JPS63163347A - Method for preventing photodiscoloration of organic coloring substance - Google Patents

Abstract

PURPOSE:To improve the photodiscoloration preventing effect of the org. coloring substance, without making the hue and the purity of a color matter or a dye worse, by jointly using the org. coloring substance and a specific compd. to the color photographic material. CONSTITUTION:The color photographic material contains jointly the org. coloring substance with at least one kind of the compd. shown by formula I where R<1> and R<2> are each hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, a heterocyclic ring, acyl, sulfonyl, phosphonyl, carbamoyl, sulfamoyl or oxycarbonyl group, Z1 and Z2 are each a single binding group or 1-4 C alkylene group, R<3> is a substituent, (m) is 0 or an integer of 1-6. Thus, the excellent photodiscoloration preventing effect of the org. coloring substance, especially, the dye of the color photographic material against the discoloration caused by the light is obtd., and the color photographic image is maintained to stable for long period.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to a method for preventing photofading of organic coloring substances, and more specifically, the present invention relates to a method for preventing photofading of organic coloring substances, such as inks, textile dyes, color photographs, etc. The present invention relates to a method of preventing photofading by improving stability to light.

[Background of the Invention] It has long been known that organic coloring substances, such as pigments or dyes, tend to fade due to light, and many methods have been developed to reduce this fading, that is, to improve light resistance. There are reports of. For example, in U.S. Pat. No. 3,432,300, organic compounds such as indophenol, indoaniline, azo and azomethine dyes are combined with phenolic type compounds having fused heterocyclic ring systems to produce visible and ultraviolet light. It is stated that the robustness against

In the field of silver halide color photographic materials, Mies (
The Theory of Photographic Process, 3rd edition (The Th@oryof) by Mees et al.
Photographic Process, 3r
(1967), azomethine dyes or indoaniline dyes are formed by the reaction of the oxide of an aromatic primary amine developing agent with a color former (coupler). .

It is desirable that the dye image obtained from such a coupler does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity.

However, the fastness of these dye images to mainly ultraviolet rays or visible light is not satisfactory, and it is known that they easily change color and fade when irradiated with these actinic rays. In order to eliminate such drawbacks, conventionally,
Methods have been proposed such as selecting and using various couplers with low fading properties, using ultraviolet absorbers to protect dye images from ultraviolet rays, and introducing groups that impart light resistance into couplers. ing.

However, in order to provide 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 of light resistance by ultraviolet absorbers. Furthermore, a method is known in which a dye image fading inhibitor having a phenolic hydroxyl group or a group that can be hydrolyzed to produce a phenolic hydroxyl group is used. Regarding these, for example,
-31256, 48-31625, 51-30
No. 462, JP-A-49-134326 and JP-A-49-134326
No. 134,327 describes phenol and bisphenols; U.S. Pat. No. 3,069,262 describes pyrogallol, gallic acid and its esters; U.S. Pat.
No. 90 and No. 4,015,990, α-tocopherols and their acyl derivatives, Japanese Patent Publication No. 52-275
No. 34, JP-A-52-14751 and U.S. Patent No. 2.
No. 735,765 has hydroquinone rust conductors, U.S. Pat.
-Hydroxychromans, U.S. Patent 3,573,050
The issue includes 5-hydroxychroman derivatives and
-20977 has 6,6'-dihydroxy-2,2'
- It has been proposed to use bisspirochromans and the like. However, although these compounds can be seen to some extent to be effective as dye fading and discoloration inhibitors, they are not sufficient.

British Patent No. 1,451,000 also describes improving the light stability of organic colored compounds using an azomethine quenching compound whose absorption peak is more bathochromic than that of the colored compound. However, since the azomethine quenching compound itself is colored, it is disadvantageous because it has a large effect on the hue of the colored substance. The use of metal complexes to prevent photodegradation of polymers has also been proposed by J.P. Guillory and GuiLlory.
, R.S., Becker).

Journal of Polymer Science, edited by Polymer Chemistry (J, Polym, Sci, Polym,
Chem.

Ed, ) vol. 12, p. 993 (1974), R.
B. R. Ranawela, G. Scotto (R,P
, R.

Ranaweera, G., 5cott), Journal of Polymer Science, Polymer Letters 1i (
J, Polym.

Sci,,Polym,Lett,Ed,, vol. 13, 7
1 (1975), etc., and a method for stabilizing dyes against light using metal complexes was published in Japanese Patent Application Laid-Open No. 1975 (1975).
-87649 and Research Disclosure 1
5162 (197δ), but these complexes do not have a large anti-fading effect and are not highly soluble in organic solvents, so it is difficult to add an amount sufficient to exhibit the anti-fading effect. Can not. Furthermore, since these complexes themselves have a large coloring property, when added in large amounts, they have an adverse effect on the hue and purity of organic coloring substances, especially pigments.

Furthermore, methods for photostabilizing dyes using various metal complexes are disclosed in JP-A-54-62826, JP-A-54-62987, and JP-A-54.
-65185, 54-89580, 54-72
No. 780, No. 54-82384, No. 54-82385
No. 54-82386, No. 54-136581,
No. 54-136582, No. 55-12129, No. 5
5-There is.

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

In addition, 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 the uncolored areas of the developed color photographic materials, especially When color photographic materials that have been processed are stored under conditions of high temperature and high humidity, the occurrence of contamination increases significantly.

Therefore, the known photofading inhibitors have a small antifading effect against light, or are colored themselves, or have problems in solubility in organic solvents, and are not sufficiently effective.
The initial objectives have not yet been achieved.

Therefore, the present inventor continued various studies in order to improve the stability against light without adversely affecting the hue and purity of organic coloring substances, and as a result, a compound having a structure represented by the general formula [11] described below was discovered. It was discovered that organic coloring substances have an antioxidant effect and are effective in stabilizing organic coloring substances against light, and the present invention was made based on this knowledge.

[Object of the Invention] An object of the present invention is to provide a method for preventing photofading in which the stability of an organic coloring substance to light is improved.

Another object of the present invention is to provide a method for preventing photofading that improves the light stability of organic coloring substances, particularly pigments or dyes, without deteriorating their hue and purity. .

Furthermore, another object of the present invention is to provide a method for preventing photofading, which improves the stability of color images against light to form color photographic images without causing contamination of uncolored areas of color photographic materials. be.

[Structure of the Invention] The above aspects of the present invention are achieved by coexisting an organic coloring substance and at least one type of compound represented by the general formula [I].

As used herein, the organic coloring substance used in the present invention refers to a substance that appears colored to the human eye under sunlight, and generally in a methanol solution at 300 nm.
It means an organic substance having at least one absorption maximum between ~800 r+m.

Also, the term light refers to the range from about 300 nm to about 800 nm.
+ means electromagnetic waves below, ultraviolet rays below about 400 rv,
Visible light from about 40 onI11 to about 700 nm and about 7
00 nm to about 800 rv.

General formula [11 [wherein R1 and R2 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, and a carbamoyl group. group, sulfamoyl group and oxycarbonyl group.

zI and z2 represent a simple bond or an alkylene group having 1 to 4 carbon atoms, and the total number of carbon atoms in % Zl and the alkylene group of 72 is 2 to 4.

Black represents single or double bonds.

R3 represents a substituent.

m lf represents O or an integer from 1 to 6, and when m represents an integer from 2 to 6, a plurality of R3's may be the same or different. ] The present invention will be explained in more detail below.

In general formula [11, the alkyl group represented by RI and R2 has 1 to 32 carbon atoms, alkenyl group,
Alkynyl groups have 2 to 32 carbon atoms, cycloalkyl groups, and cycloalkenyl groups have 3 to 12 carbon atoms.
In particular, those of 5 to 7 are preferred, and the alkyl group, alkenyl group, and alkynyl group may be straight or branched. Moreover, these groups may have a substituent. Specifically, methyl group, engineered tyl group, t-butyl group, pentadecyl group, 1-
hexylnonyl group, 2-chloro-t-butyl group, 2.4
-di-t-amylphenoxymethyl group, 1-ethoxytridecyl group, allyl group, isopropenyl group, ethynyl group, 2-propynyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group and the like.

The aryl group represented by R1 and R2 is preferably a phenyl group or a naphthyl group, and may have a substituent.

Specifically, phenyl group, 4-t-butylphenyl group,
Examples include 2.4-di-t-amylphenyl group, hexadecyloxyphenyl group, and α-naphthyl group.

The heterocyclic group represented by R+ and R2 is 5 to 7
Preferred examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group, which may be substituted or fused.

Examples of the acyl group represented by R1 and R2 include acetyl group, phenylacetyl group, dodecanoyl group, α
Examples include alkylcarbonyl groups such as -2,4-di-t-amylphenoxybutanoyl group, arylcarbonyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and p-chlorobenzoyl group.

Examples of the sulfonyl group represented by R1 and R2 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 R1 and R2 includes an alkylphosphonyl group such as a butyloctylphosphonyl group,
Examples include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by B1 and R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, N,
N-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbazoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4-di-t-
Examples include amylphenoxy)propyl)carbamoyl group.

The sulfamoyl group represented by R1 and R2 may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group,
Examples include N,N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group.

The oxycarbonyl group represented by R1 and R2 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, etc. group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

Further, the aryloxycarbonyl group may further have a substituent, for example, a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. represent an alkylene group.
The total number of carbon atoms in the alkylene groups 21 and 72 is 2 to 4. Further, the alkylene group represented by zI and z2 may be substituted with a substituent represented by R3.

Todoroki represents a single bond or a double bond.

The substituent represented by R3 is not particularly limited, but R
In addition to representing groups exactly the same as 1 and R2, anilino,
Acylamino, sulfonamide, alkylthio, arylthio, halogen atom, sulfinyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino , aryloxycarbonylamino, heterocyclic thio groups and spiro compound residues,
Also included are bridged hydrocarbon compound residues and the like.

Examples of the acylamino group represented by R3 include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R3 include an alkyl component in an alkylsulfonyl amino group and an arylsulfonyl group, and examples of the aryl component include the alkyl group and aryl group represented by nl above.

The sulfinyl group is an alkylsulfinyl group, the arylsulfinyl group is a ring acyloxy group, an alkylcarbonyloxy group,
Arylcarbonyloxy group ring; carbamoyloxy group includes alkylcarbamoyloxy group, arylcarbamoyloxy group, etc.; ureido group includes alkylureido group, arylureido group, etc.; sulfamoylamino group includes alkylsulfamoylamino group, aryl Sulfamoylamino group, etc. The heterocyclic group is preferably a 5- to 7-membered one, specifically a 2-furyl group or a 2-chenyl group.

2-pyrimidinyl group, 2-benzothiazolyl group, etc.: The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3,4.5.6-tetrahydrobilanyl-2-oxy group, 1- Phenyltetrazole-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 As a ring nispiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2,2,1
1 hebutan-1-yl, tricyclo[3,3゜1, t3
? ]]Decan-1-yl7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl and the like.

May be different.

Specific examples of the compound represented by the general formula [11] of the present invention are shown below, but the invention is not limited thereto.

Table 1 Table 2 In addition to the compounds listed in Tables 1 and 2 above, the following compounds may also be mentioned.

A-21A-22 0CIt 3 A-23A-24 2 It S
L; U U 113A -28A -29 The method for synthesizing the photofading inhibitor of the organic coloring substance represented by the general formula [I] according to the present invention is known, for example, as described in Organic Synthesis (Org, Syn, 1971). 5
pp. 1,136-13B, U.S. Pat. No. 3,502,688, U.S. Pat. No. 3,522,262, U.S. Pat.
No. 3,743,740, West German Published Patent No. 2,115,7
No. 38, No. 2,117.28Ii, No. 2,512,1
It can be synthesized according to the synthesis method described in No. 09 specification etc.

The above general formula [I] used in the photofading prevention method of the present invention
The amount of the photofading inhibitor represented by is preferably 5 to 400 mol%, more preferably 1% to 400% by mole based on the colored substance.
It is 0 to 300 mol%.

The organic coloring substances used in the method of the present invention (hereinafter also referred to as the present invention) include natural or synthetic dyes, water-soluble dyes such as basic dyes, acid dyes, direct dyes, soluble vat dyes, mordant dyes, and sulfur dyes. , vat dyes, oil-soluble dyes, disperse dyes, azoic dyes, insoluble dyes such as oxidation dyes, and reactive dyes. These organic coloring substances have a wavelength of 300 nm to 80 Or+m, preferably 400 nm in methanol solution.
It has at least one absorption maximum between nm and 700 nm.

Among these dyes, the dyes preferably used in the method of the present invention include quinone imine dyes (azine dyes, oxazine dyes, thiazine dyes, etc.), methine and polymethine dyes (
Dianine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoamine and indophenol dyes, iccoid dyes, carbonium dyes, formasan dyes, and other dyes belonging to chemical structural classes.

The organic coloring substances used in the method of the present invention include image-forming dyes used in the field of photography, such as color couplers,
It includes all dyes formed from DRR compounds, DDR couplers, amitracine compound dye developers, and dyes for silver dye bleaching methods.

Preferred dyes for use as organic colorants applied to the method of the invention include anthraquinone, quinoneimine, azo, methine, 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 yellow, magenta and cyan dye-forming types. This coupler is described in US Pat. No. 3,277.155, for example.
It may be a so-called 4-equivalent type or a 2-equivalent type as described in No. 3,458,315.

Preferred yellow dye image-forming couplers in the present invention are of the benzoylacetanilide type, pivaloylacetanilide type, or those in which the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction (so-called split-off group). There are 2-equivalent type di-rho dye image-forming couplers, and magenta dye image-forming couplers include 5-pyrazolones, pyrazolotriazoles, imidazopyrazoles, pyrazolopyrazoles, pyrazolotetrazoles, and pyrazolinos. There are 2-equivalent type magenta dye image-forming couplers having benzimidazole type, indashilon type or split-off group, and cyan dye image-forming couplers include phenol type, naphthol type, pyrazoloquinazolone type or 2-equivalent type having split-off group. type cyan dye image-forming couplers.

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

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

-t Y-3 O (nee CII'3 Hs) These yellow couplers are described in
No. 057,941, West German Publication No. 2,163,812, Japanese Patent Application Publication No. 47-26133, Japanese Patent Publication No. 48-29432,
No. 50-65231, No. 51-3631, No. 51-
No. 50734, No. 51-102636, No. 48,68
No. 835, No. 4B-94432, No. 49-1229, No. 49-10736, Special Publication No. 51-33410,
It includes the compounds described in No. 52-25733 and the like, and can be synthesized according to the methods described therein.

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

O Shi! D! O Shi! ■ Hs M-9 These magenta couplers are disclosed in, for example, U.S. Patent No. 3.68.
No. 4,514, British Patent No. 1.183,515, Japanese Patent Publication No. 40-6031, No. 4G-6035, British Patent No. 44-15
No. 754, No. 45-40757, No. 4δ-19032
No., JP-A-50-13041, JP-A No. 53-129035
No. 51-37645, No. 55-52454, U.S. Patent No. 3,725,067, British Patent No. 1,252,4
No. 18, No. 1,334,515, Japanese Unexamined Patent Publication No. 59-171
No. 956, No. 59-162548, No. 60-4365
No. 9, No. 60-33552, Research Disclosure? -(Research Disclosure)
2462B (1984), patent application No. 59-243007
No. 59-243008, No. 59-243009, No. 59-243012, No. 60-70197, No. 10-70198, 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, typical examples of cyan couplers that can be used in the present invention will be given.

Our cyan couplers are disclosed in US Pat. No. 2.423, for example.
No. 730, 2JQ, No. 1,171, JP-A No. 1983-11
No. 2038, No. 50-134644, No. 53-109
No. 630, No. 54-55380, No. 5B-1i513
No. 4, No. 5B-80045, No. 57-155538, No. 57-204545, No. 58-98731, No. 59-31953, etc., and methods described therein. It can be synthesized according to the following.

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.

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

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

l4 Additionally, other types of dyes preferably used in the present invention include tl, s, B 351,673, U.S. Pat.
No. 932,381, No. 3,928,312, No. 3,9
No. 31,144, 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. 635, No. 4,013,633, Japanese Unexamined Patent Publication No. 1986-11
No. 3624, No. 51-109! No. 128, No. 51-10
No. 4343, No. 52-41119, Patent application 1982-64
No. 533, rRe5earchDisclosure
” Magazine (Research Disclosure) (1976
(November issue) pp. 68-74, same magazine no.

13024 ('75) etc., which are formed by oxidation of DRR compounds.

Furthermore, other types of dyes that may be used in the present invention include, for example, British Patent Nos. 840,731 and 904.364.
No. 932,272, No. 1,014,725, No. 1.038,331, No. 1,066.352, No. 1
．． No. 097.064, JP-A-51-133021, 1
IsT900,029 (U, S.

dyes released or formed by the reaction of a DDR coupler with an oxidized form of a color developing agent, such as those described in U.S. Pat. can be mentioned.

Other types of dyes preferably used in the present invention include Japanese Patent Publications No. 35-182, No. 18332, No. 48-
No. 32130, No. 4 [1-43950, No. 49-26]
Examples include dye developers described in No. 18 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 (CI 290001,
Glino 7 x 2: / (Azo dyes such as CI 248951, Indigo Golden Yellow IGK (C15
9101), Indigosol Yellow 2GB (CI
61726), Arbosol Yellow GCA-CF (
CI67301), Indanthrene x Low GF
(C188420), Mikethrene Yellow GC (CI
67300), Indanthrene Yellow 4GK (C1
Examples include benzoquinone dyes such as 68405); anthraquinone dyes, polycyclic soluble vat dyes, and other vat dyes. Magenta dyes include azo dyes such as Sumilite Sublarbinol B (CI 29225L Benzo Brilliant Keranin B ((:I 15080)), indigosol brilliant pink IR (C
I 73361), Indigosol Violet 15
R (C159321), Indigosol Red Violet IRRL (C15!1311i), Indanthrene Red Violet RRX (CI67895), Mikethrene Brilliant Violet 6BK (CI [1
Indigoid dyes such as 335); benzoquinone dyes,
Examples include soluble vat dyes made of anthraquinone heteropolycyclic compounds and other vat dyes.

As a cyan dye, Direct Sky Blue 5B (
Azo dyes such as CI 24410), Direct Brilliant Blue 23 (CI 22610), Sumilight Subra Blue-G (CI34200), Sumilight Subra Turkish Blue G (CI 74180), Mikethrene Brilliant Blue 4G (II:I 741)
Examples of the dyes include phthalocyanine dyes such as 40), Indanthlen Turkey Sprue 5G (C16'1845), Indanthlen Blue-GCD (C173066), Indigosol 04G (C173046), Anthrazole Green Ill (C159826), and the like.

Furthermore, the compound represented by the general formula [I] used in the method of the present invention can also prevent colorless substances from being oxidized and colored. In particular, discoloration of non-image areas of color photographic materials can be effectively prevented.

As mentioned above, the compounds used in the method of the invention are those that stabilize organic coloring substances. These compounds of the present invention can be present in any or all of the emulsion layers of the color photographic light-sensitive material. The compounds of the invention may also be present in any of the layers comprised in the non-light-sensitive portions of the color transfer material. The methods effective for dispersing these compounds of this invention are the same as those described for dispersing couplers.

The compounds used in the method of the present invention are generally oil-soluble and are commonly used in U.S. Pat.
, No. 170, No. 2,801,171, No. 2,272,
191 and No. 2,304.940, it is preferable to dissolve it in a high boiling point solvent and, if necessary, in combination with a low boiling point solvent, disperse it, and add it to the wood-philic colloid solution. If necessary, there is no problem in using a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor, etc. In this case, two or more compounds used in the method of the present invention are used in combination. I have no problem with that either. Further, to explain in detail the method of adding the compound used in the method of the present invention, the compound having 1 fi or 2 f1 or more is added as necessary to a coupler, a hydroquinone conductor, an ultraviolet absorber, or a known dye image fading inhibitor. At the same time, organic acid amides, carbamates, esters, ketones, hydrocarbons, urea conductors, etc., especially di-n-butyl phthalate, tricresyl phosphate, Jimmy octyl azelate, di-n-
Butyl sebacate, tri-n-hexyl phosphate,
Decalin, N,N-di-ethyl-caprylamide,
High boiling point solvents such as N,N-diethyl laurylamide, n-pentadecyl funinyl ether or fluoroparaffin, and if necessary, low boiling point solvents such as ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, and tetrahydrofuran. These high boiling point solvents and low boiling point solvents that are soluble may be used alone or in combination. ) Mixed with an aqueous solution containing a wood-philic binder such as gelatin containing anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. Then, it can be emulsified and dispersed using a high-speed rotating mixer, a colloid mill, an ultrasonic dispersion device, etc., and the resulting dispersion can be added to a hydrophilic colloid solution (for example, a silver halide emulsion) for use.

Both the colorant and the compound used in the method of the invention can be present in any or several of the parent colloid layers of 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 light-absorbing 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 compound of the present invention has a molecular form that allows it to be retained in the mordant layer of the image receptor without migrating away from the dye to be stabilized. Must be.

There are several types that may be effective when using the method of the present invention to improve the lightfastness of photographic elements such as image transfer film units.

One such application is in Vivision transfer film units such as those described in US Pat. No. 2,8112.156. Yet another application is U.S. Patent 2.087,
No. 817, No. 3,185,567, No. 2,983,6
No. 06, No. 3,253,915, No. 3,227,55
No. 0, No. 3,227゜551, No. 3,227,552
No. 3,415,644, No. 3,415.645, No. 3,415,641i, No. 3,594,164 and No. 3,594,165, and Belly Patent No. 757
, No. 959 and No. 757,960.

The coloring substances and anti-photofade compounds used in the method of the present invention have a Product Licensing Index (1
'product Licensing Index),
Volume 92 (December 1971), No. 9232, 1
With materials such as those listed on pages 07-110,
It can be used according to that method. Regarding this point, see 1. of the above-mentioned document. n, it, +v, vM, vm, r
x, x.

Xl, X[[, XI, XIV, XV, XVI,
Sections X■, X■, and XX 111 are applicable.

Any type of compound of the invention should provide the improvements of the invention, and there is theoretically no upper limit to the amount that may be used.

When the invention is applied to photographic materials, it is preferred that at least 1 micromole of the compound of the invention is present per square meter of the material, with about 10 to IXIG' micromole of the compound of the invention per square meter of the material. It is even more preferable if it exists.

Generally, the colorant concentration should be equal to that commonly used in color photography techniques. These densities are well known to those skilled in color photography. Preferably, the colorant is present in an amount ranging from about 10 to 104 micromoles per square meter of light-sensitive material. Photosensitive material 1
More preferably, it is present in an amount ranging from about 100 to about 600 micromoles per square meter.

The colored substances used in the present invention generally have maximum wavelength absorption peaks in methanol solution that are smaller than 80OnI11. The maximum wavelength absorption peak of this base material is preferably in the range of 300 to 800 nm in methanol solution,
Most preferably, it is in the range of 400 to 700 nm.

In the photographic light-sensitive materials to which the method of the present invention is applied, 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, and silver iodide. , silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof.These silver halides can be produced by various methods such as the ammonia method, the neutral method, the so-called conversion method, and the simultaneous mixing method. . In addition, gelatin and derivative gelatin such as phthalated gelatin and malonated gelatin are generally used as wood-philic colloids for dispersing silver halide. , gum arabic, alginic acid, casein, partially hydrolyzed cellulose conductor, partially hydrolyzed polyvinyl acetate, polyacrylamide, imidized polyacrylamide, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used. Further, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes include, for example, cyanine dyes, merocyanine dyes, and composite cyanine dyes, which may be used alone or in combination of two or more. Further, chemical sensitization can be carried out by a conventional method. Chemical sensitizers include gold compounds such as chlorauric acid salts and gold trichloride; noble metals such as platinum, palladium, and iridium; sulfur compounds that react as silver salts to form silver sulfide, such as sodium thiosulfate; Examples include stannous salts, amines, and other reducing compounds. In addition, stabilizers such as triazoles, imidazoles, azaindenes, benzothiazoliums, zinc compounds, cadmium compounds, mercaptans, etc.; chromium salts, zirconium salts, mucochloric acid, aldehyde series, triazine series, polyepoxy compounds, Hardeners such as triethylene phosamide and ethyleneimine; plasticizers such as dihydroxyalkanes such as glycerin and 1,5-bentanediol; optical brighteners; antistatic agents; and various coating aids. Photographic additives can be used alone or in combination of two or more.

Further, the above-mentioned compounds of the present invention are dispersed in the obtained silver halide emulsion to contain a dispersion liquid, and if necessary, cellulose acetate, cellulose nitrate, polycarbonate are added via a subbing layer, an intermediate layer, a protective layer, etc. A color photographic material can be obtained by coating a support such as a synthetic resin film such as , polyethylene terephthalate, or polystyrene, baryta paper, polyethylene-coated paper, or a glass plate.

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

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, with water washing, stabilization, and other steps included as necessary. Two or more of these steps can be carried out in one bath, such as in a bleach runner. 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 were previously described as exemplified developers [1] to [12].

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 [1] to [12] 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-p-phenylenediamine, and the like can be used.

In order to form a color image in the color photographic material used in the method of the present invention, a method using a coupling reaction between the aforementioned dye-forming color coupler and an oxidized form of a p-phenylenediamine color developing agent; A method using a dye developer, a method using an oxidative burst reaction of a DRR compound, a method using a dye separation reaction due to a coupling reaction of a DDR coupler, a method using a dye forming reaction due to a coupling reaction of a DR coupler, or a method using a silver dye. Known methods such as a bleaching method can be used.

Therefore, when applying the method of the present invention to photographic light-sensitive materials, various color photographic light-sensitive materials such as color positive film, color vapor, color negative film, color reversal film, color diffusion transfer film unit, light-sensitive material for silver dye bleaching, etc. can be mentioned.

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

Example 1 Magenta dye having the following structure (maximum absorption in methanol solution: 5:18 nm) Shi! 0.5 g of dibutyl phthalate)-4 mjl and ethyl acetate (8 mj), and this solution was dissolved in a 10% solution containing 2 mg of 0.5% sodium dodecylbenzenesulfonate aqueous solution.
Gelatin solution 10a+I! It was emulsified and dispersed.

Next, this emulsified dispersion was mixed with a 5% gelatin solution (30%) and coated on a paper support laminated on both sides with polyethylene to obtain a sample. This sample is designated as No.1.

When preparing the above emulsified dispersion liquid in the same manner, 250B of the comparative compounds represented by the following structural formulas (a) and (b) were added to each, and applied in the same manner as for the above sample No. 2 and No. 2. No. 3 was created.

Further, when preparing the emulsified dispersion liquid by the method of Sample No. 1, as shown in Table 1, each of the exemplary compounds of the present invention was added at 250 mi! Twelve types of samples (Nos. 4 to 15) were prepared by adding each sample in the same manner as the sample No. 091.

Comparative compound (a)...Metal complex comparative compound (b) described in JP-A-55-12129...Same as above Each of the above samples was exposed to a xenon fade meter for 200 hours to determine the light resistance of the dye image. I looked into it. The results are shown in Table φ. However, the light resistance of the dye image was determined based on the dye residual rate.

As is clear from Table R below, the samples (Nos. 4 to 15) using photofading inhibitors used in the method of the present invention are different from the samples (Nos. 2 and 3) using known metal complexes. ) showed a superior photofading prevention effect, and almost no blackish-brown discoloration of the sample was observed.

Example 2 In Example 1, the magenta dye was used as a magenta dye having the following structure (maximum absorption of 536 nm in methanol solution).
15 types of samples (No. 16 to 30) were prepared in the same manner as in Example 1 except that the sample was changed to . The obtained sample was exposed to a xenon fade meter for 150 hours to examine the light resistance of the dye image. The results will be presented to the public.

(Magenta Dye) Table 1- It can be seen that the sample using the anti-fading agent has a superior photo-fading preventing effect than the sample using the known metal complex. Further, the sample according to the present invention had almost no blackish-brown discoloration and had a favorable hue even after the black light fastness test.

Example 3 25 g of exemplified coupler (M-8) as magenta coupler
tricresyl phosphate 25 and ethyl acetate 10
The solution dissolved in 0 mI2 was added to 5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate.
After adding to 0 mg, it was dispersed with a homogenizer, and the resulting dispersion was added to a green photosensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion 1000+aj), and N as a hardening agent,
10 mg of a 2% methanol solution of N',N''-triacryloylhexahydro-S-triazine was added, coated on polyethylene coated paper and dried to obtain a sample of a monochromatic color photographic material.This sample will be referred to as No. 31.

Samples No. 32 and No. 33 were prepared by similarly applying the above emulsified dispersion in the same manner, and adding 20 g of each of the comparative compounds (.) and shoulder having the following structures.

Seven types of samples (Nos. 34 to 40) were prepared by adding 20 g of each of the exemplified compounds listed above and applying the same in the same manner.

Comparison compound (C): Compound described in JP-A No. 54-48538 Comparison compound source: Compound described in JP-A-56-159644 After exposing each of these samples, the following processing solution and processed in the processing step.

[Developer] Add water to adjust the pH to 12, and use sodium hydroxide to adjust the pH.
Adjust to 1o, 30.

[Add bleach-fix solution and water for 1f! Bind, poa using ammonia water,
Adjust to s.

[Processing process] (30℃) Processing time Each sample on which a dye image was formed in this way was treated with a Kodak Wratten filter N, which is an ultraviolet cut filter.
Subtract 1 inch from 0028 and get 150 with a xenon fade meter.
A time fading test was conducted.

the law of nature The results are shown in the table below.

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

Table 1 (The maximum absorption of the colored magenta dye in a methanol solution was 536r+n+.) As is clear from the surface blue effect results, the anti-fade agent of the present invention is superior to conventional organic anti-fade agents. It has an anti-fading effect.

Example 4 As a cyan coupler, 35 g of the exemplary coupler (C-S) was mixed with 35 g of dioctyl phthalate and 100 m of ethyl acetate.
500 mR of a 5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate.
The resulting dispersion was added to red-sensitive silver chlorobromide (containing 30 mol% silver chloride) emulsion 100hi+, and N, N', N'' were added as hardeners.
10 mg of a 2% methanol solution of -triacryloylhexahydro-5-t-lyazine was added, coated on polyethylene coated paper and dried to obtain a sample of a monochromatic color photographic material. This sample is designated as No. 41.

When preparing the emulsifier dispersion liquid in the same manner as in Example 3, 10 g of each of the comparative compound (e) having the following structure and the exemplified compound of the present invention as shown in Expression 4 were added to prepare 9 types of samples (No.
42-50) were created.

Comparative compound (e): Compound described in JP-A-59-87456 After exposing each of these samples, the dye image obtained by processing in exactly the same manner as in Example 3 was filtered with an ultraviolet cut filter ( The same as used in Example 3) is attached to Table 1 (maximum absorption of chromogenic cyan dye in methanol solution is 6
It was 52 nm. ) As is clear from the table, the compounds of the present invention also have a great effect of preventing photofading of cyan coloring dyes.

In the method for preventing photofading, the use of the antifading agent represented by the general formula [11] is far more effective than conventional methods against fading of organic coloring substances, especially dyes in color photographic materials, due to light. It has an excellent anti-fading effect and can maintain color photographic images stably for a long period of time.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent
Patent Attorney Miki Nakajima Eloquent Hiroki Kuramochi

Claims (1)

[Claims] A method for preventing photofading of an organic coloring substance, which comprises coexisting the organic coloring substance with at least one compound represented by the general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. , a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, and an oxycarbonyl group. Z_1 and Z_2 represent simple bonds or alkylene groups having 1 to 4 carbon atoms, and the total number of carbon atoms in the alkylene groups of Z_1 and Z_2 is 2 to 4. ■ represents a single bond or a double bond. R^3 represents a substituent. m represents 0 or an integer from 1 to 6, and when m represents an integer from 2 to 6, the plurality of R^3's may be the same or different. ]