JPH0786676B2 - New cyan coupler for color photography - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel cyan coupler used as a material for a silver halide color photographic light-sensitive material, and particularly has excellent spectral absorption characteristics and fastness to heat and humidity. The present invention relates to a novel photographic coupler capable of forming a dye image.

BACKGROUND OF THE INVENTION 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. The amine color developing agent and the dye-forming coupler react with each other to form a dye, thereby forming a color image.In such a photographic method, a color reproduction method by a subtractive color method is used,
As a result, yellow, magenta, and cyan color images are formed.

Conventionally, as a photographic coupler used to form the yellow image, there is, for example, an acylacetanilide type coupler, and as a magenta 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, and a dye image obtained from these couplers can be exposed to light for a long time. Even if exposed
Further, it is desired that the color does not fade even when stored under high temperature and high humidity.

However, the above-mentioned phenol-based couplers and naphthol-based couplers, which have been researched and put into practical use as couplers for forming a cyan dye, have the following spectral absorption characteristics, heat resistance and moisture resistance of the formed cyan dye image. However, various proposals have been made in the past, including selection and investigation of substituents in couplers, aiming at this improvement, but satisfy all the requirements for these properties. Such a coupler has not been discovered yet.

Therefore, as a result of further research in view of such a situation, the present inventors have found a photographic coupler capable of forming a cyan dye image which is excellent in spectral absorption characteristics and does not cause a hue change with respect to heat and humidity. It was

OBJECTS OF THE INVENTION Therefore, a first object of the present invention is to provide a novel photographic coupler used as a material of a silver halide color photographic light-sensitive material, and a second object of the present invention is a spectral absorption. It is an object of the present invention to provide a cyan coupler for color photography which has excellent characteristics and can form a dye image which does not cause a change in hue due to heat and humidity.

[Structure of the Invention] The present invention has been invented based on the above findings, and the above object is to provide at least one electron-withdrawing group other than a carboxyl group and a halogen atom at a substitutable position excluding the active site. This is accomplished by a pyrazolo- [1 ', 5': 3,2] -quinazolone-based color photographic cyan coupler having a substituent.

[Detailed Description of the Invention] Hereinafter, the present invention will be described more specifically.

The photographic coupler of the present invention is specifically represented by the following general formula [I].
A pyrazolo- [1 ′, 5 ′: 3,2] -quinazolone represented by the general formula [I] In the formula, R ₁ and R ₂ are substituents, at least one of which represents an electron-withdrawing substituent other than a carboxyl group and a halogen atom, Y represents a hydrogen atom or a substituent, and n is 0. Represents an integer of ˜4, and when n is plural, the R _{2 s} may be the same or different from each other.

Explaining the electron withdrawing substituent in detail, the substituent may be any conventionally known electron withdrawing substituent, but preferably the substituent constant δ _p defined by Hammett is +0. 20 or more substituents, such substituents include sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, cyano, nitro, halogenated alkyl, aryl halide, halogenated alkoxy. , Aryloxy halide, furyl, pyrrolyl and tetrazolyl groups.

Examples of the sulfonyl group include groups such as alkylsulfonyl, arylsulfonyl, halogenated alkylsulfonyl, and halogenated arylsulfonyl.

Examples of the sulfinyl group include alkylsulfinyl,
Examples include groups such as arylsulfinyl.

Examples of the sulfonyloxy group include groups such as alkylsulfonyloxy and arylsulfonyloxy.

The sulfamoyl group may be substituted with an alkyl group or an aryl group.

Examples of the phosphoryl group include groups such as alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl, arylphosphoryl and the like.

The carbamoyl group may be substituted with an alkyl group or an aryl group.

Examples of the acyl group include groups such as alkylcarbonyl and arylcarbonyl.

The acyloxy group is preferably alkylcarbonyloxy or the like.

Examples of the oxycarbonyl group include groups such as alkoxycarbonyl and aryloxycarbonyl.

Examples of the halogenated alkyl group include groups such as trifluoromethyl, heptafluoroisopropyl, and nonylfluoro (t) butyl.

Examples of the halogenated aryl group include groups such as tetrafluorophenyl and pentafluorophenyl.

As the halogenated alkoxy group, an α-halogenated alkoxy group is preferable.

The halogenated aryloxy group is preferably each group such as tetrafluoroaryloxy and pentafluoroaryloxy.

Examples of the furyl group include groups such as 2-furyl.

Examples of the pyrrolyl group include groups such as 1-pyrrolyl.

Examples of the tetrazolyl group include groups such as 1-tetrazolyl.

The above electron-withdrawing group may be further substituted with a group such as a long-chain hydrocarbon group, a diffusion resistant group such as a polymer residue, or another electron-withdrawing group.

Examples of the electron-withdrawing substituent in the compound represented by the general formula [I] (hereinafter, also referred to as the compound of the present invention or the coupler of the present invention) include sulfonyl, sulfonyloxy, sulfamoyl, Carbamoyl, acyl, acyloxy, oxycarbonyl, cyano, alkyl halide and furyl groups are particularly preferred.

When _one of R ₁ and R ₂ in the general formula [I] represents a substituent other than the electron-withdrawing substituent, the substituent represented by R ₁ or R ₂ is particularly preferably Although not limited, typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups, and in addition to these, cycloalkenyl, alkynyl, Heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, heterocyclethio, thioureido, hydroxy, mercapto, sulfo, etc. Each group, spiro compound residue, bridged hydrocarbon compound residue It can be also mentioned.

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

The aryl group is preferably a phenyl 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.

Examples of the alkyl moiety and the aryl moiety contained in the alkylthio group and the arylthio group include the alkyl group and the aryl group which are mentioned as preferable examples of the alkyl group and the aryl group.

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 preferably has 3 to 12 carbon atoms, and more preferably 5 to 7 carbon atoms.

The heterocyclic group is preferably a 5- to 7-membered one, specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-
Examples thereof include a tetrazolyl group.

The heterocyclic oxy group preferably has a 5- to 7-membered heterocyclic ring, and examples thereof include a 3,4,5,6-tetrahydropyranyl-2-oxy group and a 1-phenyltetrazole-5-oxy group. To be

Examples of the siloxy group include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group.

Examples of the imide group include a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, and a glutarimide group.

Examples of the ureido group include an alkylureido group and an arylureido group.

Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group.

The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6- A thio group etc. are mentioned.

Examples of the spiro compound residue include spiro [3.3] heptan-1-yl and the like.

The bridged hydrocarbon compound residue is bicyclo [2.2.
1] heptan-1-yl, tricyclo [3.3.1.1 ^37] decane-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

The substituent may be further substituted with a group such as a long-chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Y in the general formula [I] is a hydrogen atom, or a compound which is eliminated from a compound of the present invention when the compound of the present invention reacts with an oxidized product of a developing agent, for example, as described in JP-A-61-228444. As described in JP-A-56-133734 and the like, a group capable of splitting off under alkaline conditions, and a coupling group formed by reaction with an oxidized product of a developing agent.
Substituents that turn off are preferred, and hydrogen atoms are particularly preferred.

Typical examples of the compound of the present invention represented by the general formula [I] are shown below.

Coupler number The couplers of the invention illustrated above are described in U.S. Pat.
No. 0, No. 4,261,996 and No. 4,247,55
It can be synthesized with reference to the method described in the specification of No. 5 and the like.

Next, representative synthetic methods of the compound of the present invention will be illustrated.

Synthesis Example 1 [Synthesis of Compound (1) of the Present Invention] 18.4g (0.1mol) of the above compound a and 43.2g (0.1mol) of b
It was dissolved in 50 ml of butyl alcohol and then heated under reflux for 2 hours. To the resulting solution was added 9 g of sodium carbonate and then heated under reflux for 2 hours. Butyl alcohol was evaporated from the reaction solution and concentrated. After adding water and neutralizing with hydrochloric acid, the residue was recrystallized from a mixed solvent of toluene and acetonitrile to give white crystals of the compound (1) 13.3 of the present invention. g (yield 25%) was obtained.

Synthesis Example 2 [Synthesis of Compound (4) of the Present Invention] 16.2 g (0.1 mol) of the above compound c and 34.8 g (0.1 mol) of d
After dissolving in 40 ml of methanol, the mixture was stirred at room temperature for 2 hours, then 9.8 g of sodium carbonate was added, and then the mixture was stirred at 50 ° C. for 2 hours. The reaction solution was poured into 300 ml of water, neutralized with hydrochloric acid, and the solid thus precipitated was recrystallized from a mixed solvent of toluene and acetonitrile to give 12.8 g of the above-mentioned compound e in the form of white crystals (yield). 30%) obtained.

Next, 10.0 g (0.023 mol) of this compound e was dissolved in 100 ml of acetic acid, and 35 ml of 35% hydrogen peroxide solution was slowly added dropwise to the resulting solution, followed by stirring at 50 ° C. for 3 hours. By adding 300 ml of water to this solution, neutralizing it with an aqueous sodium hydroxide solution at a temperature of 5 ° C. or lower, and then neutralizing the resulting solution with ethyl acetate, and distilling off ethyl acetate from the extract. When the produced precipitate was recrystallized using acetonitrile, 8.5 g (yield 80%) of the present compound (4) crystallized in the form of white powder was obtained.

The coupler of the present invention exemplified above can be synthesized with reference to the above synthesis examples.

The coupler of the present invention usually contains 1 × per mol of silver halide.
10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹
It can be used in the molar range and can also be used in combination with other types of couplers.

The methods and techniques used in conventional dye-forming couplers are likewise applicable to the couplers of this invention.

The coupler of the present invention can also be used as a material for forming a color photographic material by any coloring method including an external coloring method and an internal coloring method.

When the coupler of the present invention is used as a color photographic forming material by the external color development method, the coupler of the present invention is used by dissolving it in an alkaline aqueous solution or a hydrophilic organic solvent (for example, alcohol) and adding the solution to a developing solution. it can.

Further, when used as a color photographic forming material by the internal color forming method, the coupler of the present invention is used by being contained in a color photographic light-sensitive material, and typically, the coupler of the present invention is compounded in a silver halide emulsion, A method for forming a color light-sensitive material by coating this emulsion on a support is preferably used.

The coupler of the present invention is used for 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 multicolor light-sensitive material, the coupler of the present invention may be contained in any layer, but it is usually contained in the green-sensitive silver halide emulsion layer and / or the red-sensitive silver halide emulsion layer.

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, and each constituent unit is a single layer or a multi-layer emulsion layer having photosensitivity to a certain region of the spectrum. Can consist of The constituent layers of the light-sensitive material, including the layers of the image-forming constituent units, can be arranged in various orders as is known in the art, and a typical multi-color light-sensitive material contains at least one cyan material. A cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer containing a coupler, at least one of which comprises the coupler of the invention, and at least one green containing at least one magenta coupler. A magenta dye image-forming constituent unit consisting of a light-sensitive silver halide emulsion layer and a yellow dye image-forming constituent unit consisting of at least one blue light-sensitive silver halide emulsion layer containing at least one yellow coupler are supported on a support. It consists of 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 cyan coupler of the present invention into an emulsion, a conventionally known method may be used. For example, any one of a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as tricresyl phosphate and dibutyl phthalate or a low boiling point solvent having a boiling point of less than 175 ° C. such as butyl acetate and butyl propionate, or a solvent thereof is used. The coupler of the present invention alone or in combination with other types of couplers is dissolved in a mixed solution of two or more kinds, and then the mixture is mixed with an aqueous gelatin solution containing a surfactant, and then, a high-speed rotary mixer or a colloid mill. After being emulsified with, the emulsion can be added to silver halide to prepare a silver halide emulsion used in the present invention.

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

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

Silver halide emulsions are known in the photographic art as antifoggants or stabilizers for the purpose of preventing fog during production, storage or photographic processing of light-sensitive materials and / or keeping photographic performance stable. A compound can be added.

In the color light-sensitive material using the coupler of the present invention, a color antifoggant, a dye image stabilizer, an anti-UV agent, an antistatic agent, a matting agent, a surfactant and the like which are commonly used in light-sensitive materials can be used. .

Regarding these additives, for example, the description in Research Disclosure Volume 176, pages 22 to 31 (December 1978) can be referred to.

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

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

After the fixing treatment, a washing treatment is usually performed, and a stabilizing treatment may be performed instead of the washing treatment, or both may be used in combination.

[Examples] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 The following layers were sequentially coated on a paper support laminated on both sides with polyethylene from the support side to prepare a comparative sample 1 made of a red-sensitive color photosensitive material containing a comparative coupler a represented by the following structural formula. . In addition, in the following Examples, the amount of the compound added is per 1 m ^{2 of the} support (silver halide is a silver equivalent value) unless otherwise specified.

First layer: emulsion layer Red-sensitive emulsion layer consisting of 1.2 g of gelatin, 0.30 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% of silver chloride) and comparative cyan coupler 9.1 × 10 ^-4 mol dissolved in 0.25 g of dioctyl phthalate. .

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

Next, the comparative coupler a in the comparative sample 1 is first
Samples 1 to 14 of the present invention were prepared in exactly the same manner as above except that the coupler of the present invention shown in the table (the addition amount was the same molar amount as that of the comparative coupler a) was used.

Comparative sample 1 and invention sample 1 thus obtained
Each of Nos. 14 to 14 was subjected to wedge exposure according to a conventional method, and then subjected to development processing in the following steps.

(Development processing step) Color development 38 ° C 3 minutes 30 seconds Bleach fixing 38 ° C 1 minute 30 seconds Stabilization / or water washing treatment 25 ° C to 30 ° C 3 minutes Drying 75 ° C to 80 ° C 2 minutes Used in each processing step The composition of the treatment liquid is as follows.

(Color developer composition) Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4- Amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Set to 1 and adjust to pH 10.20.

(Bleaching fixer composition) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60
g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1.

(Stabilizing solution composition) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g Water is added to bring the total amount to 1.

The spectral absorption maximum wavelength (λ _max ) and the λ _{max of} the dye image generated in each sample processed as described above.
On the longer wavelength side, the reflection density becomes 0.5, and λ _max
Measure the difference in wavelength between the point on the shorter wavelength side where the reflection density is 0.5, that is, the half width (W 1/2),
Thereby, the spectral absorption characteristics and color reproducibility of each coupler were evaluated. The smaller the value of W 1/2, the sharper the spectral absorption waveform, and the better the color reproducibility of the coupler.

Furthermore, each of the above-mentioned processed samples is subjected to high temperature and high humidity (60 ° C, 80% R
H) The sample was left in an atmosphere for 14 days, and the heat and moisture resistance of each dye image was evaluated by the density of the dye measured after the dye was left, expressed as a percentage of the initial density.

The results obtained are shown in Table 1.

A KD-7 densitometer (manufactured by Konica Corporation) was used for the above measurement.

From the results shown in Table 1, in each of Samples 1 to 14 of the present invention, the half width which is significantly smaller than that of Comparative Sample 1,
Therefore, since the dye image having excellent spectral absorption characteristics is obtained and the dye residual ratio is high, all the couplers of the present invention used in Samples 1 to 14 of the present invention are comparative couplers a.
It can be seen that a robust dye image having excellent color reproducibility and excellent heat and humidity resistance is produced.

Example 2 A comparative sample 2 and a sample of the present invention, which are red-sensitive color reversal photographic light-sensitive materials containing the couplers shown in Table 2 in which the following layers are sequentially coated on a triacetyl cellulose film support from the support side. 15-21 were produced.

First layer: Emulsion layer Second layer dissolved in 1.4 g of gelatin, 0.5 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% of silver chloride) and 1.5 g of dibutyl phthalate.
Red-sensitive emulsion layer consisting of 9.1 × 10 ^-4 mol of coupler shown in the table.

Second layer: protective layer, protective layer containing 0.5 g of gelatin, 2,4-dichloro-6
-Hydroxy-s-triazine sodium salt with gelatin
0.017 g was added per 1 g.

Each sample thus obtained was subjected to wedge exposure according to a conventional method, and then developed in the next step.

[Reversal process] Process Time Temperature First development 6 minutes 38 ℃ Water wash 2〃〃 Reversal 2〃 〃 Color development 6〃〃 Adjust 2〃 〃 Bleach 6〃〃 Water wash 4〃 〃 stability 1〃 〃 dry dry normal temperature treatment liquid composition is as follows.

[First developer composition] Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Bromide Potassium 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water to make 1.

[Reversal liquid composition] Nitrilotrimethylenephosphonic acid-6 sodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 5 g Glacial acetic acid 15 ml Add water to make 1.

[Color developer composition] Sodium tetrapolyphosphate 2 g Sodium sulfite 7 g p-Aminophenol 0.1 g Sodium triphosphate (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g Ethylenediamine 3 g Water is added to make 1.

[Adjustment liquid composition] Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml l Add water to make 1.

[Bleaching solution composition] Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ethylenediaminetetraacetate ammonium iron (III) (dihydrate) 120 g Potassium bromide 100 g Water is added to make 1.

[Fixer composition] Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water is added to make 1.

[Stable solution composition] Formalin (37% by weight) 5 ml Conidax (manufactured by Konica Corporation) 5 ml Add water to make 1.

For each of the samples thus treated, the λ _max , half-value width and dye residual ratio of the dye image were obtained in the same manner as in Example 1.
The results are shown in Table 2.

However, in this example, the transmission density of the dye image was measured using the KD-7R densitometer.

From the results shown in Table 2, also in the invention samples 15 to 21, a significantly smaller full width at half maximum and a higher dye residual ratio were obtained as compared with the comparative sample, and therefore, the couplers of the invention used in the invention samples 15 to 21 were obtained. It can be seen that each of them produces a solid dye image which is superior to the comparative coupler a in spectral absorption characteristics and is also excellent in heat resistance and manifestation resistance.

[Effects of the Invention] As is clear from the above description, according to the present invention,
Provided is a cyan coupler for color photography, which is capable of forming a robust dye image having excellent heat resistance and moisture resistance as well as spectral absorption characteristics.

Claims (1)

[Claims] 1. A pyrazolo- [1 ', 5': 3,2] having at least one electron-withdrawing substituent other than a carboxyl group and a halogen atom at a substitutable position excluding the active site.
-Quinazolone color cyan coupler for color photography.