that have fused heterocyclic ring systems,
It is stated that the fastness to visible and ultraviolet light is improved.

In the field of silver herodide color photographic materials, Kab2-
The dye image obtained from is exposed to light for a long 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 rays is not satisfactory, and when irradiated with these actinic rays, they become dry! ! It is known to fade. In order to eliminate such drawbacks, conventionally, various couplers with low fading properties have been selected and used,
In order to protect the dye image from ultraviolet rays, methods have been proposed in which an ultraviolet absorber is used or a group imparting light resistance is introduced into the coupler.

However, in order to provide a satisfactory lightfastness to a dye image using, for example, a UV absorber, a relatively large amount of UV absorber is required, in which case the dye image is significantly contaminated due to the coloration of the UV absorber itself. I'm afraid I'll get hurt. 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 7-27-al hydroxyl group or a group that can be hydrolyzed to produce a 7-27-al hydroxyl group are known. 48-
No. 31625, No. 51-30462, Japanese Unexamined Patent Publication No. 49-1
:'14326 and 1.49-134327 have 7
E/L and BIS7 E/L, U.S. Patent No. 3,069
, 262 describes pyrrof-role, gallic acid and its esters, U.S. Pat.
No. 15,990 describes α-tocopherol neck and its acyl derivatives, Japanese Patent Publication No. 52-27534, Japanese Unexamined Patent Application Publication No. 1982-2753,
No. 14751, U.S. Patent No. 2,735.765 includes hydrocon derivatives, U.S. Pat. No. 3,432.300, U.S. Pat. No. 050 contains 5-hydroxychroman derivatives and Japanese Patent Publication No. 49-20977 contains 6
It has been proposed to use 6'-dihydroxy-2,2'-subia bichromans and the like. However, although these compounds are effective at preventing dyes from fading and from discoloration, 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 and adds +1, it is disadvantageous because it has a large influence 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 Op.
Polymer Science, Polymer Chemistry (J, P
olym, Sai, *Polys, Chss, Ed,)
12, 9931 (1974), Journal of Polymer Science, Polymer Letters 1i (J,
Polym, Sci, y Polyv, Lett, E
d,)s Vol. 13, p. 71 (1975), and methods for stabilizing dyes against light using metal complexes are described in JP-A-50-87649 and Research Disclosure.
Closure) No., t5162 (197B), but these complexes do not have a large anti-fading effect and do not have high solubility in organic solvents, so they must be used in an amount sufficient to exhibit the anti-fading effect. Further, since these complexes themselves are highly colored, 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.
- No. 65185, No. 54-69580, No. 54-72
No. 780, No. 54-82384, No. 54-82385
No. 54-8zass, No. 54-138581,
No. 54-136582, No. 55-12129, No. 5
No. 5-152750, No. 5B-168652, No. 56
-167138, 57-181744, Special Publication No. 5
No. 7-19770, etc.

However, even the above method is still insufficient to reduce the coloring of the complex itself, and it is not possible to eliminate the adverse effects on the hue and purity of colored substances, especially pigments or dyes.

Furthermore, when these known metal complexes are applied to silver herodenide color photographic materials (hereinafter referred to as "color photographic materials"), stains are likely to occur in the uncolored areas of the developed color photographic materials, especially during development. The occurrence of contamination increases significantly when processed color photographic materials are stored under conditions of high temperature and humidity.

[Purpose of the invention]

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

Another object of the present invention is to provide a method for improving the chemical stability of organic coloring substances, especially pigments and 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 [I]
rI1.f!= is achieved by a method for preventing photofading of an organic coloring substance, which requires the coexistence of one or more of the compounds represented by IFt.

General formula (1) In the formula, R' is a hydrogen atom, or an alkyl group, a cyclomolar group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, each of which may have a W1 substituent, Acyl group, sulfonyl group, carbamoyl group,
Represents a phosphonyl group, a sulf7moyl group, or an oxycarbonyl group.

R2 represents a substitutable group. Horse mackerel represents 0* or an integer from 1 to 6, and when - represents an integer from 2 to 6, a plurality of R2's may be the same or different and may be 6.

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 zoalkynyl group has 2 to 32 carbon atoms, and the cycloalkyl group and cycloalkenyl group has 3 to 1 carbon atoms
2, particularly those of 5 to 7 are preferred, and the alkyl group, alkenyl group and V 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, 2,4-! /-
Examples include groups such as t-7 milphenoxymethyl, 1-ethquintridecyl, allyl, impropenyl, ethynyl, 2-propynyl, cyclopentyl, cyclohexyl, and cyclohexenyl.

In the above general formula (1), the alkyl group represented by R1 has 1 to 32 carbon atoms, the alkenyl group and alkynyl group have 2 to 32 carbon atoms, and the cycloalkyl group and the cycloalkenyl group have 1 to 32 carbon atoms. Carbon number 3-1
2, particularly those of 5 to 7 are preferred, and the furkyl 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-hexyl/nyl, 2-chloro-[-butyl, 2,4-sheet t
-7-milphenoxymethyl, 1-ethquintridecyl,
7lyl, impropenyl, ethynyl, 2-propynyl,
Examples include groups such as cyclopentyl, cyclohexyl, and cyclohetocenyl.

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

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-not-amyl7! Examples thereof include a nyl group, a hexadecyl oquinophenyl group, and a J-su7tyl group.

The heterocyclic group represented by R' is preferably a 5- to 7-membered one, which may be substituted or fused, specifically a 2-7lyl group or a 2-chenyl group. , 2-pyrimidyl group, 2-benzothiazolyl group, etc.

As the acyl group represented by R1, for example, an acetyl group,
Phenyl 7cetyl group, dodecanoyl group, (1-214-
Examples include 7-arylcarbonyl groups such as alkylcarbonyl groups such as Kut-7mil7eth/xybuta/yl radicals, benzoyl groups, 3-bentadenluoquinebenzoyl groups, and p-arylbenzoyl groups.

Examples of the sulfonyl group represented by R1 include methylsulfonyl groups, alkylsulfonyl groups such as r-decylsulfonyl groups, benzenesulfonyl groups, and arylsulfonyl groups such as p4 luenesulfonyl groups.

Examples of the phosphonyl group represented by R1 include an alkoxyphosphonyl group such as a butyloctylphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, 7
Examples thereof include an alluroxyphosphonyl group such as a 1-noquinephosphonyl group, an arylphosphonyl group such as a phenylphosphonyl group, and the like.

The carbamoyl group represented by R1 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
, for example, N-methylcarbamoyl group, Hebutylcarbamoyl group, and (z-pentadecyloctylethyl)
Examples thereof include a carbamoyl group, a toethyldodecylcarpamoyl group, and an N-(3-(2,4-sheet-t-7-myl-7-ethoxy)-p-a-vir-1 carbamoyl group).

The sulfamoyl group represented by R1 may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, an N,N-quethylsul 7-amoyl group, an N-( Examples thereof include 2-pentadecyloxyethyl)sulfamoyl M, N-ethyl-N-dodecylsulfamoyl group, and N-7xnylsulfamoyl group.

The oxycarbonyl group represented by R' is preferably an alkodicarbonyl group or a 7-aryloxycarbonyl group, and the alkodicarbonyl group may further have a substituent (
Examples include methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

Further, the aryloxycarbonyl group may further have a substituent, such as a phenoquine carbonyl group, a p-chlorophenoxycarbonyl group, and a -bentadenoloxycarbonyl group.

R2 represents a substitutable group, so is 0 or 1 to 6 vl
When ll is represented and so is an integer of 2 to 6, a plurality of R3s may be the same or different.

There are no particular restrictions on the substituent represented by R, but in addition to representing groups exactly the same as R1, 7-nilino, acylamino, sulfonamide, alkylthio, 7-lylthio, halogen atom, sulfinyl, arylthio group, hetyl ringoxy, cimixi, acyloxy, carnozumoyloxy, amino, alkylami/, imide, ureido, sul77moylami/, alkodicarbonyl7mi/, 7lyloxycarbonylami/, alkoxycarbonyl, Also included are aryloquine carbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

Examples of the acylami 7 group represented by R2 include artocarbonyl 7mino group, arylcarbonyl 7mino'I&, and the like.

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

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

Sulfinyl groups include furkylsulfinyl groups and arylsulfinyl groups; acyloxy groups include alkylcarbonyloxy groups,
Arylcarbonyloxy group*: Carpamoyloxy group includes alkylcarbamoyloxy group, 7lylcarbamoylokyle group, etc.; ureido group includes alkylureido group, arylureido group, etc.; sulf77moylamif group includes alkylsulf77moyl group. 7 groups, arylsul 7 amoylamides/fuj, etc.; as heterocyclic groups, those with 5 to 7 groups are preferable (specifically, 2-furyl group, 2-chenyl group, 2-pyrimidyl group, 2-Benzothiazolyl group, etc.; the heterocyclic oxy ring preferably has 5-7 heterocycles, such as 3,4,5.6-tetrahydrobilanyl-2-okyne group, 1-7xnyltetofuzol-5- Oxy group, etc.; As a heterocyclic thio group, a 1-5-7!A heterocyclic thio group is preferable, such as a 2-bilinorthio group, a 2-benzothiazolylthio group, a 2,4-diphenodone-1,3 ,5-
) Su7zole-6-1000 group, etc.; As a siloxy group, trimethylnrokile group,) ethylne aquine group, dimethylbutyloxy group, etc.; as an imide group, co/) phosphoric acid imide group, 3-heptadecyl Succinimide group, 7-thalimide group, glutarimide group, etc.; spiro compound residues include spiro[3,31 hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue,
] hebutan-1-yl, trinculo[3°3.1.1'
='1 decane-1-yl, 7,7-nomethyl-bicyclo[2,2,11-butan-1-yl and the like.

In the general formula [,1] of the present invention, when two R2s exist adjacent to each other, the two R2s may be closed to each other to form 5 to 7 shell rings.

In addition, in the general formula [H], the case where at least one of the carbon atoms at the 2.3.5.7 and 8th positions is a spiro carbon atom is also included in the present invention. [In 11, it is particularly preferable that R1 is a furkyl, cycloalkyl, or aryl group. Specific examples of compounds represented by the general formula (11) of the present invention are shown below, but the present invention is not limited thereto. It's not something you can do.

The method for synthesizing the photofading inhibitor of the organic coloring compound represented by the general formula [11] according to the present invention is known, for example, as described in Sharnal of Heterocyclic Chemistry -
(J, HeLeroeyel, Che @)19
83t 20 (2) * Can be synthesized according to the method described in 479-481.

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 oxidation dyes and oxidation dyes, and reactive dyes.

These organic coloring substances were prepared at 300 i in a methanol solution.
s to 80Onim, preferably 400nm to 700
n+ml (both have one absorption maximum).

Among these dyes, the dyes preferably used in the present invention include quinoneimine dyes (anone dyes, oxacin dyes, thiazine dyes, etc.), methine and polymethine dyes (cyanine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoamine dyes, etc. The organic coloring substances used in the present invention include dyes belonging to chemical structural classes such as V-indophenol dyes, innovoid dyes, carbonium dyes, and formazan dyes. It includes all dyes formed from couplers, RR compounds, I)OR couplers, amitracine compound dye developers, and dyes for silver dye bleaching methods.

Preferred dyes for use as organic coloring materials of the present invention include 7thraquinone, quinoneimine, azo, methine,
These include polymethine, indoamine, indo71nol, and formazan dyes. The most preferred dyes for the present invention are methine and polymethine dyes and indoamine and indo7er dyes. This dye includes compounds having the following groups.

In the following blanks, the phenyl group represents an unsubstituted phenyl group or a substituted phenyl group, such as a phenyl group substituted with a furkyl 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 equivalents as described in No. 3,458,315! or the carbon atom at the coupling position is substituted with a substituent (split-off group) that can be separated during the coupling reaction 2! ! 1kj
It may be of l type.

In the present invention, preferred yellow dye image-forming Kabufu include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type, imidazopyrazole type, and birazo a bifusol type. system,
There are pizzolotetrazole type, pyrazoli/penlymigzole type, and ingzolone type couplers, and cyan dye image-forming couplers include 7-er/- type, naphthol type, and pyrazoloquinazolone MfJ buller.

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.

The yellow coupler used in the present invention is, for example, West German Published Patent Application No. 2,057.941, West German Published Patent Application No. 2,163
゜No. 812, g/￥ Ensho No. 47-26133, No. 48-
No. 29432, No. 50-65321, No. 51-363
No. 1, No. 51-50734, No. 51-102636, No. 48-66835, No. 48-94432, No. 4
No. 9-1229, No. 49-10736, Special Publication No. 1973-
No. 33410, No. 52-25733, etc., and can be synthesized according to the methods described therein.

Next, the magenta coupler used in the present invention is disclosed in, for example, US Pat. No. 3,684,514, British Patent L183t5i
No. 5, Special Publication No. 40-8031, No. 40-6035,
No. 44-15754, No. 45-40757, No. 46
-19032, JP-A-50-13041, JP-A-53-
No. 129035, No. 51-37646, No. 55-62
No. 454, US Patent No. 3,725,067, British Patent No. 1
, No. 252,418, No. 1,334,515, JP-A-59-171956, No. 59-162548, No. 6
No. 0-43659, No. 60-33552, Research
Dischrono + -NO, 24626 (1984),
Patent Application No. 59-243007, No. 59-243008, No. 59-243009, No. 59-243012,
It includes the compounds described in No. 60-70197, No. 60-70198, etc., and can be synthesized according to the methods described therein.

There are no particular limitations on the cyan coupler used in the present invention, but a 7-er cyan coupler is preferred.

Examples of cyan couplers used in the present invention include, for example, U.S. Pat. No. 2,42:1,730, U.S. Pat.
No. 53-109630, No. 54-55380, No. 5
No. 6-65134, No. 56-80045, No. 57-1
No. 55538, No. 57-204545, No. 58-98
No. 731, No. 59-31953, etc., and can be synthesized according to the methods described therein.

In the present invention, when such couplers are used, dyes are formed from these couplers by reaction with an oxidized aromatic primary amine/) silver lodenide developer.

The above developer is 7min 7, which is well known in the photographic material industry.
These developers can be mixed together.

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

0 ■ OL: zlli ell, 1 SO□Clh Further, other types of dyes preferably used in the present invention include U, S, B551,673, U.S. Pat.
32.381, 3,928.312, 3,93
No. 1,144, No. 3,954,476, No. 3, 92
No. 9.760, No. 3,942,987, No. 3,932
No. 380, No. 4,013,635, No. 4,013,
No. 633, JP-A-51-113824, JP-A No. 51-10
No. 9928, No. 51-104343, No. 52-481
No. 9, No. 53-149328, Research Disclosure A--No. 15157 (1976), No. 3g 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 No. 840,731, British Patent No. 904,364, British Patent No. 932t272, British Patent No. 1,014,725, British Patent No. 1
, No. 038,331, No. 1,088,352, No. 1,
No. 097,064, JP-A-51-133021, LI
ST900y029 (U, S, Defensive
Publication), U.S. Patent 3,227,55
This concludes by mentioning dyes released by reaction of DDRfJ blurs such as those described in No. 0 with oxidized forms of color developing agents or dyes formed by reaction with oxidized forms of color developing agents.

Other types of dyes preferably used in the present invention include Japanese Patent Publications Nos. 35-182, 18332, and 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.

The compounds of the present invention are generally oil-soluble and are typically used in U.S. Pat.
, No. 801゜171, No. 2,272,191 and No. V No. 2,304,940, it is dissolved and dispersed in a high boiling point solvent using a low boiling point solvent as necessary. It is preferable to add it to a hydrophilic colloid solution, and at this time, if necessary, a coupler, a hydroquinone derivative, an ultraviolet #i @ abrasion or a known dye image fading inhibitor may be used in combination without any problem. , 2. There is no problem in using two or more of the compounds of the present invention in combination. To further explain in detail the method of adding the compound of the present invention, IJ1! Alternatively, two or more of these compounds may be combined together with couplers, hydroquinone derivatives, ultraviolet absorbers, or known dye image fading inhibitors, etc., as required, such as organic acid 7amides, carba 7-F, etc.
esters, ketones, hydrocarbons, urea derivatives, etc., butyl 7-talate, tricresyl phos-7-A, no-11 octyl 7-gelate, sibutyl sepacate, trihexyl phosphate, decalin, N, N- If necessary, add ethyl acetate to a lower boiling point solvent such as diethylcabrylamide, N,N-zoethyllauryl 7mide, bentadenulfenyl ether or fluoropafine.
It is soluble in low boiling point solvents such as butyl acetate, butyl propionate, cyclohexyl, cyclohexane, tetrahydro7ran, etc., and these high boiling point and low boiling point solvents may be used alone or in combination. Anionic surfactants such as kylbenzenesulfonic acid and 1-furkylnaphthalenesulfonic acid. Hydrophilic properties such as gelatin containing/or ionic surfactants such as sorbitan sesquioleate and sorbitan monofurinate. Mix with an aqueous solution containing Pine Goo and rotate at high speed =
It can be emulsified and dispersed using a colloid mill or an ultrasonic molecule, and the resulting aliquot can be added to a hydrophilic colloid solution (for example, a silver halide emulsion) and used.

Both the colorant and the compound of this invention can be present in any or several of the hydrophilic colloid layers in the photographic element. These substances include photosensitive elements and
A coloring substance which may be present in a non-light sensitive element such as a dye circle image receptor used in a photographic magnification soft copy film unit and a compound of the invention may be present in such a non-light sensitive image recording element. They are preferably mordanted; therefore, for such uses, the compounds of the invention are preferably mordanted so that they do not migrate away from the dye to be stabilized. The molecular form must be such that it can be retained in the mordant layer of the image receptor.

The photographic material used in the method of the present invention can be produced by methods known in the photographic material II field.

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 above coupler-containing inner mold 7! P? - In photographic materials,
It is processed according to conventional methods to obtain a color image. The main steps in this case are color development, bleaching, and fixing, and if necessary, steps such as washing with water and stabilization may be included. Two or more of these steps, such as bleach-fixing, can be carried out in one bath. Color development is usually carried out in an alkaline solution containing an aromatic primary amine developing agent.

Color photographic materials to which the method of the present invention is applied are color expanded I'
lll:lv: If it is a photo film unit,
Processing of the photographic material takes place automatically within the photosensitive material. In this case, the developing agent is contained in a rupturable container.

When the method of the present invention is applied to photographic light-sensitive materials, Color B film, Color Vapor, Colorne 7Y film, Color [* film, film unit for color diffusion transfer, light-sensitive material for silver dye bleaching, color light-sensitive material for heat development, etc. Examples include various color photographic materials.

〔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 a magenta dye having the following structure (maximum absorption of 538 nm in a tar solution) was dissolved in trioctylphos 7 and 4-1 and 8 ml of ethyl acetate, and this solution was 10 containing 2t' of .5% sodium dodenlebenzene sulfonate aqueous solution
% gelatin tB solution was emulsified and dispersed.

Next, this emulsified dispersion was mixed with 5% gelatin solution 3011 and coated on 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, comparative compounds represented by the following structural formulas (i) 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 Sample No. 1, 0.5 g of each of the exemplary compounds of the present invention was added as shown in Table 1 and applied in the same manner as 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 220 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.

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 anti-fading properties than the samples using known metal complexes (Nos. 2 and 3). It was effective, 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).
Fifteen types of samples (Ha, 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 fade meter for 160 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 exposure test.

Example 3 Exemplary coupler (M-8) 30 as a magenta coupler,
A solution of 30w*l of trifrenorphosphate) and 100ml of ethyl acetate was added to a 5% aqueous gelatin solution containing 2.5g of sodium dodecylbenzenesulfonate.
After adding to 500 mZ, it was dispersed with a homogenizer, and the resulting dispersion was mixed with green photosensitive silver chlorobromide (silver chloride 30 mol%).
Contains) Emulsion 1. Added to OOO*ffi, N,N',N"-)lyacryloylhexahydro-3- as a hardening agent
Add 2% methanol of Trianon @1lllO+4,
It was 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 (e) and (d) having the following structures were added at an angle of 24°, respectively, 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 (e)... Compound described in JP-A No. 54-48538 Comparative compound (d)... Compound described in JP-A-58-159644 After each of these samples was exposed, the following treatment was performed. Processed with liquid and processing steps.

[Developer]

Bensylfurfur 12.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.9g Sodium bromide
1.4g potassium bromide
065g sodium carbonate
30.0゜N-ethyl-N-β-notanesulfonamidoethyl-4-7/aniline sulfate 5,
Add water to bring the pH to 11, and adjust the pH to 10.30 using sodium hydroxide.

[Bleach-fix solution]

Ethylenenoaminetetraacetic acid iron ammonium '7A 61.0g Ethylenenoaminetetraacetic acid 112 ammonium 5,0g Ammonium thiosulfate 124,5° Ammonium metabisulfite 13,3° Anhydrous sodium sulfite 2.7g Add water to make 11 , adjust the pH to 6.5 using ammonia water (1).

[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 UV cut filter, Kodak Wratten Filter N, to each sample with a dye image formed in this way.
o. A 160 hour fading test was conducted using a xenon 7ademeter with 2A attached.・The results are shown in Table 3.

The degree of fading was indicated by the density change in the 1°0 density area before the fading test.

T! , 3 (The absorption maximum of the colored magenta dye in a methanol solution was 536n theory.) As is clear from the results in Table 3, the anti-fading agent of the present invention has a superior light resistance to conventional organic anti-fading agents. It has the effect of preventing color development.

Example 4 As cyankabuty, 35 g of the exemplary coupler (C-6) was mixed with 35 l of 7 octyl 7 tallate and 1 OQs of V ethyl acetate.
+t' solution was added to 500ml of 5% gelatin aqueous solution containing 2.5g of sodium dodecylbenzenesulfonate.
After adding Z, it was dispersed with a homogenizer, and the resulting dispersion was added to 1,000 ml of a red-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion, and N, N',
10 l of a 2% methanol solution of N"-triacryloylhexahydro-8-triazine 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. 41.

When preparing the emulsified dispersion liquid 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 were added to prepare 9 types of samples (No. 4).
2-50) was created.

Comparative compound (e): Compound described in JP-A No. 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 240 hours using a xenon 7 oedometer with the same material as used in Example 3). The results are shown in Table 4.

Table 4 (Maximum absorption of colored cyan dye in methanol solution is 6
52n-) As is clear from Table 4, the antifading agent of the present invention has a great 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 722-carpamoylated gelatin (manufactured by Rousslow, type 17819)
PC) mixed in a 2:1 (weight ratio).

PVP...Polyvinylpyrrolidone (ni-30) solid heat solvent...p-butoxybenzamide liquid heat solvent...
1,2.4-butanetriol reduction: A mixture of the following reducing agents A and B at a 7:3 molar ratio.

1! I f Pehe 6 (A) (B) Organic silver salt...5-methylbenzotriazole silver photosensitive silver halide...Same as that described in the examples of Japanese Patent Application No. 1983-254257 was used.

Yea-Dye Donor Substance (V・-CPS)L Magenta dye-providing substance (M-CPM) CH.

Cyan dye donor 1r (C-C'PM)C11° exchange■ x:y=60:40 (weight ratio) Below - White is expressed in silver equivalent value) Preparation of heat-developable image-receiving element> Photographic baryta paper (thickness 170μ!, weight 190p/shoulder 2), apply the following image-receiving layer coating solution to a wet film thickness of 1.37.2
A heat-developable image-receiving element was prepared by coating with μl and drying (Sample No. 51).

(Image-receiving layer coating liquid) Polyvinyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., n = 1,100) 2
1.0° Tetrahydro 7 Run 190 liters When preparing the above image-receiving layer coating solution in the same manner, as shown in Table 6, a comparative compound, an ultraviolet absorber, and an exemplary compound of the present invention were added to OlS, respectively. (0.4g each if used together)
In addition, nine types of samples (Nos. 52 to 60) were prepared by coating in the same manner as Sample No. 51 above.

The heat-developable photosensitive element was exposed to 4,000 cm s of tungsten light through a stepper and a green filter, and the coated surfaces of the heat-developable image-receiving element and the heat-developable image-receiving element were overlapped and preheated at 100° C. for 4 seconds.
Pressure heating (thermal development) was performed at 0° C. for 90 seconds. Preheating and compression heating are described in Japanese Patent Application Laid-Open No. 153851/1986.
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 resistance 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 with green light using Sakura Densitometer PI)^-65 (manufactured by Konishiroku Photography I).

(Evaluation of light resistance stability) Samples with magenta images were tested with a xenon fade meter (Suge Tester HE-6X-1ie) for 5 days and 10 days.
It was irradiated with sunlight and the residual dye concentration T$ (%) was examined.

Margin below Table 6 This ultraviolet absorber (UV-t> 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 an ultraviolet absorber together, 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 light-induced discoloration and fading of the organic coloring substance, particularly pigments, dyes, etc. used in color photographic materials.

Claims (1)

[Scope of Claims] A method for preventing photofading of an organic coloring substance, which comprises coexisting the organic coloring substance and at least one compound represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Alkynyl group, aryl group,
Represents a heterocyclic group, acyl group, sulfonyl group, carbamoyl group, phosphonyl group, sulfamoyl group, or oxycarbonyl group. R^2 represents a substitutable group. m represents 0 or an integer of 1 to 6, and when m represents an integer of 2 to 6, the plurality of R^2 may be the same or different. ]