JPH03137640A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance discoloration preventive effect of a dye image without causing stains and deteriorating the color development performance of a coupler by incorporating a specified discoloration preventive agent. CONSTITUTION:At least one photographic constituent layer of this photosensitive material contains at least one kind of the discoloration preventive agent represented by formula I in which R<1> is alkyl, alkenyl, aryl, or the like, and each of R<2> - R<6> is H, alkyl, alkenyl, or the like, and embodied by a compound of formula II and the like, and this compound can be contained in a desired emulsion layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material in which an organic coloring substance such as a dye image formed in the photographic material is stabilized. More specifically, the present invention relates to a silver halide color photographic material containing a type of stabilizer for improving the stability of organic coloring substances such as dye images obtained by the silver halide photographic material. .

BACKGROUND OF THE INVENTION A common color photographic material includes red, green and blue sensitive silver halide emulsion layers containing cyan, magenta and yellow couplers, respectively, in or adjacent to the layers. When developed with a developer containing a p-fuynylenediamine color developing agent, a dye image is formed.

It is known to include stabilizers in color photographic materials to reduce the deterioration of such dye images due to the effects of light, heat and/or humidity. JP-A-62-282047 describes the use of special bisphenol derivatives to improve the fastness of color images.

However, the drawbacks of the above bisphenol derivatives are that
This is where they cause hue staining in the developed dye image. Furthermore, the effect of preventing fading of coloring pigments is not sufficient.

In addition, a hydroquinone-based conductor was published in Japanese Patent Application Laid-Open No. 54-48538.
No. 55-69141, No. 55-89836, etc., and it has been shown that the fastness of colored dye images is considerably improved, but it is still not sufficient.

[Object of the Invention] An object of the present invention is to provide a photographic material that has an excellent anti-fading effect, and a further object is to prevent fading that does not cause staining or reduce the color development of couplers. An object of the present invention is to provide a silver halide photographic material containing an inhibitor.

Still another object is to provide a silver halide photographic material that is free from precipitation and has improved dispersion stability.

[Structure of the Invention] The present invention provides a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, in which at least one of the photographic constituent layers has a compound represented by the general formula [1]. It has been found that the above object can be achieved by a silver halide color photographic light-sensitive material containing at least one of the compounds shown below.

General formula [I] 6 [wherein R1 is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Represents an arylthio group, an alkylamino group, or an arylamino group. R2 is a hydrogen atom, an alkyl group, an alkenyl group,
Represents an aryl group.

R3R4RB and Ra are hydrogen atoms, alkyl groups, alkenyl groups, halogen atoms, aryl groups, hydroxy groups, alkylthio groups, arylthio groups, alkoxy groups, aryloxy groups, alkylamino groups, arylamino groups, acylamino groups, sulfonamino groups, Represents a carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, acyl group, sulfonamino group, carbamoyl group, and any 2 of R3R4R8 and R6
may be closed to form a polynomial ring.

Furthermore, R1 and R2 may be substituted with other substituents, such as an alkyl group, a halogen atom, a nitro group, a carbamoyl group, an acylamino group, a sulfonamino group, a sulfamoyl group, a sulfo group, a carboxyl group, Examples include cyano group, alkoxy group, acyl group, sulfonyl group, hydroxy group, aryloxy group, and alkoxycarbonyl group. In addition, each of the alkyl groups mentioned above is a straight chain,
Including branched and cyclic ones. ] Specific compounds used in the present invention are shown below, but the present invention is not limited to these examples.

Margin below 5.

6.

7.

2H5 20°NHIUH3 16°17°18°19° Compounds of the present invention include, for example, 5ynthesis, 197
9. It can be synthesized with good yield in just one step by the method shown on page 366.

6 A synthesis example is shown below.

[Synthesis Example] (Synthesis of Exemplary Compound 1) 23.5 g of 4-methoxy-2-t-octylphenol
was dissolved in 300 al of toluene, and then phenylboronic acid 14. Og (manufactured by Tokyo Kasei Co., Ltd.), rose formaldehyde 1.8 g, ) lychloroacetic acid 4.0 g
was added, and water was distilled off using an ester tube, while the mixture was cooled for 15 hours. After distilling off the toluene and dissolving the residue in chloroform, the chloroform layer is thoroughly washed with water. After drying with magnesium sulfate, chloroform was distilled off and the residue was subjected to column chromatography (toluene:ethyl acetate=8:
2). It was confirmed by NMR and MS spectra that it was the desired product.

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

The organic coloring substance used in the silver halide photographic light-sensitive material of the present invention is 300 nm to 800 nm in methanol solution.
m, preferably at least 1 between 400 nm and 700 nm
refers to organic substances that have two absorption maxima, including basic dyes, acid dyes, direct dyes, soluble vat dyes, water-soluble dyes such as mordant dyes, sulfur dyes, vat dyes, oil-soluble dyes,
It includes all dyes belonging to the classification of dyeing properties such as insoluble dyes such as disperse dyes, azoic dyes, and oxidative dyes, and reactive dyes.

Among these dyes, dyes preferably used in the present invention (quinone/fmine dyes (azine dyes, oquinazine dyes, thiazine dyes, etc.), megoon and polymethine dyes (
dianine dyes, azomethine dyes, etc.), azo dyes, an-1-laquinone dyes, indoaniline and f-dophenol dyes! 1. Indicoid dye, NOJ rubonium dye,
It includes dyes 1 belonging to the chemical class of formazan dyes and the like.

Organic colored material 1 (is an image-forming dye used in the field of photography, such as color coupler 1), which is found in Kippatsu] RR
compound, D D R no J pla amitracine compound,
It includes all dyes formed from dye-producing agents, dyes for silver dye bleaching, etc.

Preferred dyes for use as organic colorants in the present invention include anthraquinone, quinoneimine, azo, methine, volumedine, indoaniline, indophenol and formazan dyes.

Dyes most preferably used in the present invention include methine JJ and polymethine dyes, indoaniline ozole dyes,
There are virazolo pime-4-, pyrazolotetrazole, pyrazolinobenzimidazole, and indasilone couplers, and cyan dye image-forming couplers include phenol, naphthol, and virazoloquinazolone couplers.

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

Next, typical examples of yellow couplers will be given.

-3 -4 -5 ell.

-6 M-1 -2 These yellow couplers are described, for example, in West German Published Patent Application No. 2.
No. 0570941, West German Published 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. 5l-10263 (No. i, No. 43-6
(No. i835, No. 48-94432, No. 49-122
No. 9, No. 49-1073 [No. 3, Special Publication No. 51-3341
No. 0, No. 52-25733, etc., and can be synthesized according to the methods described therein.

Next, a typical example of a magenta coupler will be given.

-4 -8 -9 -5 -10 -6 -7 -2 C-3 -4 -5 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, 40-0035, 44-15
No. 754, No. 45-40757, No. 40-19032
No., JP-A-50-130.41, JP-A No. 53-12903
No. 5, No. 51-37646, No. 55-62454,
U.S. Patent No. 3.725.067, British Patent No. 1,252,
No. 418, No. 1,334.515, JP-A-59-17
No. 1956, No. 59-16254.9, No. 60-43
No. 659, No. 60-33552 Research Disclosure No. 24626 (1984), Patent Application No. 59-243007, No. 59-243008, No. 5
No. 9-243009, No. 59-243012, No. 60
-70197, No. 460-70198, etc., and can be synthesized according to the methods described therein.

There are no particular restrictions on the cyan coupler, but a phenolic cyan coupler is preferred.

A typical example of a cyan coupler is given below.

C-] These cyan couplers are described, for example, in U.S. Pat. No. 2,423.
No. 730, No. 2,801.171, Japanese Unexamined Patent Publication No. 1983-11
No. 2038, No. 50-134644, No. 53-109
No. 630, No. 54-55380, No. 56-65134
No. 5 [3-80045, No. 57-155538, No. 57-204545, No. 58-98731, No. 59-31953, etc.,
And, it can be synthesized according to the methods described therein.

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

The above-mentioned developing agents include aminophenol and phenylene diamine, and these developers can be used in combination.

The above-mentioned anti-fading agent of the present invention is preferably present in the color photographic material, particularly in the organic coloring substance or the layer in which it is formed, or in a layer adjacent thereto.

The methods effective for dispersing these compounds of this invention are the same as those used for dispersing couplers.

The compounds used in the present invention are generally oil-soluble and are usually disclosed in U.S. Pat.
91 and No. 2,304,940, it is preferable to dissolve it in a high boiling point solvent, optionally in combination with a low boiling point solvent, disperse it, and add it to the hydrophilic colloid solution. If necessary, there is no problem in using a coupler, a hydroquinone conductor, an ultraviolet absorber, or a known dye image fading preventive agent.
Compounds described in No. 1, etc. can be mentioned. At this time, the compound of the present invention was added to 21! There is no problem in mixing the above.

The silver halide emulsion used in the photographic light-sensitive material of the present invention generally has silver halide grains 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.

[Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these.

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, which was designated as Sample 1.

1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide]acetanilide at 6.8a+
g/100cm2, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.2mg/100cm"
Dibutyl phthalate was coated at a coating amount of 3.5 mg/100 cm2 and gelatin was coated at a coating amount of 13.5 mg/100 cm''.

2nd layer; middle layer 0.5 mg of 2.5-di-t-octylhydroquinone
/100ca+2 0.5mg dibutyl phthalate
/I0Gcm' and gelatin 9.0mg7100cm
' It was painted so that it looked like this.

Third layer; green-sensitive silver halide emulsion layer 3.5 mg of the magenta coupler (M-5) 710
0cm', green-sensitive silver bromide emulsion (containing 80 mol% silver bromide)
2.5 m37100cm2 in terms of silver, 3.0mg7100cm2 of dibutyl phthalate and 12.0mg/11)Oc11' of gelatin were coated.

4th layer; 2-(2-hydroxy-3゜5-di-t) of the intermediate layer ultraviolet absorber
-butylphenyl)benzotriazole 0.7mg7
100cm2, dibutyl phthalate 6.0mg710
0cm2.2.5-di-t-octylhydroquinone 0.5mg7100cm'' and gelatin 12.0mg
/100cm2.

5th layer: red-sensitive silver halide emulsion layer 2-[α-(2,4-di-t-pentylphenoxy)butanamide]-4,6-dichloro-5-ethylphenol was added at 4.2 mg/I as a cyan coupler. (lQca+
", red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver is 3.0 mg/100 cm', tricresyl phosphate is 3.5 mg/loocm2, and gelatin is 11.51 Jl/1100 Cl. ” It was painted so that it looked like this.

Sixth layer: Protective layer Gelatin was coated at a concentration of 8.0 mg/100 cm'.

In Sample 1, the compounds used in the present invention were added to the third layer in the combinations shown in Table 1 at a ratio of 100 mol % to Cp to prepare Multilayer Samples 2 to 9.

After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps.

[Processing process Processing temperature Processing time Color development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Wash with water for 1 minute and 30 seconds at 33℃
Dry for 3 minutes at 50-80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] Benzyl alcohol 12fflft
Diethylene glycol IO+mQ potassium carbonate 25 g Sodium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Hydroxylamine sulfate 2.58 N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 4.5 g Water was added to make the solution 11, and the pH was adjusted to 10.2 with NaOH.

[Bleach-fix solution] Ammonium thiosulfate 120. g Sodium metabisulfite 151g Anhydrous sodium sulfite 3. g Ethylenediaminetetraacetic acid ferric ammonium salt 85 g Water was added to set Ik and 9H was adjusted to 6.7 to 6.8.

The concentrations of Samples 1 to 1O treated above were measured using a densitometer (Model D-7R, manufactured by Konica Corporation) under the following conditions.

The processed sample 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-54-48538) Comparative compound 2 (compound described in JP-A-55-89836) Table 1 Comparative compound 3 (compound described in JP-A-55-69141)
From the results shown in Table 1, the use of the compounds of the present invention was effective in stabilizing magenta dye images formed from magenta couplers, and Y-stin in unexposed areas was also improved. Further, during dissolution, there was no precipitation and the dispersion stability was good.

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. Samples 10 to 21 were the same as Sample 1 in Example 1 except that
was created.

Samples 10 to 21 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℃ 45 seconds bleach fixing
34.7±0.5℃ Stabilized for 45 seconds 30~3
Dry for 90 seconds at 4℃ 60-80℃
The composition of the treatment liquid used in each 60 second treatment step is as follows.

[Color developer] Pure water
800ml triethanolamine
88N,N-diethylhydroxyamine 5g Potassium chloride 2gN-ethyl-N
-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
30 g potassium sulfite
0.2 g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid conductor) 1 g Pure water was added to bring the total amount to 11, and the pH was adjusted to 10.2.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 6og ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70 in solution) 100mu ammonium sulfite (
4096 solution) 27.5 ml Potassium carbonate or glacial acetic acid to adjust the volume to 15 and 7, and add water to bring the total volume to 11.
And so.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1゜1-diphosphonic acid 2g Add water to make up to 1Il with sulfuric acid or potassium hydroxide to make p)l 7 ,0
Adjusted to.

The light resistance of each sample after treatment was tested and evaluated in the same manner as in Example 1. The results are shown in Table 2.

Table 2 As is clear from Table 2 below, the samples using the exemplified compounds according to the present invention exhibit good light fastness of dye images. Further, the dispersion stability was good.

Example 3 When the color image stabilizer of the present invention was added to the yellow coupler and cyan coupler of the present invention in the same way as the magenta coupler of Example 2, good light fastness of color images was exhibited.

Further, good color images were obtained and dispersion stability was also good.

[Effects of the Invention] The present invention provides a silver halide photographic material obtained by adding the compound represented by the formula [I], which is prevented from fading without reducing the coloring properties of the coupler, and furthermore: A silver halide photographic material containing this compound has excellent dispersion stability.

Claims (1)

[Scope of Claims] A silver halide photographic material having a photographic constituent layer including at least one silver halide emulsion layer on a support, in which at least one of the photographic constituent layers is represented by the general formula [I]. A silver halide color photographic material containing at least one compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an amino group. R^2 is a hydrogen atom, R^3, R^4, R^5
and R^6 is a hydrogen atom, an alkyl group, an alkenyl group, a halogen atom, an aryl group, a hydroxy group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamino group , represents a carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, acyl group, sulfonamino group, carbamoyl group, and any two of R^3, R^4, R^5 and R^6 are The ring may be closed to form a polynomial ring. Furthermore, R^1 and R^2 may be substituted with other substituents, such as an alkyl group, a halogen atom, a nitro group, a carbamoyl group, an acylamino group, a sulfonamino group, a sulfamoyl group, a sulfo group. , carboxyl group, cyano group, alkoxy group, acyl group, sulfonyl group,
Examples include hydroxy group, aryloxy group, alkoxycarbonyl group, and the like. Note that each of the alkyl groups mentioned above includes linear, branched, and cyclic ones. ]