JPH0675175B2 - Silver halide photographic light-sensitive material with improved light fastness of dye image - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material in which the fading of a dye image obtained by photographic processing due to light and the discoloration of the uncolored portion due to light are prevented.

BACKGROUND OF THE INVENTION In a silver halide photographic light-sensitive material, it is desired that a dye image obtained from a coupler does not fade even when exposed to light for a long time or stored under high temperature and high humidity.

However, the fastness of these dye images mainly to ultraviolet rays or visible rays is not yet satisfactory, and it is known that the dye images are easily discolored when exposed to these active rays. In order to remove such defects, various couplers with less fading than before are selected and used, or a method of using an ultraviolet absorber to protect the dye image from ultraviolet rays, an anti-fading agent that prevents fading due to light are used. A method of using or a method of introducing a group imparting light resistance into a coupler has been proposed.

However, for example, in order to impart satisfactory light resistance to a dye image by using an ultraviolet absorber, a relatively large amount of the ultraviolet absorber is required, and in this case, the coloring of the ultraviolet absorber itself causes the dye image to remarkably increase. It was often polluted. Further, even if an ultraviolet absorber is used, it has no effect in preventing the fading of a dye image due to visible light, and there is a limit to the improvement of light resistance by the ultraviolet absorber. Further known is a method of using a dye image anti-fading agent having a phenolic hydroxyl group or a group which is hydrolyzed to form a phenolic hydroxyl group, and JP-B-48-31256 and 48-31625,
No. 51-30462, JP-A-49-134326 and JP-A-49-134327, phenol and bisphenols, U.S. Pat.No. 3,069,262 describes pyrogallol, garlic acid and its esters, U.S. Pat. And No. 4,015,990, α-tocopherols and acyl derivatives thereof, JP-B-52-27534, JP-A-52-147.
51 and U.S. Pat.No. 2,735,765 include hydroquinone derivatives, U.S. Pat.Nos. 3,432,300 and 3,573.
4,627,6-hydroxychromans, US Pat. No. 3,573,050, 5-hydroxycoumarin derivatives, and JP-B-49-20977 disclose 6,6'-dihydroxy-2,2'-bisspirochroman. It is proposed to use a class or the like. Further, a certain p-aminophenol derivative is known from JP-A-55-6321. These compounds certainly have an effect as an agent for preventing fading and discoloration of pigments, but have a small effect or have an effect of preventing fading, but prolong the hue or generate Y-stain. Due to the presence of the compound, it has a drawback that the color developability of the coupler is lowered.

[Object of the Invention] An object of the present invention is to provide a halogen containing an anti-fading agent that has an excellent anti-fading effect and does not cause a change in hue, Y-stain, or decrease the color developability of the coupler. It is to provide a silver halide photographic light-sensitive material.

[Structure of the Invention] In a silver halide photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, at least one photographic constituent of the following general formula [I]
It was found that the above object can be achieved by a silver halide photographic light-sensitive material containing a compound represented by

General formula [I] In the formula, R ₁ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group, and R ₂ can be substituted with a benzene ring. Represents a group. m represents an integer of 0 to 4. When m is 2 or more, R _{2 s} may be the same or different, and R _{2 s} may form a ring. R ₂ may form a ring with —OR ₁ .

A represents a group of non-metal atoms necessary for forming a 5- to 8-membered ring with a nitrogen atom. [Specific Structure 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 a linear or branched alkyl group having 1 to 24 carbon atoms (for example, methyl group, ethyl group, isopropyl group, t-butyl group, 2
-Ethylhexyl group, dodecyl group, t-octyl group, benzyl group and the like) are preferable.

The cycloalkyl group represented by R ₁ is preferably a cycloalkyl group having 5 to 24 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.).

The alkenyl group represented by R ₁ is preferably an alkenyl group having 3 to 24 carbon atoms (eg, allyl group, 2,4-pentenedienyl group, etc.).

Examples of the aryl group represented by R ₁ include a phenyl group,
Examples thereof include naphthyl group.

Examples of the heterocyclic group represented by R ₁ include a pyridyl group, an imidazolyl group and a thiazolyl group.

Examples of the acyl group represented by R ₁ include an acetyl group and a benzoyl group.

Examples of the bridged hydrocarbon group represented by R ₁ include a bicyclo [2,2,1] heptyl group.

Examples of the alkylsulfonyl group represented by R ₁ include a dodecylsulfonyl group and hexadecylsulfonyl group, and examples of the arylsulfonyl group include a phenylsulfonyl group.

Each of these groups represented by R ₁ also includes those having a substituent, for example, as a substituent of an alkyl group, a hydroxy group, an alkoxy group, an aryl group, an acylamino group,
Sulfonamide group, aryloxy group, alkylthio group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, nitro group, cyano group, arylsulfonyl group, halogen atom, carboxyl group, amino group, arylamino group, alkylamino group, alkoxycarbonyl Group, an acyl group, an acyloxy group, etc., and examples of the substituent of the group represented by R ₁ other than the alkyl group include the above-mentioned substituents and alkyl groups.

Preferred as R ₁ is an alkyl group.

Typical examples of the group capable of substituting on the benzene ring represented by R ₂ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group and a sulfonamide group. (Eg, alkylsulfonamide group, arylsulfonamide group, etc.), alkoxycarbonyl group, carbamoyl group (eg, alkylcarbamoyl group, arylcarbamoyl group, etc.), ureido group (eg, alkylureido group, arylureido group, etc.), sulfamoyl group, ( Examples thereof include an alkylsulfamoyl group, an arylsulfamoyl group, etc.), an amino group (including a substituted amino group), a sulfonyl group, a nitro group, a cyano group, a carboxyl group and the like, and among these, preferred as R ₂ Is a halogen atom or an alkyl group An alkylthio group, an acylamino group,
It is a sulfonamide group. The group represented by R ₂ may further have a substituent.

m represents an integer of 0 to 4, preferably 0 to 2. When m is 2 or more, R _{2 s} may be the same or different, and R _{2 s} may form a ring. R ₂ may combine with —OR ₁ to form a ring.

Examples of the 5- to 8-membered ring formed by A include pyrrolidine, piperidine, piperazine, morpholine, pyridine and the like. These rings include those having a substituent, and examples of the substituent include those similar to the examples of the substituent of the group represented by R ₁ described above.

-OR ₁ is It can be in any position with respect to, but is preferably in the para position.

The representative examples of the compound represented by the general formula [I] (hereinafter referred to as the compound of the present invention) are shown below, but the invention is not limited thereto.

<Exemplified compound> The representative synthetic examples of the compounds of the present invention are shown below.

Synthesis Example 1 [Synthesis of Exemplified Compound (1)] To 200 cc of ethanol, 15.4 g of potassium carbonate and 21.6 g of 1,4-dibromobutane were added, and 30.5 g of p-tetradecyloxyaniline was added over 10 minutes while stirring at room temperature. Add this reaction mixture to 20
After refluxing for an hour, the mixture was filtered and ethanol was removed under reduced pressure.
To this, 200 cc of ethyl acetate was added and washed with water three times. After removing ethyl acetate under reduced pressure, the residue was subjected to column chromatography to obtain 17.5 g of colorless crystals.

Melting point 61 to 62 ° C. This substance was identified by FD mass spectrum and NMR, and it was confirmed to be the same as Exemplified compound (1).

Synthesis Example 2 [Synthesis of Exemplified Compound (11)] To 200 cc of ethanol, 15.4 g of potassium carbonate and 14.3 g of bis (chloroethyl) ether were added, and the mixture was stirred at room temperature and 27.7 g of p-dodecyloxyaniline was added over 10 minutes. 2 this reaction mixture
After refluxing for 0 hour, it was filtered and ethanol was removed under reduced pressure.
To this, 200 cc of ethyl acetate was added and washed with water three times.
After removing ethyl acetate under reduced pressure, the residue was subjected to column chromatography to obtain 16.5 g of colorless crystals.

Melting point 64.5 to 65 ° C. The substance was identified by FD mass spectrum and NMR and was confirmed to be the same as the exemplified compound (11).

In the present invention, the compound of the present invention comprises a photographic constituent layer constituting a silver halide photographic light-sensitive material, that is, a photosensitive silver halide emulsion layer which is a light-sensitive layer and a protective layer which is a non-light-sensitive layer.
It is contained in at least one of the intermediate layer, the filter layer, the undercoat layer, the antihalation layer and other auxiliary layers,
The silver halide emulsion layer preferably contains a magenta coupler most preferably. It is contained in the silver halide emulsion layer. In this case, the addition amount of the compound of the present invention is suitably 0.1 to 4 mol, preferably 0.5 to 3 mol, per 1 mol of the coupler.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative or positive film, a color photographic paper, etc., and particularly when it is applied to a color photographic paper, its excellent effect is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, a silver halide emulsion layer and a non-light-sensitive layer usually containing magenta, yellow and cyan couplers as photographic couplers in order to perform color reduction method color reproduction. Has a structure in which it is laminated on the support in an appropriate number of layers and layer order, but the number of layers and layer order may be appropriately changed depending on the priority performance and the purpose of use.

The silver halide used in the silver halide photographic light-sensitive material of the present invention is used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any one can be used.

The silver halide emulsion used in the present invention is chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization or the like.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry.

The silver halide photographic light-sensitive material of the present invention contains additives such as an antifoggant, a hardener, a plasticizer, a latex, a surfactant, a color antifoggant, an ultraviolet absorber, a matting agent, a lubricant and an antistatic agent. Can be used arbitrarily.

In order to incorporate the compound of the present invention and a hydrophobic compound such as a dye-forming coupler into a silver halide photographic light-sensitive material, various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used. it can. For example, in the oil-in-water emulsion dispersion method, the above compound is usually added to a high-boiling organic solvent having a boiling point of about 150 ° C or higher (eg, phthalic acid ester, phosphoric acid ester, etc.), if necessary, low boiling point, and / or water-soluble. It may be dissolved in an organic solvent in combination, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution with a surfactant, and then added to the desired hydrophilic colloid layer.

The silver halide photographic light-sensitive material of the present invention can form a dye image by performing any color development processing used in the art.

[Specific effects of the invention] Since the silver halide photographic light-sensitive material of the present invention has a layer containing the compound of the present invention, the formed dye image has very high light fastness, and particularly fastness to light. Generally, the fastness of a magenta dye image that is small can be improved. Specifically, discoloration to light, fading, and Y in the uncolored portion
-The effect of favorably preventing the generation of stains.

[Specific Examples of the Invention] The present invention will be specifically described with reference to the following examples.

On a paper support which has been both sides laminated with Example 1 Polyethylene, gelatin (15.0 mg / 100 cm ^2), a magenta coupler (1) shown below and (6.0 mg / 100 cm ²⁾ 2,5-di -tert- octylhydroquinone after dissolution was emulsified and dispersed in dibutyl phthalate (5.0 mg / 100 cm ²⁾ with (0.8 mg / 100 cm ^2), it was mixed with the silver chlorobromide emulsion (silver bromide 80 mol%, amount of coated silver 3.8 mg / 100 cm ²⁾ Sample 1 was obtained by coating and drying.

In the coating liquid of the above Sample 1, comparative compounds (a) and (b), which are conventionally known magenta dye image stabilizers,
Samples 2, 3, 4, and 5 were obtained in the same manner except that (c) and (d) were added in an equimolar amount to the magenta coupler (1).

In the coating liquid of Sample 1 above, among the compounds of the present invention as dye image stabilizers, exemplified compounds (1), (11), (51),
Samples 6, 7, 8, 9 and 10 were obtained in the same manner except that (53) and (59) were added in an equimolar amount to the coupler (1).

Magenta coupler (1) Comparative compound (a) Comparative compound (b) Comparative compound (c) Comparative compound (d) After exposing the sample obtained above through an optical wedge according to a conventional method,
The process was performed in the next process.

[Treatment Process] Treatment temperature Treatment time Color development phenomenon 33 ° C 3 minutes 30 seconds Bleach fixing 33 ° C 1 minute 30 seconds Water washing 33 ° C 3 minutes Drying 50-80 ° C 2 minutes The components of each processing solution are as follows.

[Color developer] Benzyl alcohol 12 ml Diethylene glycol 10 ml Potassium carbonate 25 g Sodium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Hydroxylamine sulphate 2.5 g N-Ethyl-N-β-methanesulfonamide Amidoethyl-3-methyl-4-aminoaniline Sulfate 4.5 g Add water to make 1 and adjust to pH 10.2 with NaOH.

[Bleaching fixer] Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g Ferric ammonium ammonium salt 65 g Water was added to 1 to adjust pH to 6.7-6.8.

The samples 1 to 10 treated as described above were measured for the concentration under the following conditions using a densitometer (KD-7R type, manufactured by Konishi Rokusha Kogyo Co., Ltd.).

Each treated sample was irradiated with a xenon fade meter for 10 days, and the light resistance of the dye image and the Y-stain of the uncolored portion were examined. Specifically, the density change (M density change) when the density of the magenta dye image portion before the test was set to 1.0 and the yellow coloring density change (Y-stain) in the white background portion were examined. The results obtained are shown in Table 1.

As is clear from Table 1, Samples 6 to 10 prepared by using the compound of the present invention showed discoloration of the dye image due to light and light as compared with the case of using the conventionally known dye image stabilizer. It can be seen that the fading is small and the uncolored Y-stain is also small.

Example 2 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 light-sensitive material, and a sample 11 was obtained.

First 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 was added to 6.8 mg / 100 cm ² ,
Blue-sensitive silver chlorobromide emulsion (containing 85 mol% of silver bromide) converted to silver 3.2 mg / 100 cm ² , dibutyl phthalate 3.5 mg / 100 c
m ² , dibutyl phthalate was applied at 3.5 mg / 100 cm ² , and gelatin was applied at an application amount of 13.5 mg / 100 cm ² .

Second layer: intermediate layer 2,5-di-t-octylhydroquinone 0.5 mg / 100c
m ² , dibutyl phthalate was coated at 0.5 mg / 100 cm ² , and gelatin was coated at 9.0 mg / 100 cm ² .

Third layer: green-sensitive silver halide emulsion layer The magenta coupler (1) is 3.5 mg / 100 cm ² , and the green-sensitive silver bromide emulsion (containing 80 mol% of silver bromide) is 2.5 mg / silver.
100 cm ^2, was coated with a dibutyl phthalate 3.0 mg / 100 cm ² and gelatin so that 12.0 mg / 100 cm ^2.

Fourth layer: intermediate layer An ultraviolet absorber of 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) benzotriazole was added to 0.2%.
7 mg / 100 cm ² , di-butyl phthalate 6.0 mg / 100 cm ² , 2,
5-di -t- octylhydroquinone by coating a 0.5 mg / 100 cm ² and gelatin so that 12.0 mg / 100 cm ^2.

Fifth layer: red-sensitive silver halide emulsion layer 2- [α- (2,4-di-t-pentylphenoxy) butanamide] -4,6-dichloro-5 as a cyan coupler
-Ethylphenol 4.2 mg / 100 cm ² , red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted to silver 3.0 mg / 100c
m ^2, and coated with a tricresyl phosphate and 3.5 mg / 100 cm ² and gelatin so that 11.5 mg / 100 cm ^2.

Sixth layer: Protective layer Gelatin was applied at a concentration of 8.0 mg / 100 cm ² .

In the above-mentioned sample 11, the compound of the present invention was added to the third layer in a ratio as shown in Table 2, multilayer samples 12 to 20 were prepared, exposed to light and treated in the same manner as in Example 1 to obtain light resistance. A test (irradiating a xenon fade meter for 15 days) was performed. The results are also shown in Table 2.

From the results shown in Table 2, it can be seen that the use of the compound of the present invention is effective in stabilizing the magenta dye image formed from the magenta coupler, and the effect increases as the addition amount increases.

Example-3 The compound (1) of the present invention in Sample 13 of Example-2 was converted into (12), (13), (15), (23), (25),
(27), (56), (68), (94), (98), (111),
Similar samples were prepared by substituting (113), (121), (126), and (127), respectively, and tested in the same manner as in Example-2. As a result, all samples showed very small fading of magenta dye and Good color balance as a color photographic material,
It was found that the color reproducibility was good and that the compound of the present invention worked effectively.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, and a compound represented by the following general formula [I] in at least one photographic constituent. A silver halide photographic light-sensitive material characterized by containing. General formula [I] [In the formula, R ₁ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group, and R ₂ is a benzene ring. Represents a possible group. m represents an integer of 0 to 4. When m is 2 or more, R _{2 s} may be the same or different, and R _{2 s} may form a ring. R ₂ may form a ring with —OR ₁ . A represents a group of non-metal atoms necessary for forming a 5- to 8-membered ring with a nitrogen atom. ]