JPH02277050A - Novel photographic coupler - Google Patents

Abstract

PURPOSE:To enhance fastness of a dyestuff image against heat, humidity, and light by using a specified coupler. CONSTITUTION:The silver halide photosensitive material uses the coupler of formula I in which Z is an atomic group necessary to form a 5-, 6-, or 7-membered hetero ring; each of X and Y is H or a releasable group; and R is H or a substituent. The compound of formula II and the like can be used for the coupler of formula I. The processes and techniques used for general dyestuff- forming couplers can be applied to this coupler and a magenta or cyan dyestuff image superior in fastness can be formed.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a new photographic coupler used as a color photographic material, and more particularly, to a novel photographic coupler that has excellent fastness against heat, humidity and light. This invention relates to photographic couplers that form magenta or cyan dye images.

[Background of the Invention] After a silver halide photographic material is subjected to imagewise exposure 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. As a result, pigments are produced and a color image is formed.

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

The dye formed from the 5-pyrazolone coupler, which has been widely used and studied as a magenta image forming coupler, has excellent fastness to heat and light, but has unnecessary absorption with a yellow component. This caused the color to become cloudy. As a solution to this problem, couplers such as virazolohenzimidazole, indacylon, pyrazolotriazole, imidazopyrazole, pyrazolopyrazole, and pyrazolotetrazole have been proposed, and in fact, dyes formed from these couplers are preferable in terms of color reproduction. However, it has the disadvantage of extremely low fastness to light, causing discoloration.

On the other hand, phenolic couplers, which are being researched as couplers for forming cyan dyes, have been improved in spectral absorption characteristics, light resistance, and heat/humidity resistance by devising substituents. A compound that satisfies all of these requirements has not yet been obtained.

[Object of the Invention] The 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 magenta or cyan dye images that do not change hue in response to heat, humidity, or light.

[Structure of the Invention] The above objects of the present invention have been achieved by a photographic coupler represented by the general formula [I1].

"-z' [wherein Z represents a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocyclic ring, and the 5- to 7-membered ring may have a substituent.

X and Y represent a hydrogen atom or a vine group that is released upon reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. The present invention will be explained in more detail below.

- In formula [I], the substituent represented by R is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio,
Examples include multiple groups such as arylthio, alkenyl, and cycloalkyl; in addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, and heterocycle. Oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, Also included are multiple groups such as hydroxy, mercapto, nitro, and sulfo, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

Hereinafter, in the multigroup represented by R, the alkyl group preferably has 1 to 32 carbon atoms, and may be straight 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 alkyl group and aryl group represented by R above.

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 straight or branched.

The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred.

Moyloxy group, arylcarbamoyloxy group Sulfonyl group includes alkylsulfonyl group, arylsulfonyl group, etc. Sulfinyl group includes alkylsulfinyl group, arylsulfinyl group, etc. Phosphonyl group includes alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, etc. Nyl group, arylphosphonyl group ring; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl group ring; Acyloxy group includes alkylcarbonyloxy group, arylcarbonyloxy group ring; Sulfonyloxy group includes alkylsulfonyloxy group, arylsulfonyloxy group ring; Carbamoyloxy group includes alkylcarba, etc.; Ureido group Examples of the sulfamoylamino group include an alkylureido group and an arylsulfamoylamino group; examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; the heterocyclic group is preferably a 5- to 7-membered one; specifically, is a 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group: The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle. , for example 3,4,5.6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group etc.: As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole -6 Monothio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc. Imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc. ; As a spiro compound residue, 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”
]]Decan-1-yl7,7-dimethyl-bicyclo[2
,2,l]butan-1-yl and the like.

The above group 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 is released by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkylene, alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy. , alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxy carbonylamino, aryloxycarbonylamino, carboxyl, -z''(R' has the same meaning as the above R, Y' and Z' have the same meanings as the above Y and Z, Ra and Rh are hydrogen atoms, aryl groups, alkyl groups or a heterocyclic group), preferably a halogen atom.

Y represents a hydrogen atom or a filling, and a preferable substituent is one that is eliminated after reacting with an oxidized developing agent.
28444, etc., under alkaline conditions, or by reaction with an oxidized developing agent as described in JP-A No. 56-133734, etc., coupling-off can be achieved. Y is preferably a hydrogen atom.

Therefore, among the compounds of the present invention represented by the general formula [I1], particularly preferred is the compound represented by the general formula [+1].

Represents a genus atomic group. Further, the 5- to 7-membered heterocycle may have a substituent as necessary.

The 5- to 7-membered heterocycle may be saturated or unsaturated;
The petero atom contained in the 7-membered heterocycle is preferably a nitrogen atom, a sulfur atom, or an oxygen atom, for example, in the general formula [
■! ] The compound represented by the following general formula [II a ] ~
It is represented by the general formula [I1i] etc., but is not limited thereto.

The following margin [where R%X and Z are R in the general formula [I]]
Same meaning as %X and Z. ] Z is a non-gold general formula necessary to form a 5- to 7-membered heterocycle (
Ila) General formula (Ila) General formula (Ilb) General formula (Ile) General formula [IC] General formula (Elf) - Numerical formula [■g] General formula (Ilhl General formula (Ili) [Wherein, R and X are , - formula [II and - formula [II
] has the same meaning as R and X.

Further, R1 represents a substituent, and specific examples include an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, a sulfonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. ] Also, the 5- to 7-membered heterocycle in formula [IIa] to general formula [I1il may have a substituent as necessary.

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

Margin below 10° 14° 15° 16° Cp.

11゜2゜13゜17゜8゜r 9゜20゜21゜22゜27゜28゜29゜+ttltsNHL;U 23゜24゜25゜(Acta (:himica Hungar
ica) 1985, 118(3), pages 221 to 223, and can be synthesized according to the synthesis method described therein.

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

The couplers of the present invention can also be used in combination with other types of 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 color photographs 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 the 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 in color photographic materials such as color negative and positive films and color photographic paper.

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

Multicolor light-sensitive materials have dye image-forming constituent 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 photographic material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler and at least one green emulsion layer containing at least one magenta coupler. a magenta dye image-forming unit consisting of a light-sensitive silver halide emulsion layer (at least one of the cyan coupler and/or magenta coupler being a coupler of the present invention), at least one blue-sensitive image-forming unit containing at least one yellow coupler; It consists of a yellow dye image-forming structural unit consisting of a silver halide 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 coupler of the present invention can 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. alone or in combination, mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotary mixer or colloid mill, and then added to silver halide to obtain the halogenated compound used in the present invention. Silver emulsions can be prepared.

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 in the photographic industry as anti-capri agents or stabilizers can be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable.

Color photosensitive materials using the coupler of the present invention can contain color antifoggants, dye image stabilizers, ultraviolet inhibitors, antistatic agents, matting agents, surfactants, etc. that are commonly used in photosensitive materials. .

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

An image can be formed on the 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 material using the coupler according to the present invention is
A color developing agent is contained in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof,
Treatment can also be carried out using an alkaline activation 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 specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 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. Incidentally, the amount of the compound added is shown per 1 m2 unless otherwise specified (silver halide is a silver equivalent value).

1st layer: Emulsion layer 1.2 g of gelatin, red-sensitive silver chlorobromide emulsion (silver chloride 96
Comparative cyan coupler a9, I dissolved in 0.30 g (containing mol %) and 1.35 g of dioctyl phosphate
Red-sensitive emulsion layer consisting of Xl0-' moles.

Second layer: Protective layer Protective layer containing 0.50 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 gram of gelatin.

Next, Samples 2 to 8 of the present invention were prepared in exactly the same manner as in 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 process) Color development 38℃ 3 minutes 30 seconds bleach fixing
Stabilization treatment at 38°C for 1 minute and 30 seconds/or washing treatment at 25°C to 30°C for 3 minutes Drying at 75°C to 80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) Benzyl alcohol Ethylene glycol 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 conductor) Add potassium hydroxide water to bring the total volume to pH 10.

(Bleach-fix solution) Ferric ethylenediaminetetraacetic acid 2.0g Adjusted to 20 5IIIR 15mj) 2.0g 0.7g 0.2g 30.0g 3.0g 2.5g 5.5g 1.0g Ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate C70% solution) 100mj + Ammonium sulfite (40% solution) 27.5mA + Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11
shall be.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g Add water to l
Let it be ji.

The concentrations of samples 1 to 8 treated above were measured using a densitometer (K (+-78 type) manufactured by Konica Corporation), and each of the above-treated samples was measured at high temperature (60℃, 80% R
H) The dye image was left in an atmosphere for 14 days, and the heat resistance and moisture resistance of the dye image were examined.

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

Comparison coupler a CsH+ + (t) Shi! Table 1 As is clear from the results in Table 1, the samples using the coupler of the present invention had a higher dye residual rate than the samples using the comparative coupler, and the color did not fade even when placed at high temperatures. It turns out that it is difficult for this to occur.

Example 2 0.35 g of green-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) in place of 0.30 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) in Sample 1 of Example 1 using
Comparison cyan coupler a9. Magenta couplers (8) (11) and (
Samples 9, 10 and 11 were prepared in the same manner as in Example 1, except that 5.1 x 10-' moles of each of Samples 20) were used, and the same exposure and development treatments as in Example 1 were performed.

The heat resistance and moisture resistance of each of the above-mentioned treated samples were examined in the same manner as in Example 1. In addition, after irradiating each sample for 3 days with a xenon fade meter, the concentration was measured and the initial concentration was 1.0.
The light resistance of the dye image was investigated from the dye residual rate after the light resistance test.

As a result, it was found that the obtained magenta dye image was extremely resistant to heat and humidity, and was also relatively fast to light, and had the effects of the present invention.

Example 3 The following layers were sequentially coated on a triacetyl cellulose film from the support side to prepare red-sensitive color reversal photographic materials 12 to 16 containing the couplers shown in Table 2.

1st layer: Emulsion layer 1.4 g of gelatin, 0.5 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 1.5 g of dibutyl phthalate.
A red-sensitive emulsion layer consisting of 9.1 x 10-4 mol of the coupler shown in Table 2 dissolved in g.

2nd layer: Protective layer Protective layer containing ceratin o, sg, 2 as a hardening agent
．． 4-dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 g per gram of gelatin.

[Reversal processing process] Process Processing temperature Processing time 1st development 38°C 3 minutes Water washing
Invert for 2 minutes at 38℃
38℃ 2 minutes color development
38℃ 6 minute adjustment 38℃
2 minute bleach 38
℃ 6 minutes fixation
Wash with water at 38℃ for 4 minutes
Stable at 38℃
Drying at 38°C The composition of the room temperature treatment solution is as follows.

[First developer Cotetra Sodium polyphosphate Sodium sulfite Hydroquinone monosulfonate Sodium carbonate (monohydrate) l-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0,1 % solution) Add water [Reverse solution conitrilotrimethylenephosphonic acid, hexasodium salt, stannous chloride (dihydrate) p-aminophenol 4 minutes 1 minute g 2.5 g 1.2 g 2 m・1 1000 mJ2 g g 0.1g Sodium hydroxide Add glacial acetic acid water [Color developer] Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (12 hydrate) Potassium bromide Potassium iodide (0.1% solution) Sodium hydroxide Citrazine Add acid N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline/sulfate ethylenediamine water [adjustment solution] Sodium sulfite Sodium ethylenediaminetetraacetate (dihydrate) g 15 ml 1 1000 ml 2 g g 6 g g 0mJ2 g 1.5 g 1 g g 1000mf1 2 g g Thioglycerin Add glacial acetic acid water [Bleach solution] Sodium ethylenediaminetetraacetate (dihydrate) Ammonium ethylenediaminetetraacetate iron (III) (
dihydrate) Add potassium bromide water [Fixer] Add ammonium thiosulfate sodium sulfite sodium bisulfite water [Stabilizer] Formalin (37% by weight) Konidax (manufactured by Konica Corporation) Add water and add 0.4 ml2 mal 1000ml2 g 20 g 00 g 000ml g 1000mj2 ml ml2 1000ml For each sample treated above, the heat resistance and moisture resistance of the dye image were examined in the same manner as in Example 1.

The results are shown in Table-2.

However, in this example, the transmission density was measured using a D-7R type densitometer.

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. I understand that.

Example 4 0.58 g of green-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) was used in place of 0.5 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) in Sample 12 of Example 3. Comparative cyan coupler a 9. Sample 17 and Sample 18 were prepared in the same manner as in Example 3, except that 5.1 x 10-' mol of magenta couplers (28) and (29) of the present invention were used in place of I x 10-' mol. death,
The same exposure and development treatments as in Example 3 were performed.

When the heat resistance, humidity resistance, and light resistance of the processed sample were examined in the same manner as in Example 2, the obtained magenta dye image was robust to heat, humidity, and light, and was found to have the effects of the present invention. I understand.

[Effects of the Invention] Cyan or magenta images formed from the couplers of the invention were robust to heat, humidity and light, and were useful in color photographic materials.

Patent applicant Co Nika Co., Ltd. Representative Patent Attorney Miki Nakajima Yugai-na

Claims (1)

[Claims] A photographic coupler represented by the general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. May have. X and Y represent a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ]