JPH07261345A - Novel photographic coupler - Google Patents

Abstract

PURPOSE:To obtain a novel coupler used as stock of a silver halide color photographic sensitive material and to form a color image free from a change of hue by using pyrrolo[3,2-b]furans or pyrrolo[2,3-b]furans as a photographic coupler. CONSTITUTION:This photographic coupler is pyrrolo[3,2-b]furans represented by formula I or pyrrolo[2,3-b]furans represented by formula II. In the formulae I, and II, each of R1-R3 is H or a substituent, this substituent is not especially limited but is typically alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl or cycloalkyl and X is H or a group which is released by a reaction with the oxidized body of a color developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel coupler used as a material for a silver halide color photographic light-sensitive material, and more specifically to a novel photographic material capable of forming a dye image having excellent fastness to heat, moisture and light. It is about couplers.

[0002]

2. Description of the Related Art Generally, in the case of producing a color photograph, a silver halide color photographic light-sensitive material is exposed to light and then subjected to color development processing. Amine color developing agents and dye-forming couplers react to form dyes to form color images, but in such photographic methods a subtractive color reproduction method is used, whereby yellow, magenta and cyan are used. An image of each color is formed.

Conventionally, as a photographic coupler used for forming the above yellow color image, there is, for example, an acylacetanilide type coupler, and as a magenta color image forming coupler, for example, pyrazolone, pyrazolobenzimidazole, Pyrazolotriazole or indazolone couplers are known, and as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used,
It is desired that the dye image obtained from these couplers does not deteriorate even when exposed to light for a long time or stored at high temperature and high humidity.

[0004]

However, the above-mentioned phenol-based couplers and naphthol-based couplers, which have been studied and put into practical use as couplers for forming cyan dyes, are not suitable for forming cyan dye images. Spectral absorption characteristics, heat resistance and moisture resistance, etc. are still insufficient, and therefore various proposals have been made in the past, including the selection and search of substituents in couplers, with the aim of improving this. No coupler has yet been found that meets all the requirements for these properties.

On the other hand, a dye formed from a 5-pyrazolone type coupler, which has been widely put to practical use as a magenta color image forming coupler and has been studied, has excellent fastness to heat and light, but has a yellow component. In order to solve this, pyrazolobenzimidazole, indazolone,
Couplers such as pyrazolotriazole, imidazopyrazole, pyrazolopyrazole, and pyrazolotetrazole series have been proposed. In fact, these couplers are preferable from the viewpoint of color reproducibility, but the dye formed from the coupler is an optical dye. Is extremely low in fastness to, and is liable to cause discoloration.

Therefore, a first object of the present invention is to provide a novel photographic coupler used as a raw material for a silver halide color photographic light-sensitive material, and a second object of the present invention is to provide heat and humidity and It is an object of the present invention to provide a color photographic coupler capable of forming a color image without causing a change in hue due to light.

[0007]

The above object of the present invention has been achieved by the following constitution or.

Pyrrolo [3,2-b] furans or Pyrrolo [2,3-b] furans Photographic couplers.

The above pyrrolo [3,2-b] furans or pyrrolo [2,3-b] furans are each represented by the above general formula [I].
Alternatively, the photographic coupler as described in the above item, which is represented by the general formula [II] "Chemical formula 1".

The present invention will be described in detail below.

First, the photographic coupler represented by the general formula [I] or the general formula [II] will be described.

[0012]

[Chemical 2]

In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

In the general formula [I], R ₁ , R ₂ and R
The substituent represented by ₃ is not particularly limited, but typically includes each group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, and the like. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino,
Alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro, sulfo and other groups, and spiro A compound residue, a bridged hydrocarbon compound residue, etc. are also mentioned. R ₂ and R ₃ may combine with each other to form a ring.

Hereinafter, in each of the groups represented by R ₁ , R ₂ and R ₃ , the alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. A phenyl group is preferred as the aryl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and aryl component in the alkylthio group and the arylthio group are the above R ₁ , R ₂ and R _{3 respectively.}
And an alkyl group and an aryl group represented by. The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred. Alkylsulfonyl group, arylsulfonyl group, etc. as sulfonyl group; alkylsulfinyl group, arylsulfinyl group, etc. as sulfinyl group; alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group as phosphonyl group Etc .; as the acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .;
The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group or the like; the sulfamoyl group is an alkylsulfamoyl group, an arylsulfamoyl group or the like;
An alkylcarbonyloxy group as the acyloxy group,
Arylcarbonyloxy group, etc .; Sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc .; Carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .; Ureido group, alkylureido group, arylureido group, etc. Etc .; as a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, 2-thienyl group Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6 -Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; as a heterocyclic thio group, 5 To 7-membered heterocyclic thio groups are preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group is trimethyl Siloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; succinimide group as imide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc .; spiro compound residues as spiro [3,3 ] Heptan-1-yl, etc .; bridged hydrocarbon compound residues include bicyclo [2,2,1] heptan-1-yl, tricyclo [3,3,1,1 ^{3 7} ]
Decan-1-yl, 7,7-dimethyl-bicyclo [2,2,1] heptan-1-yl and the like can be mentioned.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Examples of the group which can be split off by the reaction with the oxidation product of the color developing agent represented by X are, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy and sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom,
Each group such as alkyloxycarbonylamino, aryloxycarbonylamino, carboxy and the like can be mentioned, but a halogen atom is preferable.

Next, typical examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

The couplers of the present invention described above are known, for example, S. Soth, M. Farnier and C. Paulmier, Can. J. Chem., 56 .
It can be synthesized according to the synthetic method described in 1429 (1978), for example, according to the following synthetic scheme.

[0030]

[Chemical 9]

The coupler of the present invention can be used usually in the range of 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol per mol of silver halide.

The coupler of the present invention can also be used in combination with other types of cyan couplers and magenta couplers. The methods and techniques used in conventional dye-forming couplers are likewise applied to the couplers of this invention.

The coupler of the present invention can be used as a material for forming a color photograph by any coloring method, and specific examples thereof include an external coloring method and an internal coloring method. When used as an external color-developing method, the coupler of the present invention can be dissolved in an aqueous alkali solution or an organic solvent (eg alcohol) and added to the developing solution for use.

When the coupler of the present invention is used as a color photographic material by the internal color forming method, at least one of the couplers of the present invention is contained in a photographic light-sensitive material.

Typically, a method in which the coupler of the present invention is blended with a silver halide emulsion and the emulsion is coated on a support to form a color light-sensitive material is preferably used.

The couplers of the present invention are used in color photographic light-sensitive materials such as color negative and positive films and color photographic paper.

The light-sensitive material using the coupler of the present invention, such as this color photographic paper, may be monochromatic or multicolor. In the multi-color light-sensitive material, the coupler of the present invention may be contained in any layer, but it is usually contained in the green light-sensitive silver halide emulsion layer and / or the red light-sensitive silver halide. The multicolor light-sensitive material has a dye image-forming constituent unit having photosensitivity in each of the three primary color regions of the spectrum. Each building block can consist of a single layer or multiple emulsion layers sensitive to certain regions of the spectrum. The constituent layers of the light-sensitive material, including the layers of the image-forming constituent units, can be arranged in various orders as known in the art.

A typical multicolor photosensitive material is at least 1
Cyan dye image-forming structural unit comprising at least one red-sensitive silver halide emulsion layer containing one cyan coupler, and a magenta dye image comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler. A yellow dye image forming layer comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler (at least one of the cyan coupler and / or the magenta coupler is a coupler of the present invention) forming unit. It consists of a structural unit supported on a support.

The light-sensitive material can have additional layers such as filter layers, intermediate layers, protective layers, subbing layers and the like.

In order to incorporate the coupler of the present invention into an emulsion, a conventionally known method may be used. For example, tricresyl phosphate, a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as dibutyl phthalate or a low boiling point solvent such as butyl acetate or butyl propionate, alone or as necessary in a mixed solution thereof, the coupler of the present invention. Is dissolved alone or in combination, then mixed with an aqueous gelatin solution containing a surfactant, then emulsified with a high-speed rotating mixer or colloid mill, and then added to silver halide to be used in the present invention. Emulsions can be prepared.

The silver halide composition preferably used in the light-sensitive material using the coupler of the present invention is silver chloride, silver chlorobromide or silver chloroiodobromide. Further, it may be a combination mixture such as a mixture of silver chloride and silver bromide. That is,
When the silver halide emulsion is used for color photographic paper, particularly rapid developing property is required. Therefore, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and a chloride containing at least 1% of silver chloride. Particularly preferred is silver, silver chlorobromide or silver chloroiodobromide.

The silver halide emulsion is chemically sensitized by a conventional method. Further, it can be optically sensitized to a desired wavelength range.

The silver halide emulsion contains an antifoggant or stabilizer in the photographic industry for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage, or photographic processing and / or keeping the photographic performance stable. Compounds known as can be added.

The color light-sensitive material using the coupler of the present invention includes a color fog-preventing agent, a dye image stabilizer, an anti-UV agent, an antistatic agent, a matting agent, which are usually used in light-sensitive materials.
A surfactant or the like can be used.

Regarding these, for example, Research Disclosure Vol. 176, 22-31
The description on page (December 1978) can be referred to.

The color photographic light-sensitive material using the coupler of the present invention can form an image by performing color development processing known in the art.

The color photographic light-sensitive material using the coupler according to the present invention may contain a color developing agent in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof, and may be processed with an alkaline activating bath. it can.

The color photographic light-sensitive material using the coupler of the present invention is subjected to bleaching treatment and fixing treatment after color development.
The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, a stabilizing treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0050]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 A red light-sensitive color light-sensitive material sample 1 was prepared by sequentially coating the following layers from the support side on a paper support laminated on both sides with polyethylene. Unless otherwise specified, the addition amount of the compound is per 1 m ² (silver halide is a silver conversion value).

First Layer: Emulsion Layer Red consisting of 1.2 g gelatin, 0.35 red-sensitive silver chlorobromide emulsion (containing 99.5 mol% silver chloride) and comparative cyan coupler a 7.5 × 10 ^-4 mol dissolved in 0.50 g dioctyl phosphate. Sensitive emulsion layer.

Second layer: protective layer A protective layer containing 0.50 g of gelatin. As a hardener, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added to 0.017 g per 1 g of gelatin.

Next, in the same manner as in Sample 1, except that the comparative coupler a in Sample 1 was replaced by the coupler shown in Table 1 (the addition amount was the same molar amount as that of Comparative coupler a), Sample 2 of the present invention was used.
~ 7 were produced.

The samples 1 to 7 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

Treatment process Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30 ° C. to 34 ° C. 90 seconds Dry 60 ° C. to 80 ° C. 60 seconds Treatment liquid used in each processing step The composition is as follows.

(Color developer) Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine tetra Acetic acid 1.0 g Catechol-3,5-disulfonate disodium 1.0 g Diethylene glycol 10 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 4.5 g Optical brightener (4 , 4'-Diaminostilbenedisulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1000 ml, and the pH is adjusted to 10.20. (Bleach-fixing solution) ethylenediaminetetraacetate ferric ammonium dihydrate 60.0 g ethylenediaminetetraacetic acid 3.0 g ammonium thiosulfate (70% aqueous solution) 100.0 ml ammonium sulfite (40% aqueous solution) 27.5 ml Add water to bring the total volume to 1000 ml, Adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1- Diphosphonic acid 2.0g o-Phenylphenol sodium 1.0g Ethylenediaminetetraacetic acid 1.0g Ammonium hydroxide (20% aqueous solution) 3.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5g Adjust the volume to 1000 ml and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The concentrations of the samples 1 to 7 treated as described above were measured using a densitometer (KD-7 type manufactured by Konica Corporation), and the treated samples were treated at high temperature and high humidity (60 ° C, 80
% RH) and left for 14 days to examine the heat and humidity resistance of the dye image.

The results are shown in Table 1. However, the heat resistance and humidity resistance of the dye image are expressed by the percentage of dye residue after the heat and humidity resistance test with respect to the initial density of 1.0.

[0061]

[Chemical 10]

[0062]

[Table 1]

As is clear from the results in Table 1, the samples using the couplers of the present invention have a higher dye residual rate than the samples using the comparative couplers, and the samples faded even when exposed to high heat and high humidity. It turns out that is unlikely to occur.

Example 2 The red-sensitive silver chlorobromide emulsion (silver chloride) in Sample 1 of Example 1 was used.
0.35 g of green-sensitive silver chlorobromide emulsion (containing 99.5 mol% of silver chloride) was used in place of 0.35 g, and comparative cyan coupler a was replaced with 9.1 × 10 ^-4 mol of comparative magenta coupler b and The magenta coupler of the present invention is
Sample 8 was prepared in the same manner as in Example 1 except that ^{x10 -4} mol was used.
~ 14 were produced and subjected to the same exposure and development processing as in Example 1.

The densities of the samples 8 to 14 treated above were measured using a densitometer (Konica Corporation KD-7 type). Furthermore, each treated sample above is processed under high temperature and high humidity (60 ℃, 80
% RH) for 12 days and the dye image was examined for heat resistance and wetness. The obtained results are shown in Table 2. However, the heat and humidity resistance of the dye image is expressed as the percentage of dye residue after the heat and humidity resistance test with respect to the initial density of 1.0.

Further, each sample was irradiated with a xenon fade meter for 4 days, the density was measured, and the light resistance of the dye image was examined from the residual ratio of the dye after the light resistance test with respect to the initial density of 1.0.

The results are shown in Table 2.

[0068]

[Chemical 11]

[0069]

[Table 2]

From the results shown in Table 2, Sample Nos. 9 to 14 using the couplers represented by the general formulas [I] and [II] have higher light resistance than Sample No. 8 using the comparative coupler b. It is understood that the dye image is significantly improved, and the heat resistance and the moisture resistance are excellent, and a robust dye image is formed.

[0071]

According to the present invention, firstly, a novel photographic coupler used as a material for a silver halide color photographic light-sensitive material can be provided. Secondly, it is possible to provide a color photographic coupler capable of forming a color image without causing a change in hue due to heat, humidity and light.

Claims (2)

[Claims] 1. A pyrrolo [3,2-b] furan or pyrrolo [2,3-b] furan photographic coupler. 2. The pyrrolo [3,2-b] furans or pyrrolo [2,3-b] furans are represented by the following general formula [I] or general formula [II], respectively. Claim 1
The photographic coupler described. [Chemical 1] [In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]