JPH03142444A - Silver halide photographic sensitive material improved in fastness of dye image - Google Patents

Abstract

PURPOSE:To enhance fastness of a dye image by incorporating a specified compound in a photographic constituent layer. CONSTITUTION:At least one of the photographic constituent layers of this photosensitive material contains as the discoloration preventive agent the compound of formula I in which R1 is alkyl, aryl, or the like; each of R2 - R5 is H or a substituent; X is merely a bonding or a linking group; Y is O, S, or the like; and (n) is 0 or 1. This compound can be embodied by formula II and the like, and they can be added to a desired color sensitive emulsion layer or its adjacent layer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to the stabilization of organic coloring substances, such as dye images, which are incorporated into photographic materials. In particular, the present invention relates to the use of a class of bis-type phenolic derivative stabilizers to improve the stability of organic coloring materials such as dye images obtained by silver halide photographic materials.

[Background of the invention]

A typical color photographic material contains red, green and blue sensitive silver halide emulsion layers containing cyan, magenta and yellow couplers, respectively, in or adjacent to the layers, p- When developed with a developer containing a 722 diamine color developing agent, a dye image is formed.

It is known to include stabilizers in color photographic materials to reduce deterioration of dye images due to the effects of light, heat and/or humidity. Japanese Patent Publication No. 48-31256 describes the use of special bisphenol derivatives to improve the fastness of color images.

However, the above-mentioned bisphenol derivatives did not have a sufficient anti-fading effect.

[Purpose of the invention]

An object of the present invention is to provide a photographic material having an excellent anti-fading effect.

[Structure of the invention]

The above object was achieved using a silver halide photographic material having the following structure.

In a silver halide photographic material having a photographic constituent layer including at least one silver halide emulsion layer on a support, at least one of the photographic constituent layers has the following general formula (1).
A silver halide photographic material containing a compound represented by:

General formula (I) In the formula, %R1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R2-R3 represents a hydrogen atom or a substituent, and at least one of R5-R3
One is a halogen atom, ORs, SRs7 / 11 N (Rs is an alkyl group, cycloal\R.

Kyl group, alkenyl group, aryl group or heterocyclic group,
R and R represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an acyl group, a sulfonyl group, or a carbamoyl group. ), X represents a bond or a divalent bonding group, and Y is 10-, -S, -NH, or -NR+- (RI has the same meaning as R1 above. However,
The two R's may be the same or different. ) represents. n represents 0 or l.

[Specific structure of the invention]

The compound represented by general formula (I) will be explained.

In the general formula [I], the alkyl group represented by RI includes, for example, a methyl group, ethyl group, propyl group, or butyl group; the dichloroalkyl group includes, for example, a cyclohexyl group; the alkenyl group includes, for example, an allyl group; an aryl group; The group includes, for example, a phenyl group; the heterocyclic group includes, for example, a 2-pyridyl group or a 2-furyl group,
Each group represented by R1 includes those having a substituent.

Examples of the divalent bonding group represented by , for example, an ethylene group; an alkyleneoxy group, such as an ethyleneoxy group; and an alkylenethio group, such as an ethylenethio group. Among these, preferred as X are alkylidene groups and heteroatoms.

Representative examples of groups that can be substituted on the benzene ring represented by R8-R5 include a halogen atom, -OR, and the like.

\R Todoroki alkyl group, cycloalkyl group, alkenyl group, aryl group, acyl group, alkoxycarbonyl group, carbamoyl group (e.g. alkylcarbamoyl group, arylcarbamoyl group, etc.), sulfamoyl group (e.g. alkylsulfamoyl group, arylsulfamoyl group, etc.) moyl group, etc.), sulfonyl group, nitro group, cyano group, carboxyl group, etc.

Alkyl group, cycloalkyl group represented by R, ~R,
Examples of the alkenyl group, aryl group, and heterocyclic group represented by R6 include those exemplified above for R.

Examples of the acyl group represented by R, R include an alkylcarbonyl group, an arylcarbonyl group, etc.; examples of the sulfonyl group include an alkylsulfonyl group, an arylsulfonyl group, etc.
Examples of the carbamoyl group include an alkylcarbamoyl group and an arylcarbamoyl group.

Specific examples of the compounds of the present invention are shown below.

-1 ■ +1 ■ 3 ■ 14 Shinn3 LJL, 11° ■ 15 1-21 0 Typical synthesis examples of the compounds of the present invention are shown below.

Synthetic Leather Example (Synthesis fR of Exemplified Compound I-4) 2,2'-methylenebis(4-butoxy-
6-7-butylphenol) and a catalytic amount of triethylamine hydrochloride were added. 17 g of dichlorophenylphosphine was slowly added to this, and the mixture was further stirred overnight. After filtering the reaction solution, the filtrate was neutralized with dilute hydrochloric acid, toluene was distilled off under reduced pressure, and 22.5 g of the target product was obtained by column chromatography.

When this substance was identified by FD mass spectrum and NMR, it was confirmed that it was the same as the exemplified compound. Other exemplified compounds represented by the general formula [I] can also be made into synthetic leather by the same method.

The amount of the anti-fading agent of the present invention used is preferably 5 to 400 mol%, more preferably 10 to 3 mol%, based on the organic coloring substance.
00 mol%.

The organic coloring substance in the present invention means 300 nm to 8001, preferably 400 nm to 7 in methanol solution.
Refers to an organic substance that has at least one absorption maximum in 0.000000000000000000000000000000000000000000 hours is an organic substance that has at least one absorption maximum, and includes basic dyes, acidic dyes, direct dyes,
Water-soluble dyes such as soluble vat dyes and mordant dyes, insoluble dyes such as sulfur dyes, vat dyes, oil-soluble dyes, disperse dyes, azoic dyes, oxidation dyes, and reactive dyes. Includes all dyes that belong to this category.

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 (dianine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoaniline and indophenol dye,
It includes dyes belonging to chemical structural classes such as indicoid dyes, carbonium dyes, and formazan dyes.

The organic coloring substance in the present invention is an image-forming dye used in the field of photography, such as a color coupler DRR compound,
DDR couplers include all dyes formed from amithracine compounds, dye developers, dyes for silver dye bleaching methods, etc.

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

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

Among the above groups, the benzene ring may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, or an amino group in the dye.

The foregoing couplers include those of the yellow, magenta and cyan dye-forming types. This coupler is described, for example, in U.S. Pat.
The so-called 4-equivalent type as described in No.
or the coupling position is substituted with a substituent that can be separated during the coupling reaction (split-off group) 2
It may be of equivalent type.

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, naphthol-based, pyrazoquinazolone-based, pyrazolopyrimidine-based, pyrazolotriazole-based, and imidazole-based couplers. There is a coupler.

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 will be given.

-6- 7- -9 〇． H.

4Hs These yellow couplers are described, for example, in West German Published Patent Application No. 2.
0570941, West German Published Patent Application 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, Japanese Patent Publication No. 51-33410, Japanese Patent Publication No. 52-25733, etc., and can be made into synthetic leather according to the methods described therein.

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

-5 M-7 -8 -9 -10 -11 ShiU -17 These magenta couplers are described, for example, in U.S. Pat.
No. 4,514, British Patent No. 1.183.515, Japanese Patent Publication No. 40-6031, No. 40-6035, No. 44-15
No. 754, No. 45-40757, No. 46-19032
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. 59-162548, No. 60-436
No. 59, No. 60-33552 Research Disclosure No. 24626 (1984), Patent Application No. 1984
-243007, 59-243008, 59-
No. 243009, No. 59-243012, No. 60-7
It contains the compounds described in No. 0197, No. 60-70198, etc., and can be made into synthetic leather according to the methods described in any of them.

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

A typical example of a cyan coupler is given below.

-2 -3 -6 C3H, (i) Cα -7 ShiU These cyan couplers are described, for example, in 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
4, No. 56-80045, 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 an oxidized aromatic primary amine silver halide developer.

The above developers include aminophenol and phenylenediamine, 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 of the present invention are generally oil-soluble and are typically used in U.S. Pat.
．． No. 801171, No. 2,272,191 and No. 2
, 304.940, in which the coupler is dissolved and dispersed in a high-boiling point solvent, if necessary in combination with a low-boiling point solvent, and added to the hydrophilic colloid solution. There is no problem in using a hydroquinone derivative, an ultraviolet absorber, a known dye image fading inhibitor, or the like in combination. Known dye image fading inhibitors include compounds described in JP-A-61-143754.

At this time, there is no problem even if two or more of the compounds of the present invention are used as a mixture.

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.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 62 g of cyan coupler (C-2) and exemplified compound (I-
1) A solution of 62 g dissolved in a high boiling point organic solvent (DBP) and ethyl acetate was added to an 8% aqueous gelatin solution containing a dispersion aid (dodecylbenzenesulfonic acid sodium salt) and dispersed with a homogenizer.

The resulting dispersion was finished to 1500++12 and heated at 40°C.
It was kept warm for 3 hours. This dispersion was added to 1000 ml of a 3% aqueous gelatin solution for coating, and then red-sensitive silver chlorobromide emulsion 4
00 g (containing 80% mole of silver bromide) was added to prepare a coating solution for a red-sensitive emulsion layer.

This coating solution was kept at 40°C for 2 hours.

Coating solutions for each layer were prepared in the same manner, and coated on a polyethylene-coated paper support at a coating speed of 100 m/min to have the following composition.

1st layer diblue photosensitive emulsion layer yellow coupler (Y-2) at 8 mg/dm
A blue-sensitive silver chlorobromide emulsion (containing 20 mol% silver chloride and 80 mol% silver bromide) was 3 mg/dm in terms of silver, a high boiling point organic solvent (DBP) was 3 mg/dm, and gelatin was 1
Apply the coating so that the coating amount is 6mg/dm.

2nd layer: Intermediate layer hydroquinone derivative (HQ-1) 0.45mg/d
Coat m2 and gelatin to a coating amount of 4 mg/dm.

The third green-sensitive emulsion layer contained magenta coupler (M-2) at 4 mg/dm'', green-sensitive silver chlorobromide emulsion (silver chloride 20 mol%, silver bromide 80 mol%).
4 mg/dm'' in terms of silver, high boiling point organic solvent (DBP) 4 mg/dm'' and gelatin 16 m
Apply the coating so that the coating amount is g/dm2.

4th layer: Intermediate layer ultraviolet absorber (IIV-1) 3 mg/dm2, (
IIV-2) at 3 mg/d+n'', high boiling point organic solvent (
DBP) at 4 mg/dm”, hydroquinone derivative (
HQ-2) at 0.45 mg/dm” and gelatin at 14
Apply the coating to a coating amount of "B/dm".

5th layer: Red photosensitive emulsion layer cyan coupler (C-2) at 4 mg/di", high boiling point organic solvent (DBP) at 4 mg/dm", exemplified compounds
(■l) at 4 mg/dm'', a red-sensitive silver chlorobromide emulsion (
Containing 20 mol% of silver chloride and 80 mol% of silver bromide) was coated to give a coating amount of 3 mg/d- in terms of silver and 16 mg/d- of gelatin.

6th layer: Interlayer ultraviolet absorber (UV-3) 4 mg/dm", DBP
and gelatin at a coating amount of 2 mg/d- and 6 mg/d-.

7th layer: protective layer Apply gelatin to a coating amount of 9mg/d-.

(Compound used for sample preparation) DBP dibutyl phthalate v UV This sample is designated as sample 1.

Next, Samples 2 to 8 were prepared in the same manner as Sample 1 except that the exemplary compounds in the fifth layer of Sample 1 were changed as shown in Table 1. (
The exemplified compound was added in equimolar amounts to Sample 1. ) These samples were subjected to optical wedge exposure with red light using a sensitometer (model KS-7, manufactured by Konica Corp.), and then subjected to the following treatments.

Processing process Processing temperature Processing time Color development phenomenon
32.8°0 3 minutes 30 seconds bleach fixing 32.8
℃ Wash with water for 1 minute 30 seconds 32.8
℃ 3 minutes 30 seconds (color developer set FR) N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate
4.0g hydroxylamine sulfate
2.0g potassium carbonate
25.0g sodium chloride
0.1g Sodium Bromide 0.
2g Anhydrous sodium sulfite 2.0g
Benzyl alcohol io, 0m12
Polyethylene glycol (average degree of polymerization 400) 3.0
Add m12 water to 1a and use sodium hydroxide to make p
Adjust to H1O,o.

(Bleach-fix solution composition) Ethylenediaminetetraacetic acid iron sodium salt 60.0g Sodium thiosulfate loo, 0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water to 1
12 and pu7. using sulfuric acid. Adjust to O.

The color image light fastness of each sample obtained after the treatment was evaluated in the following manner.

Dark image light resistance〉 The dye image formed on each sample was examined using a 100,000 lux xenon fade meter (200 hours of irradiation represents the initial density (1,0), and D represents the density after irradiation). It was measured.

Comparative Compound - Comparative Compound-2 As is clear from Table 1, the samples using the exemplary compounds according to the present invention exhibit good light fastness of color images. Also, good color images were obtained.

Also, instead of exemplified compound I-1 of sample 1, I-7,1-
8,l-11,! The effects of the present invention were also observed for samples using -15, I-19, and I-22.

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 yellow coupler was changed to Y-11. Coupler Y
-11 (4 mg/dm”)
) was changed as shown in Table 2.
Samples similar to (Samples 9 to 18) were prepared.

Samples 9 to 18 were subjected to light wedge exposure with blue light according to a conventional method, and then subjected to the following treatments.

Treatment process Treatment temperature Treatment time Color development phenomenon 3
5.0±0.3°O 45 seconds bleach fixing 35.0±0
．． Stabilize at 5°O for 45 seconds Dry at 30-34°C for 90 seconds Naturally dry at room temperature (25°C) Color developer Pure water 800m12
trietanol amin
logN, N-diethylhydroxylamine 5g potassium bromide
0.02g potassium chloride
2g potassium sulfite 0.
3g 1-hydroxyethylidene-1-1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1. Og Catechol-3,5-disulfonic acid disodium salt 1.0gN-
Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium carbonate
Add 27g water and make the total amount IQ,
Adjust pH = 10.10.

Bleach-fix solution Ferric ammonium dihydrate ethylenediaminetetraacetic acid 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% aqueous solution) 100ml12 Ammonium sulfite (40% aqueous solution) 27.5ml12 Add water to bring the total volume to la, potassium carbonate or glacial acetic acid pH at
= 6.2.

Stabilizing liquid 5-chloro-2-methyl-4-inchazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20 % aqueous solution) 3.0g ammonium sulfite 3.0g optical brightener (4,4'
-diaminostilbendisulfonic acid derivative)
Add 1.5 g of water to make IQ, and adjust the pH to -7.0 with sulfuric acid or potassium hydroxide.

Each sample after treatment was evaluated in the same manner as in Example 1.

The results are shown in Table 2.

As can be seen from the results of Example 1 and Compound Table 2, when the compound according to the present invention was used, the light resistance was improved.

or, good color Image obtained.

Also, instead of 1-1 of sample 13! -17,I -2
1 was also used, the effects of the present invention were observed.

Example 3 In the DBP of the third layer of sample 9, it was
Similar samples (Samples 19 to 26) were prepared except that the compound shown in No. 3 (7 mg/da'') was added.

Samples 19 to 26 were subjected to light wedge exposure with green light according to a conventional method, and then treated in the same manner as in Example 2. Each sample obtained after the treatment was evaluated in the same manner as in Example 1.

Table 3 As can be seen from the results in Table 3, when the compound according to the present invention was used, the light resistance of the magenta image was improved as in Example 1.2, and a good color image was obtained.

Furthermore, the effects of the present invention were also observed in samples in which l-18 and l-20 were used instead of I-1 in sample 22.

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, at least one of the photographic constituent layers has the following general formula [I
] A silver halide photographic material characterized by containing a compound represented by the following. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group,
R_5 represents a hydrogen atom or a substituent, and at least one of R_2 to R_3 is a halogen atom, -OR_■, -SR_
■or▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_■ is an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group, R_7 and R_8 are hydrogen atoms, alkyl groups, cycloalkyl groups, and aryl groups. , represents an alkenyl group, acyl group, sulfonyl group or carbamoyl group.), X represents a bond or a divalent bonding group, and Y represents -
It represents O-, -S-, -NH-, or -NR_1- (R_1 has the same meaning as R_1 above. However, two R_1 may be the same or different.). n represents 0 or 1. ]