JPH04116553A - Novel photographic coupler - Google Patents

Abstract

PURPOSE:To obtain the photographic coupler capable of forming cyan dye images which do not cause a change in hue to heat, moisture and light by constituting the coupler having a specific chemical structure. CONSTITUTION:The coupler of the chemical structure expressed by formula I is constituted. In the formula I, R1 to R3 and Y denote a hydrogen atom or substituent; Z denotes 0 or S; X denotes a hydrogen atom or the group which is eliminated by reacting with the oxidant of a color developing agent. The photographic coupler capable of forming the cyan dye images which do not cause the change in hue to the heat, moisture and light is obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel photographic coupler used as a color photographic material, and more specifically, it forms a dye image with excellent fastness to heat, humidity, and light. Regarding photographic couplers.

[Background of the Invention] After a silver halide photographic material is exposed to light and then subjected to color development processing, the oxidized aromatic primary amine color developing agent and the dye-forming coupler react in the exposed area. Pigments are produced and a colored image is formed.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and hisyan color images.

Examples of photographic couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and Indacylon couplers are known, and as couplers for forming cyan images, for example, phenol or naphthol couplers are generally used.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity.

However, phenolic couplers and naphthol couplers, which have been studied as couplers for forming cyan dyes, have poor spectral absorption characteristics, heat resistance, moisture resistance, light resistance, etc. of the formed cyan dye images. This is still unsatisfactory, and various proposals have been made to improve this, including devising substituents, but a compound that satisfies all of these has so far not been obtained.

Therefore, the present inventors conducted further research regarding the above points, and as a result, discovered a photographic coupler that can form a cyan dye image that does not change in hue due to heat, humidity, or light.
The present invention has now been completed.

[Object of the Invention] A first object of the present invention is to provide a novel photographic coupler that can be used as a color photographic material.

A second object of the present invention is to provide a photographic coupler that forms a cyan dye image that does not change in hue due to heat, humidity, or light.

[Structure of the Invention] The above object of the present invention has been achieved by a photographic coupler (hereinafter referred to as the coupler of the present invention) represented by -Funzo [I].

General formula [I1 [wherein R1, R2, R3 and Y represent a hydrogen atom or a substituent, and Z represents O or S]. X represents a hydrogen atom or a group that reacts with an oxidized product of a color developing agent and leaves the group. ] Hereinafter, the present invention will be explained in more detail.

- The substituent represented by R1 in Shipura [I] is:
Alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl,
Examples include groups such as cycloalkyl, but also halogen atoms, cycloalkenyl, alkynyl, heterocycle,
Sulfonyl, sulfinyl, sulfonyloxy, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino , aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl,
Also included are groups such as hydroxy, mercapto, nitro, and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues.

The alkyl group described above preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

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.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the aforementioned alkyl groups and aryl groups.

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 12 carbon atoms, especially 5
-7 is preferred.

Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and arylphosphonyl groups. Examples of nearacyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the 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, a 2-thienyl group , 2-pyrimidinyl group,
2-benzothiazolyl group, l-pyrrolyl group, 1-tetrazolyl group, etc.; As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, such as 3,4,5.6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
The heterocyclic thio group such as oxy group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-hendithiazolylthio group, 2,4-diphenoxy-1,3,5-)lyazole- 6-thio group etc.

Siloxy groups include trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxy, etc.; imide groups include succinimide, 3-heptadecylsuccinimide, phthalimide, cultarimide, etc.; spiro compound residues include spiro [3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
]hebutan-1-yl, tricyclo[3°3.1.1'
-7] Decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, etc.

Examples of the substituents represented by R3 and R1 include multiple groups such as alkyl, aryl, alinino, acylamino, sulfonamide, alkenyl, and cycloalkyl; in addition, cycloalkenyl, alkynyl, heterocycle, sulfonyl, Sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, amino and spiro compound residues, bridged Also included are multiple groups such as hydrocarbon compound residues.

Specific examples of the above-mentioned multiple groups include the same specific examples as those listed for R1.

The substituents represented by R, R, and R3 may further have a substituent such as a long-chain hydrocarbon group, a diffusion-resistant group such as a polymer residue, or an electron-withdrawing group.

Examples of the group that is released by reaction with the oxidized product of the color developing agent represented by , alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxy carbonylamino, aryloxycarboniamino, carboxyl, 2' (R1, R2, R5, Y' and Z' are the above R1, R7
, R1, Y and Z, respectively, and Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group. ), preferably a halogen atom, particularly a chlorine atom.

Y represents a hydrogen atom or a substituent, and a preferable substituent represented by Y is one that leaves the compound of the present invention after it reacts with an oxidized developing agent; for example, when Y is The substituents represented are those described in JP-A No. 61-22844.
4, etc., under alkaline conditions, or by reaction with an oxidized form of a developing agent, as described in JP-A-58-133734, etc. Examples include substituents that cause ring-off. Preferably Y is a hydrogen atom.

Next, specific examples of the compound represented by -Funazura [I] are shown in a table.

The coupler of the present invention described above is made of Sulfur Letters (S
Ulfur, Lett, ) 1983.1 (14)
, pages 119 to 125, and can be synthesized according to the synthesis method described therein.

The couplers of the invention typically have IX per mole of silver halide.
10-3 mol to 1 mol, preferably IX to-2
It can be used in the range of -8 x 10-' moles.

The coupler of the present invention can also be used in combination with other types of cyan couplers.

The methods and techniques used in conventional dye-forming couplers apply similarly to the couplers of the 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 include external coloring method and internal coloring method. When used as an external coloring method, the coupler of the present invention can be dissolved in an alkaline aqueous solution or an organic solvent (for example, alcohol) and added to a developing solution.

When the coupler of the present invention is used as a material for forming a color photograph by an internal coloring method, the coupler of the present invention is incorporated into a photographic light-sensitive material.

Typically, a method is preferably used in which the coupler of the present invention is blended into a silver halide emulsion and this emulsion is coated on a support to form a color light-sensitive material. The coupler of the present invention is used, for example, in color photographic materials such as color negative and positive films and color photographic paper.

This color photographic paper and other light-sensitive materials using the coupler of the present invention may be monochromatic or multicolor. In a multicolor light-sensitive material, the coupler of the present invention may be contained in any layer, but it is usually contained in a red-sensitive silver halide emulsion layer.

Multicolor photosensitive materials contain dye image-forming units that are sensitive to each of the three primary color regions of the spectrum. Each building block can consist of a single or multiple emulsion layer sensitive to a certain region of the spectrum. The constituent layers of the photosensitive material, including the layers of image-forming units, can be arranged in various orders as is known in the art. A typical multicolor light-sensitive material is a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler (at least one of the cyan couplers is the cyan coupler of the present invention). ), a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler. It consists of a yellow dye image-forming structural unit consisting of an emulsion layer supported on a support.

The photosensitive material may contain additional layers such as filter layers, interlayers,
It can have a protective layer, an undercoat layer, etc.

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

Silver halide compositions preferably used in the light-sensitive material using the coupler of the present invention include silver chloride, silver chlorobromide, and silver chloroiobromide. Furthermore, a combination mixture such as a mixture of silver chloride and silver bromide may be used. That is, when a silver halide emulsion is used for color photographic paper, particularly fast developability is required, so it is preferable that the halogen composition of the silver halide contains chlorine atoms, and at least 1%.
It is particularly preferable to use silver chloride, silver chlorobromide, or silver chloroiodobromide containing silver chloride.

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

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known as antifoggants or stabilizers in the photographic industry may be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

In the color photosensitive material using the coupler of the present invention, color antifoggants, dye image stabilizers, ultraviolet inhibitors, antistatic agents, matting agents, surfactants, etc., which are normally used in photosensitive materials, can be used. .

Regarding these, for example, Research Disclosure +
-(Research Disclosure)
The description in Vol. 176, pp. 22-31 (December 1978) may be referred to.

An image can be formed on a color photographic material using the coupler of the present invention by subjecting it to a color development treatment known in the art.

The color photographic light-sensitive material using the coupler of the present invention can contain a color developing agent in the hydrophilic colloid layer as the color developing herbal agent itself or as its precursor, and can be processed in an alkaline activating bath.

A color photographic material using the coupler of the present invention is subjected to a bleaching treatment and a fixing treatment after color development.

Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

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

Example 1 A red-sensitive color photosensitive material sample 1 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side. Note that the amount of the compound added is per unit unless otherwise specified (silver halide is a silver equivalent value).

1st layer: Emulsion layer Comparative cyan coupler a dissolved in 1.5 g of gelatin, 0.30 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 1.50 g of dioctyl phosphate9. O
A red-sensitive emulsion layer consisting of x to-' moles.

2nd layer: Protective layer Protective layer containing 0.50 g of gelatin. In addition, as a hardening agent, 2
, 4-dichloro-6-hydroxy-5-) riazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

Next, Samples 2 to 8 of the present invention were prepared in exactly the same manner as Sample 1, except that comparative coupler a was replaced with the coupler shown in Table 1 (the amount added was the same molar amount as comparative coupler a).

Samples 1 to 8 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

[Development processing step Color development 38℃ 3 minutes 30 seconds Bleach fixing 38℃ 1 minute 30 seconds Stabilization treatment 25℃ ~ 3 (1'0 3 minutes drying)
Drying 75°C to 80°C The composition of the treatment liquid used in the 2-minute combination treatment step is as follows.

[Color developer] Benzyl alcohol 15ml pEthylene glycol 15ml! Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate Hydroxylamine sulfate Polyphosphoric acid (TPPS) 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate Optical brightener (4, 4'-Diaminostilbendisulfonic acid derivative) Add potassium hydroxide water to bring the total amount to 1 g.

[Bleach-fix solution Ferric ammonium coethylenediaminetetraacetate dihydrate Ethylenediaminetetraacetic acid Ammonium thiosulfate (70% solution) Ammonium sulfite (40% solution) pHl [I,20 2.0g 0.7 g- 0.2g 30. 0 g 3.0 g 2.5 g 5.5 g ■, adjust to Og 2.0 g 0 g 3 g 100 ml 27.5 m 1) Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to is 11.

[Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g Add water to 1 g
shall be.

The concentrations of Samples 1 to 8 treated above were measured using a densitometer (Model KD-7 manufactured by Konica Corporation), and each of the above-treated samples was measured at high temperature and high humidity (60°C, 80% RH).
) Under atmosphere 1. : The dye image was left to stand for 360 hours, and the heat resistance and moisture resistance of the dye image were examined.

Further, each sample was irradiated with a xenon fade meter for 270 hours, and then the density was measured to examine light resistance. The results are shown in Table-1. However, the heat resistance, moisture resistance, and light resistance of the dye image are expressed as the percentage of dye remaining after heat, moisture resistance, and light resistance tests with respect to an initial density of 1.0.

Comparative coupler a I Table 1 As is clear from the results in Table 1, the samples using the coupler of the present invention all had a higher dye residual rate and better heat resistance and moisture resistance than the samples using the comparative coupler. It can be seen that it has excellent properties and is robust. Furthermore, it can be seen that the light resistance is also the same or higher, which indicates that the light resistance is excellent.

Example 2 A red-sensitive color photosensitive material (sample 9) was prepared by sequentially coating the following layers on a subbed triacetate film from the support side. Incidentally, the amount of the compound added is per 1rrl' unless otherwise specified (silver halide is a silver equivalent value).

1st layer: Emulsion layer Comparative cyan coupler b8, OXl0 dissolved in 1.4 g of gelatin, 1.5 g of red-sensitive silver iodobromide emulsion (containing 4 mol% silver iodide) and 1.3 g of tricresyl phosphate.
−' red-sensitive emulsion layer consisting of mol.

2nd layer: Protective layer Protective layer containing 1.5 g of gelatin. In addition, as a hardening agent, 2,
4-dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 g per 1 g of gelatin.

Next, for sample 9, the comparison cyan coupler b is shown in Table-2.
Samples 10 to 1 of the present invention were prepared in exactly the same manner except that the coupler shown in (the amount added was the same molar amount as the comparative coupler) was used.
6 was produced.

The obtained film samples were wedge exposed in a conventional manner and color developed according to the color processing steps described below.

Comparative coupler b [Processing process] Color development bleaching water washing fixing water landing washing (processing temperature 38°C) processing time 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds Stabilization 1 minute 30 seconds The composition of the processing liquid used in each drying process is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxyamine 1/2 sulfate 2.0g anhydrous potassium carbonate
37.5g sodium bromide
1.3 g Trisodium nitrilotriacetic acid (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 g, and adjust to I) H10.8 using sodium hydroxide.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0 g of water to make 1 g, and adjust the pH to 6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1g,
Adjust the pH to 6.0 using acetic acid.

[Stabilizing liquid] Formalin (37% aqueous solution) 1.5 mg
Konidax (manufactured by Konica Corporation) 7.5 mJ7 Add water to make 1 p.

For the samples 9 to 1B treated above, the transmission density was measured using a densitometer (model KD-7R manufactured by Konica Corporation), and each of the above treated samples was measured at high temperature and high humidity (60°C, 8°C).
The dye image was left in an atmosphere (0% RH) for 360 hours, and the heat resistance and moisture resistance of the dye image were examined.

In addition, each sample was irradiated with a xenon fade meter for 270 hours to examine light resistance. The results are shown in Table-2. However, the heat resistance, moisture resistance, and light resistance of the dye image are expressed as the percentage of dye remaining after the heat resistance, moisture resistance, and light resistance tests with respect to the initial density of 10.

Table 2 As is clear from the results in Table 2, the samples using the coupler of the present invention all had higher dye residual rates and superior heat and moisture resistance than samples using the comparative coupler. You can tell it's sturdy. Furthermore, it can be seen that the light resistance is also the same or higher, which indicates that the light resistance is excellent.

Example 3 The following layers were sequentially coated on a triacetyl cellulose film support from the support side to prepare red-sensitive color reversal photographic materials 17 to 22 containing the couplers shown in Table 3.

1st layer: Emulsion layer 1.5 g of gelatin, 0.5 g of red silver chlorobromide emulsion (containing 96 mol% silver chloride) and 1.5 g of dibutyl phthalate.
Coupler shown in Table 3 dissolved in 6g 9.0×10−
Red-sensitive emulsion layer consisting of 4 moles.

2nd layer: protective layer protective layer containing 0.5 g of gelatin. In addition, as a hardening agent, 2,
0.017 g of 4-dichloro-6-hydroxy-5-) riazine sodium salt was added per 1 g of gelatin.

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

[Reversal processing step Time: Temperature first development 6 minutes 38℃ water washing
2 minutes 38℃ inversion 2 minutes 38℃ color development 6 minutes 38℃ adjustment
Bleach at 38℃ for 2 minutes
6 minutes 38℃ fixation
Wash with water at 38℃ for 4 minutes
4 minutes Stable at 38℃ 1 minute Dry at 38℃
Drying The following composition was used for the room temperature treatment solution.

[First developer] Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone
Monosulfonate sodium carbonate (monohydrate) 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone potassium bromide.

Potassium thiocyanate Potassium monoiodide (0.1% solution) Add water [reverse solution] Nitrilotrimethylenephosponic acid, hexasodium salt Stannous trichloride (dihydrate) 1p-aminophenol
0.1 Sodium hydroxide
5 Glacial acetic acid I5 Add water 1000 [Color developer Sodium polyphosphate Sodium sulfite Sodium tertiary phosphate (decahydrate) g g 0g 0g 8 g g g g g 2ml) 1000ml I il Potassium bromide 1 Iodide Potassium (0.1% solution) 90 Sodium hydroxide 3 Citrazic acid 1.5 N-ethyl-N-(β-
Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11 Ethylenediamine 3 Add water
1000 [Adjustment solution Sodium sulfite 12 Sodium ethylenediaminetetraacetate (dihydrate) 8 Thioglycerin 0.4 Glacial acetic acid
3 Add water 100
0 [Bleach solution] Sodium ethylenediaminetetraacetate (dihydrate) 2.0 Iron(III) ethylenediaminetetraacetate ml) ml) g m(1 Ammonium (dihydrate) 120.0 g Potassium bromide too, o g Water Add 1000 mfl [fixer] Ammonium thiosulfate go, o g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Add water
1000 mO [stabilizing liquid coformin (37% by weight) 5.0 mjl
1 Konidax (manufactured by Konica Corporation) 5.0 m (1000 mi with addition of 1 water) For each sample treated above, the heat resistance, moisture resistance, and light resistance of the dye image were examined in the same manner as in Example 2. Table the results.
Shown in 3.

Margin Table 3 below As is clear from Table 3, the samples using the coupler of the present invention all have a higher dye residual rate, superior heat resistance and moisture resistance, and are more durable than samples using the comparative coupler. It can be seen that it is. Furthermore, it can be seen that the light resistance is also the same or higher, which indicates that the light resistance is excellent.

Effects of the Invention Dye images formed from couplers of the invention are robust to heat, humidity and light.

Claims (1)

[Claims] A photographic coupler characterized by being represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3 and Y represent a hydrogen atom or a substituent, and Z represents O or S. X represents a hydrogen atom or a group that reacts with an oxidized product of a color developing agent and leaves the group. ]