JP2663182B2 - Silver halide photographic material with improved dye image fastness - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to the stabilization of organic coloring substances such as dye images formed in photographic materials. Specifically, the present invention relates to the use of certain bis-type phenol derivative stabilizers to improve the stability of organic colorants, such as dye images, obtained with silver halide photographic materials.

[Background of the Invention]

Common color photographic materials include red, green, and blue-sensitive silver halide emulsion layers, in or adjacent to those layers, each containing a cyan, magenta, and yellow coupler, and p- When developed with a developer containing a phenylenediamine-based color developing agent, a dye image is formed.

It is known to include stabilizers in color photographic materials to reduce the degradation of dye images due to the effects of light, heat and / or humidity. JP-B-48-31256 describes that the color image fastness is improved by using a special bisphenol derivative.

However, the bisphenol derivative described above did not have a sufficient fading prevention effect.

[Object of the invention]

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

[Configuration of the invention]

The above object was achieved by a silver halide photographic material having the following constitution.

In a silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion layer on a support, at least one of the photographic component layers contains a compound represented by the following general formula [I]. A silver halide photographic material.

General formula [I] In the formula, R ₁ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, R _{2 to} R ₅ represent a hydrogen atom or a substituent, and at least one of R _{2 to} R ₅ is halogen. Atom, -OR ₆ , -SR ₆ or (R ₆ is an alkyl group, a cycloalkyl group, an alkenyl group,
R ₇ and R _{8 each} represent an 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 linking group;
Represents -O-, -S-, -NH- or -NR _1- (R ₁ has the same meaning as R ₁ above, provided that two R ₁ may be the same or different). n represents 0 or 1.

[Specific configuration of the invention]

 The compound represented by the general formula [I] will be described.

In the general formula [I], the alkyl group represented by R ₁ is, for example, a methyl group, an ethyl group, a propyl group or a butyl group; the cycloalkyl group is, for example, a cyclohexyl group; the alkenyl group is, for example, an allyl group; Examples of the aryl group include a phenyl group; examples of the heterocyclic group include a 2-pyridyl group and a 2-furyl group, and each group represented by R ₁ includes those having a substituent.

Examples of the divalent linking group represented by X include an alkylidene group such as a butylidene group or a 3,5,5-trimethylhexylidene group; a hetero atom such as an oxygen atom or a sulfur atom; a sulfonyl group; a sulfinyl group; Groups such as an ethylene group; alkyleneoxy groups such as an ethyleneoxy group; alkylenethio groups such as an ethylenethio group. Of these, X is preferably an alkylidene group or a hetero atom.

The group which can be substituted on the benzene ring represented by R _{2 to} R _{5 is} , as a typical example, a halogen atom, -OR ₆ , -SR ₆ , (R _{6 to} R ₈ are as defined above), alkyl group, cycloalkyl group, alkenyl group, aryl group, acyl group, alkoxycarbonyl group, carbamoyl group (for example, alkylcarbamoyl group, arylcarbamoyl group, etc.), sulfamoyl group (Eg, alkylsulfamoyl group, arylsulfamoyl group, etc.), sulfonyl group, nitro group, cyano group, carboxyl group and the like.

The alkyl group represented by R ₆ to R _8, a cycloalkyl group, an alkenyl group, the aryl group, the heterocyclic group represented by R _6, include those exemplified as R ₁ described above.

As the acyl group represented by R ₇ and R ₈ , an alkylcarbonyl group, an arylcarbonyl group or the like; a sulfonyl group such as an alkylsulfonyl group or an arylsulfonyl group; and a carbamoyl group or the like as an alkylcarbamoyl group or an arylcarbamoyl group Is mentioned.

 Hereinafter, specific examples of the compound of the present invention are shown.

Hereinafter, typical synthesis examples of the compound of the present invention are shown.

Synthesis Example (Synthesis of Exemplified Compound I-4) 2,2'-Methylenebis (4-butoxy-
45.6 g of 6-t-butylphenol) and a catalytic amount of triethylamine hydrochloride were added. To this, 17 g of dichlorophenylphosphine was slowly added, and the mixture was further stirred overnight. After filtration of the reaction solution, the filtrate was neutralized with dilute hydrochloric acid, toluene was distilled off under reduced pressure, and the target product 22.5 was purified by column chromatography.
g was obtained.

When this substance was identified by FD mass spectrum and NMR, it was confirmed that the substance was the same as the exemplified compound.
Other exemplified compounds represented by the general formula [I] can be synthesized in the same manner.

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

The organic coloring substance in the present invention refers to an organic substance having at least one absorption maximum at 300 nm to 800 nm, preferably at 400 nm to 700 nm in a methanol solution, and is a basic dye, an acid dye, a direct dye, Soluble vat dyes, water-soluble dyes such as mordant dyes, sulfur dyes, vat dyes,
All dyes belonging to the class of dyeing properties such as insoluble dyes such as oil-soluble dyes, disperse dyes, azoic dyes and oxidation dyes, and reactive dyes are included.

Among these dyes, the dyes preferably used in the present invention are quinone imine dyes (azine dyes, oxazine dyes,
Thiazine dyes), methine and polymethine dyes (dianine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoaniline and indophenol dyes, indicoid dyes, carbonium dyes, formazan dyes, etc. Include.

The organic coloring matter in the present invention is an image forming dye used in the field of photography, for example, a color coupler, a DRR compound, a DDR coupler, an amidrazone compound, a dye formed from a dye developing agent, a dye for a silver dye bleaching method, and the like. Include all.

Preferred dyes to be used as organic coloring substances in the present invention are anthraquinone, quinone imine, azo, methine, 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.

In the above groups, the benzene ring may have a substituent in the dye, for example, an alkyl group, an alkoxy group, a halogen atom, an amino group and the like.

The aforementioned couplers include those of the yellow, magenta and cyan dye forming types. This coupler may be a so-called 4-equivalent type coupler as described in, for example, U.S. Pat. Nos. 3,277,155 and 3,458,315, or may be substituted with a substituent capable of leaving at a coupling position during a coupling reaction (a split-off group). May be a two-equivalent type.

Preferable yellow dye image forming couplers in the present invention include benzoylacetanilide type and pivaloylacetanilide type couplers, and magenta dye image forming couplers include 5-pyrazolone, pyrazolotriazole, imidazopyrazole and pyrazolopyrazole. Type, pyrazolotetrazole type, pyrazolinobenzimidazole type, indazolone type couplers, and as the cyan dye image forming coupler, phenol type, naphthol type, pyrazoloquinazolone type, pyrazolopyrimidine type, pyrazolotriazole type, There are imidazole couplers.

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

 Next, typical specific examples of the yellow coupler will be described.

These yellow couplers are, for example, West German Patent 2,
No. 0570941, West German Patent 2,163,812, JP 47-21613
No. 3, No. 48-29432, No. 50-65321, No. 51-3631,
No. 51-50734, No. 51-102636, No. 48-66835, No. 48
-94432, 49-1229, 49-10736, Tokiko Sho 51-
The compounds include the compounds described in Nos. 33410 and 52-25733, and can be synthesized according to the methods described therein.

 Next, typical specific examples of the magenta coupler will be described.

These magenta couplers are described, for example, in U.S. Pat.
No. 514, British Patent No. 1,183,515, Japanese Patent Publication No. 40-6031, No. 40
-6035, 44-15754, 45-40757, 46-1903
No. 2, JP-A-50-130,41, JP-A-53-129035, JP-A-51-376
No. 46, No. 55-62454, U.S. Patent 3,725,067, UK Patent
Nos. 1,252,418, 1,334,515, JP-A-59-171956,
No. 59-162548, No. 60-43659, No. 60-33552, Research Disclosure No. 24626 (1984), Japanese Patent Application No. 59-24
No. 3007, No. 59-243008, No. 59-243009, No. 59-2430
No. 12, No. 60-70197, No. 60-70198, etc., and can be synthesized according to the methods described therein.

The cyan coupler is not particularly limited, but is preferably a phenolic cyan coupler.

 Representative specific examples of the cyan coupler will be given.

These cyan couplers are described, for example, in U.S. Pat.
No. 0, No. 2,801,171, JP-A-50-112038, No. 50-13
No. 4644, No. 53-109630, No. 54-55380, No. 56-65134
No. 56-80045, No. 57-155538, No. 57-204545
And the compounds described in JP-A Nos. 58-98731, 59-31953, etc., and can be synthesized according to the methods described therein.

In the present invention, when using such a coupler,
Dyes are formed from these couplers by reacting with oxidized aromatic primary amine silver halide developers.

The above-mentioned developers include aminophenol and phenylenediamine, and these developers can be used as a mixture.

The anti-fading agent of the present invention described above is preferably present in a color photographic material, particularly in an organic coloring substance or a layer in which it is formed or a layer adjacent thereto. Effective methods for dispersing these compounds of the present invention are the same as those used for dispersing the coupler.

The compounds of the present invention are generally oil-soluble, and are usually U.S. Pat.Nos. 2,322,027, 2,801,170, 2,801,171, 2,2
No. 72,191 and 2,304,940 It is preferable to dissolve in a high-boiling solvent according to the method described in No. 2,304,940, optionally using a low-boiling solvent in combination, disperse and add to the hydrophilic colloid solution. A coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading inhibitor may be used in combination. Known dye image discoloration inhibitors include the compounds described in JP-A-61-143754.

At this time, a mixture of two or more compounds of the present invention can be used.

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

〔Example〕

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

Example 1 62 g of cyan coupler (C-2) and exemplary compound (I-
1) A solution in which 62 g was dissolved in a high boiling point organic solvent (DBP) and ethyl acetate was added to an 8% aqueous gelatin solution containing a dispersing agent (dodecylbenzenesulfonic acid sodium salt), and dispersed with a homogenizer. The resulting dispersion was made up to 1500 ml and kept at 40 ° C. for 3 hours. This dispersion was added to 1000 ml of an aqueous gelatin solution at 3% for coating, and a red-sensitive silver chlorobromide emulsion was further added.
400 g (containing 80% mol of silver bromide) was added to prepare a coating solution for a red-sensitive emulsion layer.

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

Similarly, the coating solution for each layer was prepared and coated on a polyethylene-coated paper support at a coating speed of 100 m / min so as to have the following structure.

First layer: Blue-sensitive emulsion layer The yellow coupler (Y-2) was converted to silver at 8 mg / dm ² , and the blue-sensitive silver chlorobromide emulsion (containing 20 mol% of silver chloride and 80 mol% of silver bromide) was converted to silver. 3 mg / dm ² , high-boiling point organic solvent (DBP) 3 mg / dm ² and gelatin 16 mg / dm ²

Second layer: Intermediate layer The hydroquinone derivative (HQ-1) was coated so as to have a coating amount of 0.45 mg / dm ² and gelatin at a coating amount of 4 mg / dm ² .

Third layer: green photosensitive emulsion layer Magenta coupler (M-3) was converted to silver at 4 mg / dm ² , and green-sensitive silver chlorobromide emulsion (containing 20 mol% of silver chloride and 80 mol% of silver bromide) was converted to silver. 4 mg / dm ² , high boiling organic solvent (DBP) 4 mg / dm ²
And gelatin is applied so that the application amount is 16 mg / dm ² .

Fourth layer: intermediate layer UV absorbent (UV-1) 3mg / dm 2, the 3mg / d (UV-2)
m ² , high boiling organic solvent (DBP) 4 mg / dm ² , hydroquinone derivative (HQ-2) 0.45 mg / dm ² and gelatin 14 mg / dm ²
Is applied so that the application amount is

Layer 5: Red-sensitive emulsion layer cyan coupler (C-2) a 4 mg / dm ^2, the high-boiling organic solvent (DBP) 4mg / dm ^2, Exemplified Compound (I-1) and 4 mg / d
m ² , red-sensitive silver chlorobromide emulsion (silver chloride 20 mol%, silver bromide 80
Mol%) and converted to silver at 3 mg / dm ² and gelatin at 16 mg /
Coated so that the applied amount is dm ² .

Sixth layer: Intermediate layer An ultraviolet absorber (UV-3) was applied so as to have a coating amount of 4 mg / dm ² , DBP of 2 mg / dm ² and gelatin of 6 mg / dm ² .

Seventh layer: protective layer Gelatin was applied so that the applied amount was 9 mg / dm ² .

(Compound used for sample preparation) DBP: Dibutyl phthalate This sample was designated as sample 1.

Next, Samples 2 to 8 were prepared in the same manner as in Sample 1 except that the exemplified compounds in the fifth layer of Sample 1 were changed as shown in Table 1.
(Exemplary compounds were added in an equimolar amount to Sample 1.) These samples were subjected to light wedge exposure with red light using a sensitometer (KS-7, manufactured by Konica Corporation), and then subjected to the following processing. .

Processing step Processing temperature Processing time Color development phenomenon 32.8 ° C 3 minutes 30 seconds Bleaching and fixing 32.8 ° C 1 minute 30 seconds Rinse 32.8 ° C 3 minutes 30 seconds (color developing solution composition) N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.0 g hydroxylamine sulfate 2.0 g potassium carbonate 25.0 g sodium chloride 0.1 g sodium bromide 0.2 g anhydrous sodium sulfite 2.0 g benzyl alcohol 10.0 ml polyethylene glycol (average degree of polymerization 400) 3.0 ml water To pH 1 using sodium hydroxide to pH 10.0.
Adjust to

(Composition of bleach-fixing solution) Sodium salt of iron ethylenediaminetetraacetate 60.0 g Sodium thiosulfate 100.0 g Sodium bisulfite 20.0 g Sodium metabisulfite 5.0 g Water was added to 1 to adjust the pH to 7.0 using sulfuric acid.

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

<Color image lightfastness> Fading rate when the dye image formed on each sample was irradiated for 200 hours using a 100,000 lux xenon fade meter (%) (Where D ₀ represents the initial concentration (1.0) and D represents the concentration after irradiation).

As is evident from Table 1, the samples using the exemplified compounds in the present invention exhibit good color image light fastness. In addition, a good color image was obtained.

In addition, instead of Exemplified Compound I-1 of Sample 1, I-7, I-
For samples using 8, I-11, I-15, I-19, I-22,
The effect of the present invention was recognized.

Example 2 A silver chlorobromide emulsion containing 99.5 mol% of silver chloride was used in place of each of the silver halide emulsions used in Example 1, the yellow coupler was changed to Y-11, and the coupler Y was used in the DBP of the first layer. Samples (Samples 9 to 18) similar to Sample 1 of Example 1 were prepared except that the compound of the present invention (4 mg / dm ² ) added together with -11 was changed as shown in Table 2.

Samples 9 to 18 were exposed to light wedges using blue light according to a conventional method, and then subjected to the following processing.

Processing process Processing temperature Processing time Color development phenomenon 35.0 ± 0.3 ℃ 45 seconds Bleaching and fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-40 ℃ 90 seconds Drying Natural drying at room temperature (25 ℃) Color developer Pure water 800ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid Sodium salt 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to make the total amount 1 and adjust the pH to 10.10.

Bleaching / fixing solution Ethylenediaminetetraacetic acid ammonium ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to make the total volume 1 and add potassium carbonate or glacial acetic acid Adjust the pH to 6.2 with.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-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) 3.0 g Ammonium sulfite 3.0 g Optical brightener (4,4'-diaminostilbenzenesulfonic acid derivative) 1.5 g Add water to make 1 and add sulfuric acid or potassium hydroxide to pH =
Adjust to 7.0.

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

 Table 2 shows the results.

As can be seen from the results in Table 2, when the compound according to the present invention was used, the light fastness was improved. In addition, a good color image was obtained.

The effect of the present invention was also observed when I-17 and I-21 were used in place of I-1 in Sample 13.

Example 3 Table 9 with coupler M-2 in DBP of the third layer of sample 9.
The same samples (samples 19 to 26) were prepared except that the compound shown in No. 3 (7 mg / dm ² ) was added.

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

As can be seen from the results in Table 3, when the compound according to the present invention was used, the light fastness of the magenta image was improved as in Examples 1 and 2, and a good color image was obtained.

The effect of the present invention was also observed for each sample using I-18 and I-20 instead of I-1 of Sample 22.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-113536 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion layer on a support, wherein at least one of the photographic component layers is represented by the following general formula [I]. Silver halide photographic light-sensitive material, characterized by containing a compound to be prepared. General formula [I] Wherein R ₁ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, R _{2 to} R ₅ represent a hydrogen atom or a substituent, and at least one of R _{2 to} R ₅ A halogen atom, -OR ₆ , -SR ₆ or (R ₆ is an alkyl group, a cycloalkyl group, an alkenyl group,
R ₇ and R _{8 each} represent an 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 linking group;
Represents -O-, -S-, -NH- or -NR _1- (R ₁ has the same meaning as R ₁ above, provided that two R ₁ may be the same or different). n represents 0 or 1. ]