JPH01271751A - Silver halide color photographic sensitive material containing novel photographic coupler - Google Patents

Abstract

PURPOSE:To improve the anti-fading and the heat- and moisture-resisting proper ties of the title material, and to make it possible to form a color image having excellent durability by incorporating a specified photographic coupler in the photosensitive material. CONSTITUTION:The photographic coupler shown by formula I is incorporated in the photosensitive material. In formula I, R1-R4 and Y are each hydrogen atom or a substituting group, X is a group capable of being released by allowing it to react with the oxidant of a color developing main agent. And the novel photographic coupler shown by formula I is composed of 4,7-dihydropyrazolo(1,5- a)pyrimidine derivative, and the substituting group of the coupler is exemplified by alkyl or aryl group, etc. Thus, the anti-fading and the heat and moisture- resisting properties of the photosensitive material are improved, and the color image having the excellent durability can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material containing a novel photographic coupler. This invention relates to silver chemical color photographic materials.

[Background of the Invention] When a silver halide photographic light-sensitive material is subjected to color development treatment after imagewise exposure, an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye. An image is formed.

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

Examples of couplers used to form the above-mentioned yellow image include acylacetanilide couplers, and examples of couplers for forming magenta images include pyrazolone couplers, and further known couplers for forming cyan images. As the coupler, for example, a phenol or naphthol coupler is generally used.

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

However, although dyes formed from 5-pyrazolone couplers, which have been widely used and studied as macenta color image forming couplers, have excellent fastness to heat and light, they suffer from unwanted absorption with yellow components. This presence caused color turbidity. As a means to solve this problem, couplers such as pyrazolobenzimidazole, 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, these couplers have the disadvantage that their fastness to light is extremely low, causing discoloration and fading.

On the other hand, phenolic couplers, which are being researched as couplers for forming cyan dyes, have been improved in their 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 silver halide color photographic light-sensitive material containing a novel photographic coupler and used as a color photographic material.

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

[Structure of the invention]

The above objects of the present invention have been achieved by a silver halide color photographic light-sensitive material containing a photographic coupler represented by - machining allowance (1).

General formula [I] [wherein R,, R2, R,, R4 and Y represent hydrogen atoms or substituents, and X represents a group that reacts with and leaves the oxidized form of the color developing agent. ] Hereinafter, the present invention will be explained in detail.

The novel photographic coupler represented by the general formula [I] used in the present invention is 4,7-cyhydropyrazolo (1,
5-a) It is a pyrimidine derivative.

The compound represented by the general formula (1) used in the present invention will be explained in detail.

R1, R2, R3, and R4 in general formula (1) represent a hydrogen atom or a substituent, and examples of the substituent include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. Each prefecture is listed, but in addition to these, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, sulfonyloxy, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy , carbamoyloxy, amine, alkylamino, imide, ureido, sulf7moylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, as well as spiro compound residues, bridged hydrocarbons Also included are compound residues and groups such as thioureido, carboxy, hydroxy, mercapto, nitro, and sulfo.

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, arylthio, etc. 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.; bosbonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and aryl groups. Phosphonyl 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; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group ring; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, 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 ring; 1-tetrazolyl group, ■
-pyrrolyl group, etc.; as a heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, for example, 3,4,5.6-
Tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-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-hendithiazoli group, etc. ruthio group, 2,4-diphenoxy-1゜3.5-1-riazole-6 monothio group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glucurimide group, etc.; as a spiro compound residue, spiro(3,3)heptane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2゜2.1
] Hebutan-1-yl, tricyclo(3,3,L137
] Decane-1-yl, 7,7(2,2,1)hebutan-1-yl, and the like.

- In the removal allowance (1), R1 is preferably any of the above-mentioned substituents, R2 is particularly preferably an alkyl group, alkoxyalkyl group, or aryloxyalkyl group, and R3 is particularly preferably an alkoxycarbonyl group or an aryloxycarbonyl group. R4 is preferably an aryl group or a heterocyclic group.

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

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
carboxyl, [R3', R2', R3', R, I and Y' have the same meanings as the above R1, R2, R3, R4 and Y, and Ra and Rb are hydrogen atoms, aryl groups, alkyl groups or heterocycles; represents a group. ], preferably a halogen atom, especially a chlorine atom.

Y in the general formula CI) 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 the oxidized developing agent. For example, the substituent represented by Y may be a group that can be separated under alkaline conditions as described in JP-A-61-228444, or a group that can be separated under alkaline conditions, as described in JP-A-61-133734.
Examples include substituents that are eliminated by reaction with the oxidized developing agent, as described in No. 1, etc. Preferably Y is a hydrogen atom.

Next, a synthesis example of the compound represented by the general formula (1) will be shown.

Synthesis Example 1 3.05 g of methyl 4-(2-(phthalimido)ethoxy-3-oxobutyrate, 1.3 g of 2-cyanohenzaldehyde and 10 m of ethanol were dissolved, and 1 drop each of acetic acid and piperidine were added. , and heated under reflux for 4 hours.The solvent was distilled off, and 3-amino-4-bromopyrazole 1 was added to the residue.
．． Add 65 g and 5 ml of dimethylborumamide,
Heated at 100°C for 5 hours. The solvent was distilled off, the residue was purified by silica gel column chromatography, and recrystallized from methanol to give methyl-3-bromo-7-(2
-cyanophenyl)-512-(phthalimido)ethoxymethyl)-4,7-cyhydropyrazolo(1,5-a)
1.57 g of pyrimidine-6-carboxylate was obtained, which was dissolved in 20 ml of tetrahydrofuran and 1.5 ml of water was obtained.
Add 3ml of potassium hydroxide and 0.34g of potassium hydroxide, and stir at room temperature.
Stir for hours. Next, 13 mk of 2N hydrochloric acid was added, and the mixture was heated under reflux for 3 hours. After cooling, the mixture was neutralized with potassium carbonate and extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, ethanol-hydrochloric acid was added, and the precipitated crystals were collected by filtration. This was recrystallized from ethanol and methyl-5-(2-
aminoethoxymethyl)-3-bromo-7-(2-cyanophenyl L4,7-dihydrosylate (1-a) 0.
7 g (0,0015 mol) were obtained.

Elemental analysis calculated value C50゜01 H4,20N16.20 Actual value C50,97H4,09N16.15 (1-a
) A solution of 0.49 g of hexadecanesulfonyl chloride in ethyl acetate 5 in 20 d of 0.70 g of ethyl acetate solution.
mfl was added, and further 0.4 g of triethylamine was added, and the mixture was stirred at room temperature for 2 hours, and the precipitated crystals were collected by filtration. This was washed with water and further recrystallized with acetonitrile to obtain 0.80 g of white needle crystals of Compound 1.

Elemental analysis calculated value C56,66H6,99N9.72 actual value
C57,02H6,85N9.78 Synthesis Example 2 3.6 g of isopropyl 4-C2-Cphthalimido)ethoxy]-3-oxoacetate and 1.5 g of 2-fluorohenzaldehyde were dissolved in Hensen 200d, and acetic acid and piperidine were dissolved. Add 1 drop of each and Dean-Stark
A trap was attached and the mixture was refluxed for 3 hours while removing water. The solvent was distilled off, and the residue contained 1.1 3-aminopyrazole.
g and 10 ml of dimethylformamide, and heated to 100°C.
It was heated for 4 hours. The solvent was distilled off and the residue was purified by silica gel column chromatography to obtain oily isopropyl 5-(2-(phthalimido)ethoxymethyl)-7.
-(2-fluorophenyl)-4,7-cyhydropyrazolo[1,5-a)pyrimidine-6-carboxylate 3
I got g.

[Thin layer chromatography: Rf=0.61 (Merck ART'5715, chloroform:acetonitrile-9
:1)) Obtained isopropyl 5-(2-(phthalimido)ethoxymethyl)-7-(2-fluorophenyl)-4,7
-Cihydropyrazolo[C5-a) 0.33 g of pyrimidine-6-carboxylate was dissolved in 30 m2 of methanol, and 440 μ of hydrazine hydrate was obtained! was added and heated at 50°C for 6 hours. The solvent was distilled off, and the residue was purified by silica gel column chromatography and crystallized from ethyl acetate to give isopropyl 5-(2-aminoethyl-xymethyl).
0.2 g of -7-(2-fluorophenyl)-4,7-cihydropyrazolo[1°5-a]pyrimidine-6-carboxylate (2-a) was obtained.

Melting point: 117-119°C, mass spectrum 2m/Z3
74, Thin layer chromatography: Rf = 0.2 (Merck ART5715, chloroborum:methanol-8:2) Same as Synthesis Example 1 using 0.2 g of (2-a) and 018 g of p-dodecanphenyloxymethyl carbonyl chloride The reaction and treatment were carried out to obtain 0.28 g of white needle-like crystals of Compound 3.

Elemental analysis calculation direct C69,211-T 7.8 9
N 8.2 8 Actual measurement C69,93N7.78
N8.21 Next, examples of compounds represented by -Noshiro N) will be shown, but the present invention is not limited thereto.

H A coupler represented by the general formula CI) used in the present invention (
Hereinafter, it will also be referred to as a coupler used in the present invention. ) can be synthesized with reference to the synthesis example described above.

The coupler used in the present invention is usually one halogenated coupler, one coupler, and one halogenated coupler.
1 x 10-3 mol to 1 mol per mole, preferably 1 x 1
It can be used in the range of 0-2 mol-8X10-' mol. Moreover, the coupler used in the present invention can be used in combination with other types of couplers.

The methods and techniques used for conventional dye-forming couplers are similarly applicable to the couplers used in the present invention.

The coupler used in the present invention can be used as a material for forming color photographs using any coloring method, but
Specific examples include an external coloring method and an internal coloring method.

When used as an external color method, the coupler used in the present invention can be prepared in an alkaline aqueous solution or in a water-compatible organic solvent (
For example, it can be used by dissolving it in alcohol, etc.) and adding it to a developing solution. Further, when used as a material for forming a color photograph by an internal coloring method, the coupler used in the present invention is used by being incorporated into the photographic light-sensitive material. Typically, a method is preferably used in which the coupler used in 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 used in the present invention is used, for example, in color photographic materials such as color negative and positive films and color photographic paper.

The color photographic paper and other light-sensitive materials using couplers used in the present invention may be monochrome or multicolor.

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, 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, a yellow dye image-forming unit consisting of a blue-sensitive silver halide emulsion layer containing at least one yellow coupler, and a yellow dye image-forming unit consisting of a blue-sensitive silver halide emulsion layer are provided on a support. The photosensitive material may have additional layers such as a filter layer, an intermediate layer, a protective layer, an undercoat layer, etc.

In order to incorporate the coupler used in the present invention into an emulsion, a conventionally known method may be followed. For example, the temperature of tricresyl phosphate, dibutyl phthalate, etc. is 175°C.
After dissolving the coupler used in the present invention in the above-mentioned high-fluorescence point organic solvents or low-fluorescence point solvents such as butyl acetate and butyl propionate, either alone or in a mixture thereof as necessary. can be 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 prepare the silver halide emulsion used in the present invention.

Silver halide compositions preferably used in the light-sensitive material using the coupler used in the present invention include silver chloride, silver chlorobromide, and silver chloroiodobromide. 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 a chlorine atom, and at least 1% silver chloride. Silver chloride, silver chlorobromide or silver chloroiodobromide are particularly preferred.

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.

The color photosensitive material using the coupler used in the present invention includes color antifoggants, dye image stabilizers, ultraviolet inhibitors, antistatic agents, capping agents,
Surfactants and the like can be used.

Regarding these, for example, research, disclosure (Research Disclosure)
176, pages 22-31 (December 1978) can be referred to.

An image can be formed on the color photosensitive material using the coupler used in the present invention by subjecting it to a color development process known in the art.

The color light-sensitive material using the coupler used in the present invention contains a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and can be processed in an alkaline activation bath.

The color photosensitive material using the coupler used in 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 A red-sensitive color photosensitive material sample 1 was prepared by sequentially applying the following layers to a paper support laminated on both sides with polyethylene from the support side. In addition, in the following examples,
The amount of compound added is per 1M unless otherwise specified (
Silver halide is silver equivalent value).

1st layer: Emulsion layer 1.2 g of gelatin, 0.35 g of green-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) and 1.2 g of dioctyl chloride.
Comparative coupler a dissolved in 35 g 5.1 X10-
Red-sensitive emulsion layer consisting of 4 moles.

2nd layer: MW retention layer Protective layer containing 0.50 g of gelatin. As a hardening agent, 2,4-dichloro-6-hydroxy-5-) rearan 1-lium salt was added in an amount of 0.017 g per 1 g of gelatin.

Next, Samples 2 to 11 of the present invention were prepared in exactly the same manner except that comparative coupler a in Sample 1 was replaced with the coupler used in the present invention shown in Table 1 (the amount added was the same molar N as that of comparative coupler a). It was created.

Samples 1 to 11 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

(Development process) Color development Bleach fixing at 38°C for 3 minutes and 30 seconds
Stabilization treatment at 38°C for 1 minute and 30 seconds/Washing treatment at 25°C to 30°C for 3 minutes Drying at 75°C to 80°C2 The composition of the treatment liquid used in the pollution treatment step is as follows.

(Color developer) Benzyl alcohol 15ml1 Ethylene glycol 15ml! Potassium sulfite 2゜0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30.0 g hydroxylamine sulfur salt 3
．． 0 g Polyphosphoric acid (TPPS) 2.5
g3-Methyl-4-amino-N-ethyl-N-(β-
Methanesulfonamide ethyl) Aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilhenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water and see the entire view! and adjust the pH to 10.20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100mR Ammonium sulfite (40%
solution) with 27.5d potassium carbonate or glacial acetic acid
Adjust to H7.1 and add water to bring the total volume to IIV.

(Stabilizing liquid) 5-ri-4-2-methyl-4-isothiapurin-3-one 1.0 g Ethylene glycol 10 g Add water to make 1 p.

The concentrations of Samples 1 to 11 treated above were measured using a densitometer (model Kl-7R manufactured by Konica Corporation). Furthermore, each of the above-mentioned treated samples was heated at high temperature and high humidity (60°C, 180°C).
%RH) atmosphere for 20 days to improve the heat resistance and
We investigated moisture resistance. The results obtained are shown in Table 1. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining 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, and then the density was measured, and the light resistance of the dye image was examined from the dye residual rate after the light resistance test with respect to an initial density of 1.0.

Comparative coupler a Table 1 As can be seen from the results in Table 1, samples Nos. 2 to 10 using the coupler represented by - machining allowance [I] have better light resistance than sample No. 1■ using comparative coupler a. It has greatly improved properties and has excellent heat and humidity resistance, so a strong dye image can be formed.

〔Effect of the invention〕

The present invention makes it possible to obtain a silver halide color photographic material that forms a robust dye image with excellent light resistance and heat/humidity resistance by using the coupler represented by - machining allowance (1).

Applicant Konica Co., Ltd. Agent Patent Attorney Miki Nakajima 1 person

Claims (1)

[Claims] A silver halide color photographic material containing a coupler 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, R_4 and Y are
It represents a hydrogen atom or a substituent, and X represents a group that reacts with the oxidized product of the color developing agent and leaves it. ]