JPH02197839A - Method for preventing photofading of organic colored material - Google Patents

Abstract

PURPOSE:To improve stability of the organic colored material against light by adding a specified dyestuff image stabilizer to a the organic colored material. CONSTITUTION:The compound to be used together with the organic colored material selected from all kinds of dyes including water-soluble dyes, such as basic dyes, acidic dyes, direct dyes, soluble vat dyeing dyes, and mordant dyes, and insoluble dyes, such as sulfide dyes, vat dyeing dyes, oil-soluble dyes, disperse dyes, azo dyes, and oxidation dyes, and reactive dyes, is at least one of the compounds represented by general formula I in which X is -O-, -S-, or -NR3; and A is a nonmetallic atomic group necessary to form an imidazolyl, pyrrolyl, pyrazolyl, triazolyl, or tetrazolyl group.

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 has been conducted to prevent such photospeciation 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,
- Numerically 30OnI11-800 in methanol solution
refers to an organic substance that has at least one absorption maximum in nm.

Furthermore, in this specification, the term light refers to approximately 30 On
+ means electromagnetic waves of approximately 800no+ or less, approximately 400no+
This includes sub-nm ultraviolet light, visible light from about 400 nm to about 700 am, and infrared light from about 700 nm to about 800 nm.

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

In the field of silver halide color photographic materials, dye images obtained from couplers are exposed to light for long periods of time,
It is desirable that the product does not change color 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 it is known that the color changes 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 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. There have been times when I have been Further, even if an ultraviolet absorber is used, it has no effect on preventing dye images from fading due to visible light, and there are limits to the improvement in light resistance by ultraviolet absorbers.

Furthermore, a method using a dye image fading inhibitor having a phenolic hydroxyl group or a group that generates a phenolic hydroxyl group by hydrolysis is known; for example, Japanese Patent Publication No. 48-312
No. 56, No. 48-31625, No. 51-30462, JP-A-49-134326 and No. 49-13432
No. 7 includes phenol and bisphenols, U.S. Pat.
, 069.262 describes pyrogallol, gallic acid and its esters, U.S. Pat.
．． No. 015,990 describes α-tocopherols and their acyl derivatives, Japanese Patent Publication No. 52-27534, Japanese Unexamined Patent Application Publication No. 1987-52
-14751 and U.S. Pat. No. 2,735,765, hydroquinone derivatives, U.S. Pat. 5-hydroxychroman derivatives and 6 in Japanese Patent Publication No. 49-20977.
．． It has been proposed to use 6'-dihydroxy-2,2'-subirobichromans, etc. However, although these compounds have some effect as dye fading and discoloration inhibitors, they are not sufficient.

British Patent No. 1,451.000 also describes improving the light stability of organic colored compounds using an azomethine quenching compound whose absorption peak is more bathochromic than that of the colored compound. However, the azomethine quenching compound itself is colored, which is disadvantageous because it greatly affects the hue of the colored substance. In addition, the use of metal complexes to prevent photodegradation of polymers has been reported in the Journal of Polymer Science, edited by Polymer Chemistry (J, P
olym, Sci.

Polym, Chem, Ed.) Volume 12, Page 993
(1974), Journal of Polymer Science, edited by Polymer Letters (J, Polys, Sci.
Polym, Lett, Ed.), vol. 13, p. 71 (
1975), and a method for stabilizing dyes against light using metal complexes was disclosed in JP-A-50-87.
No. 649 and Research Disclosure
Arch Disclosure) No. 15162
(1976), these complexes
In addition to the fact that the anti-fading effect itself is not large, it is not highly soluble in organic solvents, so it is not possible to add a sufficient amount to exert the anti-fading effect.Furthermore, these complexes themselves have a large coloration. Therefore, when added in large quantities,
Adversely affects 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. 54-82386, No. 54-136581,
54.136532, 5542129, 55
-152750, 56-168652, 56-
No. 167138, No. 57-161744, Special Publication No. 1983
-19770 etc.

However, even the above methods are still insufficient to reduce the coloration of the complex itself, and organic coloring substances,
In particular, the negative effect on the hue and purity of the pigment or dye cannot be overestimated.

Furthermore, when these known metal complexes are applied to silver halide color photographic materials (hereinafter referred to as color photographic materials), stains are likely to occur in uncolored areas of the developed color photographic materials. In particular, when a developed color photographic material is stored under conditions of high temperature and high humidity, the occurrence of contamination increases significantly.

Further, a certain p-aminophenol derivative is known from JP-A No. 63-95439, and although it is found to have an effect on fading of dyes, it is still not sufficient.

[Purpose of the invention]

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

Another object of the invention is to provide a method for improving the light stability of organic coloring substances, especially pigments or dyes, without deteriorating their hue and purity.

Yet another object of the present invention is to provide a method for improving the light stability of color images forming color photographic images without contaminating the uncolored areas of the color photographic material.

[Structure of the invention]

The above object of the present invention is to provide an organic coloring substance and the following formula (I).
This can be achieved by coexisting at least one of the compounds represented by.

General formula (1) In the formula, xR1 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group,
It represents an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, or an oxycarbonyl group, and R1 represents a substituent. X is -0
-, -S-, -NR3-, and R3 represents the same group as R1. n represents an integer of 0 to 4, and when n is 2 or more, a plurality of R2s may be the same or different. Further, when R1X and R7 are located at adjacent positions, R1X and R may be bonded to each other to form a 5- to 7-membered ring. A represents a nonmetallic atomic group necessary to form an imidazolyl, pyrrolyl, pyrazolyl, triazolyl or tetrazolyl group.

The present invention will be explained in more detail below.

In the above 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 cycloalkenyl group have 1 to 32 carbon atoms. Numbers 3 to 12,
In particular, those having 5 to 7 are preferred, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched. Moreover, these groups may have a substituent. Specifically, methyl, ethyl, t-decyl, pentadecyl, 1-hexylnonyl, 2-chloro-t-butyl, benzyl, 2+4-sheet t-alumiphenoxymethyl, 1-ethoxytridecyl, allyl, impropenyl, Examples include groups such as ethynyl, 2-propynyl, cyclopentyl, cyclohexyl, and cyclohexenyl.

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

Specifically, phenyl, 4-nitrophenyl, 4-t-
Butylphenyl, 214-sheet t-amylphenyl, 3
Examples include groups such as -hexadecyloxyphenyl and a-naphthyl.

The heterocyclic group represented by R4 is preferably a 5- to 7-membered one, which may be substituted or fused.

Specific examples include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R3 include acetyl group,
Alkylcarbonyl groups such as phenylacetyl group, dodecanoyl group, α-2,4-di-t-amylphenoxybutanoyl group, arylcarbonyl group such as benzoyl group, 3-pentadecyloxypenzoyl group, p-chlorobenzoyl group etc.

Examples of the sulfonyl group represented by R1 include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group.

The phosphonyl group represented by R is an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group,
Examples include arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by R□ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, an N+-dibutylcarbamoyl group, an N-(2-pentylcarbamoyl group, Examples thereof include a decyl octylethyl) carbamoyl group, an N-ethyl-N-dodecyl carbamoyl group, and an N-(3-(2,4-di(-amylphenoxy)propyl) carbamoyl group).

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

The oxycarbonyl group represented by R1 is preferably an alkoxycarbonyl group or an aryloxycarbonyl group.

The alkoxycarbonyl group may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group, and the like. Further, the aryloxycarbonyl group may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, a m-pentadecyloxyphenoxycarbonyl group, and the like.

There are no particular restrictions on the substituent represented by R1, but R1
In addition to representing the same groups as halogen atoms and anilino, acylamino, sulfonamide, alkylthio, arylthio, sulfinyl, cyano, alkoxy, aryloxy, heterocyclicoxy, heterocyclicthio, siloxy, acyloxy, carbamoyloxy, amino, alkylamino ,
Also included are imide, ureido, sulfimoylamino, alkoxycarbonylamino, aryloxycarbonylamino groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

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

Examples of the sulfonamide group represented by R8 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 R8 include the alkyl group and aryl group represented by R1 above.

As a sulfinyl group, an alkylsulfinyl group, arylsulfinyl 1ml, as an acyloxy group, an alkylcarbonyloxy group,
Arylcarbonyloxy groups, etc.: Carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; sulf7 amoylamino groups include alkylsulfamoylamino groups, arylsulfamoyloxy groups, etc. Famoylamino group, etc.: The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3.4.5.6-tetrahydrobilanyl-2-oxy group, l-7enyltetrazole-5 −
Oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole -6 monothio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc. Spiro compound residues include spiro [3,31hebutan-1-yl, etc.; bridged hydrocarbon compound residues include bicyclo [2゜2.
11 Heno 9-1-i L, To! J Schiff O [3,3,
Examples include 1,1"1 decane-1-yl, 7,7-siphthyrubicyclo[2,2,11-hebutan-1-yl, and the like.

In the present invention, - among the compounds represented by formula [I],
The substitution of XR is preferably at the p-position with respect to N[child, and more preferably X is an O atom.

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

Next, a typical method for synthesizing the compound of the present invention will be described.

Synthesis Example 1 (Synthesis of Exemplary Compound 2) l-(4-hydroxyphenyl)imidazole 169,
Add 20g of a 28% methanol solution of sodium methylate to 100IllIl of dimethylformamide,
Dodecyl bromide 259 was added over 10 minutes at 90°C, and the mixture was further stirred for 4 hours. The reaction solution was poured into 200 aiffi of ice water, extracted with 150 aiffi of ethyl acetate, and then subjected to column chromatography to obtain 24 g of the desired product.

Identification is done by NMR, mass spectrum, and elemental analysis.
It was confirmed that it was Exemplified Compound 2.

Synthesis Example 2 (Synthesis of Exemplified Compound 14) 16 g of 1-(4-hydroxyphenyl)pyrazoline.

Add 20 g of a 28% methanol solution of sodium methylate to 100 Q of dimethylformamide and heat to 80-90°C.
Then, 25 g of dodecyl bromide was added over 10 minutes, and the mixture was further stirred for 4 hours. The reaction solution was poured into 200 cc of ice water, extracted with 150 mL of ethyl acetate, and then subjected to column chromatography to obtain 24 g of the desired product.

Identification is done by NMR, mass spectrum, and elemental analysis.
The structure of Exemplified Compound 14 was supported.

The amount of the compound of the present invention used is preferably 5 to 400 mol%, more preferably 10 to 300 mol%, based on the organic coloring substance used in the invention.

The organic coloring substances used in the present invention include basic dyes, acid dyes, direct dyes, soluble vat dyes, water-soluble dyes such as mordant dyes, sulfur dyes, vat dyes, oil-soluble dyes, disperse dyes, azoic dyes, It includes all dyes belonging to the classification of dyeing properties such as insoluble dyes such as oxidative dyes or reactive dyes.

These organic coloring substances are 300a in methanol solution.
m to 800nm, preferably 400n+a to 700nm
It has at least one absorption maximum in 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, indoamine dyes, and It includes dyes belonging to chemical structural classes such as indophenol dyes, indigoid dyes, carbonium dyes, and formazan dyes.

The organic coloring substance used in the present invention is an image-forming dye used in the field of photography, such as a color coupler, I)
It includes all dyes formed from RR compounds, DDR couplers, amitracine compounds, dye developers, and dyes for silver dye bleaching methods.

Preferred dyes for use as organic colorants of the present invention include anthraquinone, quinone imine, azo, methine,
These include polymethine, indoamine, indophenol and formazan dyes.

The dyes most preferably used in the present invention are methine and polymethine dyes and indoamine and indophenol dyes. This dye includes compounds having the following groups.

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

Dye-forming couplers suitable for use in this invention include those of the yellow-magenta and cyan dye-forming types. This coupler is described in US Pat. No. 3,277.155, for example.
Substituted with a so-called 4-equivalent type, as described in No. 3,458.315, or a substituent (splint-off group) from which the carbon atom at the coupling position can be released during the coupling reaction. It may also be a 2-equivalent base.

Preferred examples of yellow dye image-forming couplers in the present invention include benzoylacetanilide-type and pivaloylacetanilide-type couplers, and examples of magenta dye-image-forming couplers include 5-pyrazolones, pyrazolotriazoles, imidazopyrazoles, and pyrazolopyrazoles. system,
There are pyrazolotetrazole-based, pyrazolinobenzimidazole-based, and indasilone-based couplers, and cyan dye image-forming couplers include phenol-based, narlatol-based, and pyrazoloquinazolone-based couplers.

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

Next, these yellow couplers that can be used in the present invention include, for example, West German Published Patent Application No. 2,
No. 057.941, Nishisuna Publication Patent 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, Magenta Cub M-5 that can be used in the present invention C! H.S. C4H.

These magenta couplers are described, for example, in U.S. Pat.
4.514, British Patent No. 1.183.515, Japanese Patent Publication No. 40-6031, 40-6035, 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.

No. 725,067, British Patent No. 1,252.418, British Patent No. 1,334.515, JP-A-59-171956,
No. 59-162548, No. 60-43659, No. 6
No. 0-33552, Research Disclosure + -N
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. 60-70198, etc., and can be synthesized according to the methods described therein.

Although there are no particular limitations on the cyan coupler used in the present invention, a phenolic cyan coupler is preferred.

Next, these cyan couplers that can be used in the present invention are disclosed in, for example, U.S. Pat.
．． No. 730, No. 2,801.171, Japanese Unexamined Patent Publication No. 1973-1
No. 12038, No. 50-134644, No. 53-10
No. 9630, No. 54-55380, No. 56-6513
No. 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 phenylenediamine, and these developers can be used in combination. Among the developers that can be combined with various couplers to produce colored compounds according to the present invention, , representative examples are listed below.

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

(F-1) CF-2) H 2H5 C! H.

2Hs L;H,1,:tl! (JH (F-7) (F-8) (F-5) (F-9) NH5O2CH3 Further, other types of dyes preferably used in the present invention include U, S, B551.673, U.S. Pat. 3,932
．． No. 381, No. 3,928.312, No. 3,931.
No. 144, No. 3,954.476, No. 3,929.7
No. 60, No. 3,942,987, No. 3,932゜38
No. 0, No. 4,013,635, No. 4,013.633
No., JP-A-51-113624, JP-A No. 51-10992
No. 8, No. 51-104343, No. 52-4819,
No. 53-149328, Research Disclosure +
-No. 15157 (1976), same magazine No. 13
Examples include dyes formed by oxidation of DRR compounds described in, for example, 024 (1975).

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
, 038.331, 1,066.352, 1,
No. 097.064, Japanese Patent Publication No. 51-133021, US
T900,029 (U, S, Defensive P
publication), U.S. Patent 3,227.550
Mention may be made of dyes released by the reaction of DDR couplers such as those described in No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2010-12, and dyes released by the reaction of DDR couplers with oxidized products of color developing agents, or dyes formed by the reaction of DDR couplers with oxidized products of color developing agents.

Other types of dyes preferably used in the present invention include Japanese Patent Publications No. 35-182, No. 18332, No. 48-
No. 32130, No. 46-43950, No. 49-261
Examples include the dye developers described in No. 8 and the like.

Furthermore, other dyes used in the present invention include various dyes used in silver dye bleaching methods. Yellow dyes that can be used for this purpose include Direct Fast Yellow GC (C,1,29000), Glyphen (C,1-24895) nato(') azo dye, Indigo Golden Yellow rGK (C,1
゜59101), Indigothy/L, Ixa-2
G [(C, 1, 61726), arbosol Ie o-0
CA-CF (C, 1,67301), Indanthrene Yellow-GF (C, 1,68420), Mikethrene Yellow GC (C, 1,67300), Indanthrene Yellow 4 GK (C, 168405), etc. Benzoquinone dyes include anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes. As a magenta dye, Sumilite Sabralbinol B (c
, r, 29225), penzoprilliantgalanin B (
azo dyes such as C, R, 15080), Indigosol Brilliant Pink IR (C, 1,73361), Indigosol Bio L/T 15R (C, 1,59321)
), Insicosol Red Violet IRRL (c
-+, 59316), Intanthrene Red Violet RRK (c, 1.67895), Mikethrene Brilliant Violet BBK (C, 1,6335), etc. Indigoid dyes: Consists of benzoquinone-based and anthraquinone-based heteropolycyclic compounds Examples include soluble vat dyes and other vat dyes.

As a cyan dye, Direct Sky Blue 6 B
(C, 1, 24410), Direct Brilliant Blue 2 B (C, 1, 22610), Sumilight Subra Blue-G (C, 1, 34200), etc., SumiLite Subra Turkish Blue (, (C ,1,741
80), Mikethren Brilliant Blue 4 G (C,
1,74140), Indance Lenterkey Sprue 5 G (c, +, 69845
), Indan Stremburu-GCD (c, +, 7306
6), Indigosol 04G (C, 1,73046)
, Anthrazole Green IB' (C, 1,5982
6), etc.

The compounds of the present invention are generally oil-soluble and are typically used in U.S. Pat.
, 801゜171, No. 2,272.191 and No. 2,304,940 by dissolving and dispersing in a high boiling point solvent together with a low boiling point solvent as necessary. It is preferable to add it to a colloidal solution, and at this time, if necessary, a coupler hydroquinone derivative, an ultraviolet absorber, a known dye image fading inhibitor, etc. may be used in combination without any problem. At this time, there is no problem even if two or more of the compounds of the present invention are used as a mixture. To further explain in detail the method of adding the compounds of the present invention, one or more of the compounds may be added to an organic acid amide at the same time as a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor. such as carbamates, esters, ketones, hydrocarbons and urea derivatives, especially dibutyl phthalate, tricresyl phosphate, di-
If necessary, add to a high boiling point solvent such as octyl azelate, digtyl sebacate, trihexyl phosphate, decalin, N,N-diethylcaprylamide, N,N-diethyl laurylamide, pentadecyl phenyl ether or fluoroparaffin. These high-boiling point solvents and low-boiling point solvents may be used alone or in combination. ) An aqueous solution containing a hydrophilic binder such as gelatin containing an anionic surfactant such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate. A high-speed rotating mixer (colloid mill) emulsifies and disperses with an ultrasonic dispersion device or the like, and the resulting dispersion is added to a hydrophilic colloid solution (for example, a silver halide emulsion) for use.

Both the colorant and the compounds of this invention can be present in any or several of the parent colloid layers in the photographic element. These materials may be present in light-sensitive elements as well as non-light-sensitive elements such as dye image receivers used in photographic diffusion transfer film units. When coloring substances and compounds of the invention are included in such non-light-sensitive image recording elements, they are preferably mordanted. Therefore, for such uses, the compounds of the present invention have a molecular form that allows them to be retained in the mordant layer of the image receptor so that they do not migrate away from the dye to be stabilized. must be maintained.

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

These silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Further, chemical sensitization can be carried out by a conventional method in the field of photography.

Silver halide emulsions are known as antifoggants or stabilizers in the photographic industry for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or keeping photographic performance stable. Compounds that are present can be added.

In addition, various photographic additives such as hardeners, plasticizers, optical brighteners, antistatic agents, and coating aids may be used alone or in combination.
More than one species can be added and used in combination.

The color photographic material to which the present invention is applied may be an internal color photographic material containing a coupler or an external color photographic material in which a developer contains a coupler.

The above-mentioned coupler-containing internal color photographic material is processed in a conventional manner to obtain a color image. The main steps in this case are color development, bleaching, and fixing, and if necessary, steps such as washing with water and stabilization may be included. Two or more of these steps, such as bleach-fixing, can be carried out in one bath. Color development is usually carried out in an alkaline solution containing an aromatic primary amine developing agent. Preferred specific examples of these aromatic primary amine developing agents are described above as exemplified developers D-1 to D-6.

When the color photographic material to which the method of the invention is applied is a film unit for color diffusion transfer, processing of the photographic material takes place automatically within the light-sensitive material. In this case, the developing agent is contained in a rupturable container. As the developing agent, in addition to the compounds represented by D-1 to D-6 above,
N-methylaminophenol, l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-hydroxymethyl-3-pyrazolidone, 3-methoxy-N,N -diethyl-p-7 enylene diamine, etc. can be used.

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

〔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 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic material, and sample 1 was obtained. (In the following examples, the amount added is shown per 100 cm of light-sensitive material.) 1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2°4
-dioquine-1-benzylimidazolidin-3-yl)
・6.8 mg of 2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide
, 3-2 mg of blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) in terms of silver, 3.5 B of dibutyl phthalate
and a layer containing 13.5 mg of gelatin.

2nd layer: Intermediate layer 2.5-G[-octylhydroquinone (L5+g
, 0.5+ gg of dibutyl 7tate and 9 gg of gelatin
．． Layer containing 0+gg.

3rd layer: Green-sensitive silver halide emulsion layer The magenta color (M-13) is 3.5a+g, and the green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) is 2.5mg in terms of silver5 dibutyl Layer containing 3.0 mg phthalate and 12.0+ gg gelatin.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3,5-di-t)
・0.7+g of butylphenyl)benzotriazole,
6.0I1g of di-butyl phthalate, 2.5-di-
A layer containing 0.5 mg of t-octylhydroquinone and 12.0+gg of gelatin.

5th layer: red-sensitive silver halide emulsion layer 4.2 mg of 2-[α・(2,4-di-t-pentylphenoxy)butanamide)-4,6-dichloro-5-ethylphenol as a cyan coupler1 red-sensitive Silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver is 3.9+
mg, a layer containing 3.5 mg of tricresyl phosphate and 11.5-g of gelatin.

6th layer: protective layer A layer containing 8.0+mg of gelatin.

In the above Sample I, the compounds of the present invention were added to the third layer in the combinations shown in Table 1 at a ratio of 100 mol % to the coupler to create Multilayer Samples 2 to I2.

After exposing the sample obtained above through an optical wedge according to a conventional method,
Processed in the next step.

Processing process Processing temperature Processing time Color development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Washing with water for 1 minute and 30 seconds, drying at 33°C for 3 minutes, and drying at 50 to 80°C for 2 minutes The components of the treatment solution are as follows.

Color developer benzyl alcohol 12.0@ll
Diethylene glycol 10.0 ■a Potassium carbonate 25.0 g Sodium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Hydroxylamine sulfate 2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline Add 4.5g of sulfate water to make tQ, and adjust the pH to 10.2 with sodium hydroxide.
Adjust to.

Bleach-fix solution Ammonium thiosulfate 120.0g Sodium metabisulfite 15-0g Anhydrous sodium sulfite 3. OgEDTA ferric ammonium salt 65.0g Add water to lQ
and adjust the pH to 6.7-6.8.

The concentration of sample 1-12 treated above was measured using a densitometer (model KD-7R manufactured by Konica Corporation) under the following conditions.

Each of the above-mentioned processed samples was exposed to a xenon fade meter for 16 days to examine the light fastness of the dye image.

Comparative compound 1 (compound described in JP-A No. 54-48538) QC1H1 Comparative compound 2 (compound described in JP-A-63-95439) Comparative compound 3 (compound described in U.S. Pat. No. 3,573,050) Comparative compound 4 From the results in Table 1, the use of the compound of the present invention was effective in stabilizing magenta dye images formed from magenta couplers, and Y stain in unexposed areas was also improved.

Example 2 A silver chlorobromide emulsion containing 99.5 mol % of silver chloride was used in place of each silver halide emulsion used in Example 1, and the magenta coupler and dye image stabilizer in the third layer were prepared as shown in Table 2. A sample similar to Sample 1 of Example 1 except for the changes shown in (Sample 1)
3 to 28) were created.

Samples 13 to 28 were subjected to light wedge exposure according to a conventional method, and then subjected to the following treatments.

Processing process Processing temperature Processing time Color development 34.7±0.3°C 45 seconds Bleach fixing 34.7±0.5°C 45 seconds Stabilization 30~
Dry at 34℃ for 90 seconds 60-80℃ for 60 seconds Color developer Pure water
800+mg triethanolamine
8g N,N-diethylhydroxylamine
5g potassium chloride 2
gN-ethyl-N~β-methanesulfonamidoethyl-
3-Methyl-4-aminoaniline sulfate
5g sodium tetrapolyphosphate
2g potassium carbonate
30g potassium sulfite 0.2
g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) Add 1 g of pure water to bring the total volume to 112, and adjust the pH to 10.2.

Bleach-fix solution Ferric ammonium dihydrate ethylenediaminetetraacetic acid 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100 Q Ammonium sulfite (40% solution) 27.5 IQ Add water to bring the total volume to IQ, add potassium carbonate or Adjust the pH to 5.7 with glacial acetic acid.

5-Chloro-2-methyl-4-inthiazolin-3-one 1g 1-hydroxyethylidene-1,1-diphosphonic acid 2g Add water to adjust to IQ, and adjust pH to 7.0 with sulfuric acid or potassium hydroxide. 0
Adjust to.

The light resistance of each sample after treatment was evaluated in the same manner as in Example 1.

Table 2 Similar to the magenta coupler of Example 2, the yellow coupler of the present invention and the cyan coupler also exhibited good light fastness of color images when the dye image stabilizer of the present invention was added to the cyan coupler. In addition, good color images were obtained.

〔Effect of the invention〕

By using the dye image stabilizer of the present invention as a stabilizer for a dye capable of forming an image, a photographic image obtained from a silver halide photographic light-sensitive material has an excellent fading prevention effect. The Y-stin has also been improved.

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] [In the formula, R_1 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group,
It represents a phosphonyl group, a carbamoyl group, a sulfamoyl group, or an oxycarbonyl group, and R_2 represents a substituent. x
represents -O-, -S-, -NR_3-, and R_3 is R_
Represents the same group as 1. n represents an integer from 0 to 4, and n is 2
In the above case, the plurality of R_2 may be the same or different. Also, if R_1X and R_2 are adjacent to each other, R_1X
and R_2 may be combined with each other to form a 5- to 7-membered ring. A represents a nonmetallic atomic group necessary to form an imidazolyl, pyrrolyl, pyrazolyl, triazolyl or tetrazolyl group. ]