JPS63177135A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the formalin and light resistances of a dye image by incorporating a magenta coupler obtd. by substituting a specified substituent at the 6-position of a magenta coupler of 1H-pyrazolo[5,1-c]-1,2,4-triazole type into at least one of silver halide emulsion layers. CONSTITUTION:A magenta coupler obtd. by substituting a substituent represented by formula I at the 6-position of a magenta coupler of 1H- pyrazolo[5,1-c]-1,2,4-triazole type is incorporated into at least one of silver halide emulsion layers formed on a supporting body. In the formula I, each of Y1 and Y2 may be the same or different and is H atom, alkyl or cycloalkyl group but both of Y1 and Y2 are not H atom simultaneously and Y1 and Y2 may bond to each other together with N atom to form a 5- or 6-membered hetero ring. Thus, the light and formalin resistances of a magenta dye image are remarkably improved and high color developability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a halogenated magenta coupler-containing magenta dye image that is highly chromogenic and has improved storage stability, particularly light fastness and formalin fastness. The present invention relates to silver photographic materials, and more particularly to silver halide color photographic materials containing a novel magenta coupler.

[Background of the Invention] Pyrazolone type couplers have been used in practice to form magenta dyes, but they have unfavorable side absorption and have poor storage stability, especially resistance to formalin gas (formalin resistance). ).

In order to improve the above problems, various 1H-pyrazolo[5,1-e]-1,2,4-triazole magenta couplers have been proposed. For example, U.S. Patent No. 3,725,067, British Patent No. 1,252,41
No. 8 and No. 1,334,515.

The compounds described in both patents are, of course, superior to pyrazolone magenta couplers in terms of side absorption, but the improvement in formalin resistance is insufficient, and little improvement has been made in terms of color development and image light resistance. . Research Disclosure
ure) The compound described in No. 12443 cannot be put to practical use at all in terms of color development. 1H-pyrazolo[5,1-c]-1,2,4-) described in JP-A-58-42045
Although lyazole type magenta couplers have been significantly improved in terms of formalin resistance and color development, there has been little improvement in light resistance.

Although the couplers described in JP-A No. 59-99437 and JP-A No. 59-125732 have been improved in color forming properties, there is still no improvement in the light resistance of dye images based on the described couplers.

In the technique described in JP-A-59-125732, the light resistance of images is simply improved by the additives used in combination. However, although the light resistance of the coupler of Compound Example 19 described in the specification of JP-A No. 59-99437 has been slightly improved, it is still not sufficient.

In other words, 1H-pyrazolo[5], which has attracted attention for its lack of side absorption and high formalin resistance,
.

Therefore, the present inventors discovered that 1H-pyrazolo[5,1-C]-
As a result of intensive research into the light resistance of 1,2,4-triazole magenta couplers, it was discovered that those having a certain type of substitution at the 6-position have good light resistance.

Therefore, the present invention has been made based on this knowledge.

[Object of the invention] The object of the present invention is to have no side absorption, good formalin resistance,
Moreover, it is an object of the present invention to provide a silver halide color photographic material which has high color development and excellent light resistance.

[Structure of the Invention] The object of the present invention is to provide at least one silver halide emulsion layer on a support, in which 1H-pyrazolo[5,1-c] is present in at least one silver halide emulsion layer. −
This is achieved by a silver halide photographic material containing a magenta coupler in which the 6-position of a 1,2,4-triazole type magenta coupler is substituted with a substituent represented by the following general formula [1].

General formula [I] In the formula, Y and Yl may be the same or different and each represents a hydrogen atom, an alkyl group, or a cycloalkyl group, and Yl and Yl are not both hydrogen atoms. . In addition, Yl and Y are bonded to each other and together with the nitrogen atom, 5
or 6-membered heterocycle.

1H-pyrazolo[5,1-c]-1,2, of the present invention
The 4-triazole type magenta coupler has the following general formula % Formula % General formula [II] In the general formula [II ], Y1 and Yl are the general formula [
I], and R1 represents a hydrogen atom or a substituent.

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized color developing agent.

The alkyl groups represented by Yl and Yl in the general formula [I] include alkyl groups having 1 to 20 carbon atoms (methyl, ethyl, propyl, i-propyl, butyl, i-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl group, etc.)
As the cycloalkyl group, a cyclopentyl group or a cyclohexyl group can be mentioned.

Yl and Yl combine with each other to form 5 with nitrogen atoms
Examples of the membered or 6-membered heterocyclic group include the following.

The alkyl group, cycloalkyl group, and heterocyclic group represented by Y1 and Y2 may further have a substituent,
Substituents include halogen atoms (fluorine, chlorine, bromine atoms, etc.), alkyl groups having 1 to 20 carbon atoms (methyl, ethyl, propyl, butyl, hexyl, octyl, decyl,
dodecyl, pentadecyl, octadecyl, eicosyl groups, etc.), aryl groups (phenyl, naphthyl groups, etc.), alkoxy groups (methoxy, ethoxy, butoxy, octyloxy, dodecyloxy groups, etc.), aryloxy groups (phenoxy, 2,4-di -t-amylphenoxy, 4-(4-
(dodecylphenylsulfonyl) phenoxy, naphthoxy groups, etc.), alkylthio groups (methylthio, ethylthio, butylthio groups, etc.), arylthio groups (phenylthio, naphthylthio groups, etc.), alkylcarbonyl groups (acetyl,
propionyl, butyryl groups, etc.), arylcarbonyl groups (benzoyl, 4-methoxybenzoyl groups, etc.), alkylsulfonamide groups (methanesulfonamide, butanesulfonamide groups, etc.), arylsulfonamide groups (benzenesulfonamide, p-tolylsulfone amide group, etc.)
, arylsulfinyl group (ethylsulfamoyl, dimethylsulfamoyl group, etc.), arylsulfamoyl group (phenylsulfmonyl group, etc.), acylamino group (
acetamide, hexaneamide, benzamide groups, etc.),
Alkylcarbamoyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylcarbonyloxy group, arylcarbonyloxy group, hydroxyl group, carboxyl group, amino group or substituted amino group, nitro group, Examples include a cyano group and a heterocyclic group.

The substituent represented by R is not particularly limited, but specifically includes a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, and a sulfonyl group. , sulfinyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, Sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group,
Examples include aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

More detailed examples of the above groups include Japanese Patent Application No. 1983-
Specification No. 113371, page 7, line 13 to page 19, line 3
The groups explained in line 1 can be mentioned.

Groups that can be separated by a coupling reaction with the oxidized color developing agent represented by X include halogen atoms (for example, fluorine, chlorine, bromine atoms, etc.), amino groups, substituted amino groups (
For example, acylamino, diacylamino, alkylamino, arylamino groups, etc.), azo groups, aryloxy groups (
For example, phenoxy, p-methoxyphenoxy, p-butanesulfonamidophenoxy, p-carboxyphenoxy, etc.), alkoxy groups (such as methoxy, ethoxy,
2-methoxyethoxy group, etc.), arylthio group (e.g., phenylthio, p-carboxyphenylthio group, etc.), alkylthio group (e.g., methylthio, 2-hydroxyethylthio group, etc.), heterocyclic thio group (e.g., 1-ethyltetrazole-5), -thioyl, 2-pyridylthio, etc.), heterocyclic groups (e.g. 1-pyrazolyl, 1-imidazolyl, 2.
(5-pyrazolinedione-1-yl group, etc.), a carboxy group, a sulfo group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, and the like.

Among the groups represented by X, halogen atoms are preferred, and chlorine atoms are particularly preferred.

Next, specific examples of the magenta coupler represented by the above general formula [11] are shown below, but the present invention is not limited thereto.

Below margin 'I'' -11- h---= × ω ω
cJ (J ro)
To + +
＋ ＋VX
ω = e
w u-h -enemy -c-× Q
ω ω
QW Magenta couplers according to the present invention can be synthesized using various synthetic methods, such as U.S. Pat. No. 3,725,067, Re5search
It can be synthesized by referring to the method described in Disclosure No. 12443 and the like.

A specific synthesis example is shown below.

Synthesis example (synthesis of exemplary coupler (2)) The reaction scheme is as follows.

(I) (II) (C2H5)JCOCHCCR)CO2C2H5H3 (Ill) (IV) II(3 (V) ■ (Vl) Product (Exemplary coupler (2)) Synthesis of intermediate (I) 1-Pendylidenethiocarbono 19.4 g of hydrazide and 35.3 g of 4-dodecylsulfonyl-2-methyl-butanoic acid chloride were added to 300 mj of ethyl acetate, and 15.0 g of triethylamine was added dropwise. After heating under reflux for 2 hours, triethylamine hydrochloride was removed by filtration while hot. Ta.

The furnace liquid was cooled, and the precipitated crystals were collected in the furnace and further recrystallized from ethanol to obtain 43.4 g of Intermediate (1).

Synthesis of Intermediate (1) 20.4 g of the above intermediate (1) and 6.6 g of 50% hydroxylamine aqueous solution were added to 400 mj of ethanol and heated under reflux for 2 hours. The reaction solution was cooled, and the precipitated crystals were collected in an oven. 12.2 g of intermediate (II) was obtained.

Synthesis of intermediate (III) 10.1 g of the above intermediate (II) and ethyl-2-chloro-
5.5 g of 2-(N,N-diethylaminocarbonyl)acetate and 3.0 g of triethylamine were added to 10 hj of acetonitrile, and the mixture was heated under reflux for 3 hours. Triethylamine hydrochloride was removed by passing through a hot furnace, the mother liquor was concentrated under reduced pressure, and then recrystallized from ethanol to obtain intermediate (III) 11.
．． 8g was obtained.

Synthesis of intermediate (IV) 11.5 g of the above intermediate and 3.1 g of phosphorus oxychloride were added to 80 ml of toluene, and 0.1 mj+ dimethylformamide was added. After heating under reflux for 4 hours, the solvent was distilled off under reduced pressure. did. 80 ml of ethanol and 5 g of triethylamine were added to the residue, and the mixture was further heated under reflux for 2 hours. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 7.8 g of candy-like intermediate (IV) (ethyl acetate-hexane mixed solvent).

Synthesis of Intermediate (V) 7.5 g of the above intermediate (■) was heated under reflux in 20 mJ of dodecane for 4 hours under a nitrogen atmosphere. After removing insoluble matter by hot filtration, the mixture was cooled. The precipitated solid was separated in a furnace and recrystallized from acetonitrile to obtain 4.6 g of intermediate (V).

Synthesis of intermediate (Vl) 4.4 g of the above intermediate (V) was mixed with 25 ml of acetic acid and 12 ml of sulfuric acid.
1! and 1.2 ml of water, and the mixture was heated under reflux for 1 hour. After pouring 50 mj of water into the reaction solution, it was neutralized with a 4N aqueous sodium hydroxide solution. Then ethyl acetate 2
The intermediate (V
l) 3.8 g was obtained.

Other 1H-pyrazolo[5,1-c]-1,2,4-
The triazole nucleus itself was synthesized in accordance with the above synthesis example. Introduction of X other than a chlorine atom can be carried out by various methods, for example, with reference to the synthesis examples described in Japanese Patent Publication No. 46-43947, Japanese Patent Application Laid-open No. 59-99437, and Japanese Patent Application Laid-open No. 60-140241.

The amount of the magenta coupler according to the present invention added to the color photographic light-sensitive material according to the present invention is 1.5 X per mole of silver.
A range of 10-' to 7.5 x 10-' moles is preferred, more preferably I x 10-2 to 5 x to-'
It is in the molar range.

The color photographic material of the present invention includes, for example, color negative and positive films, and color photographic paper.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of a multicolor silver halide photographic light-sensitive material, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually formed on a support in an appropriate number of layers. Although it has a structure in which the layers are stacked in the order of layers, the number of layers and the order of the layers may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used.

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 photographic light-sensitive material of the present invention, color antifoggants, dye image stabilizers, ultraviolet light inhibitors, antistatic agents, matting agents, surfactants, etc. which are commonly used in light-sensitive materials can be used.

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

The color photographic material according to the present invention may contain a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath.

After color development, the color photographic material of the present invention is subjected to bleaching and fixing. 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 Magenta coupler (1) according to the present invention as shown in Table 1
) , (2) , (4) , (9) , (15
) , (28) , (31) and comparative couplers 1 to 3 described below in an amount of 0.1 mol per mol of silver,
Tricresyl phosphate in an amount of one time the coupler weight and ethyl acetate in an amount three times the weight of the coupler were added and heated to 60° C. to completely dissolve. This solution was mixed with 120ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
5% gelatin aqueous solution containing j! mixed with
The mixture was emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion.

Next, this dispersion was added to 4 kg of green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol) was added as a hardening agent. = 1~1) 12hj! was added, coated on the subbed transparent polyester base, dried, and prepared as samples 1-1 to 1.
-10 was produced. (Coated silver amount 20mg 7100cm2
).

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. The specific sensitivity, formalin resistance, and light resistance of each sample will be described later l) to 3).
The maximum concentration was measured as follows.

(Development process) Color developer 38℃ 3 minutes 15 seconds Bleaching
Liquid 38℃ 4 minutes 20 seconds Water
Washing 38℃ 3 minutes 15 seconds Fixing solution 38℃ 4 minutes 20
Wash with water for 38℃ Stable for 3 minutes and 15 seconds Liquid 38℃
Dry for 1 minute 30 seconds 47℃±5.5℃ 16 minutes 3
The composition of the treatment liquid used in each treatment step is as follows.

(Color developer composition) Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 5 g Sodium bromide 1.3 g Potassium iodide
2 mg hydroxylamine m
Acid salt 2.5g Sodium chloride 0.6g Sodium diethylenetotriminepentaacetate
2.5g4-amino-3-methyl-N-ethyl-N-(
β-hydroxyethyl)aniline sulfate
4.8g potassium hydroxide
Add 1.2 g of water and adjust to pH 10.06 using potassium hydroxide or 20% sulfuric acid.

(Bleach solution composition) Ethylenediaminetetraacetic acid iron ammonium salt
100 g ethylenediaminetetraacetic acid
10 g ammonium bromide 15
0g glacial acetic acid 40m! Add sodium bromate to 1 ft with 10K water and make p with aqueous ammonia or glacial acetic acid.
Adjust to H3.5.

(Fixer composition) Ammonium thiosulfate 180 g Anhydrous sodium sulfite 12 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetic acid o, s
g Sodium carbonate 10 g Add water to make one sentence.

(Stabilizing liquid composition) Formalin (37% aqueous solution) 2tal
! Konidax (manufactured by Konishiroku Photo Industry) 5vaR
Add water to make 11.

The measurement results are shown in Table 1. From Table 1, samples using the coupler according to the present invention not only have high color development (that is, high specific sensitivity and maximum density comparable to conventional ones), but also formalin resistance, and have even better light resistance. I understand.

Umbrella l Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1, and sample No. using comparative coupler (1),
1-1 was set as 100.

*6m of 0.9% formalin aqueous solution, temperature and humidity controlled to 230℃ and 62%RH! 2. Add 3 samples to a sealed container.
After a day of exposure, color development is performed. For comparison, samples not treated with formalin are also developed. In addition, formalin resistance was calculated|required according to the following formula.

Formalin resistance = Medium 3 The sample after color development treatment was irradiated with a xenon fade meter for 5 days, and the dye residual percentage was shown at an initial density of 0.1.

1.0 Comparative coupler 1 Compound described in JP-A-46-43974) Comparative coupler 2 Compound described in JP-A-59-125732) Comparative coupler 3 Compound described in JP-A-60-65245) Example-2 In Example-1 Samples 1-1 to 1-1O were used as Example-1
Wedge exposure was performed in the same manner as above, and the following development processing was performed. These results are shown in Table 2. Note that the specific sensitivity and light resistance were measured by the same method as in Example-1.

(Development processing process) Color development 38°C 3 minutes 30 seconds Bleach fixing 33°C 1 minute 30 seconds Stabilization treatment/or washing treatment 25-30°C drying for 3 minutes
75-80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) Benzyl alcohol 15 mj)
Ethylene glycol 15 mA'
Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPP
S) 2.5g 3-methyl-4
-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.5gFluorescent brightener (4,4°-diaminostyl
1.0g benzisulfonic acid derivative) Potassium hydroxide 2.0g Water is added to bring the total amount to tjZ, and the pH is adjusted to 10.20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 80 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100 mf Ammonium sulfite (40%!?) 27.5 mA + pH 7.1 with potassium carbonate or glacial acetic acid and add water to make the total volume IJ2.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g As is clear from the results in Table 2, Samples 2-4 to 3 containing couplers according to the present invention 2-10 has excellent color development (i.e., high specific sensitivity,
It can be seen that the maximum density is comparable to that of conventional products) and that it has excellent light resistance.

Table 2 Example 3 A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on polyethylene resin-coated paper containing anatase-type titanium oxide.

The amounts added below are per 100 cm2.

(1) Blue containing 20 mg of gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion, and 3 mg of dioctyl phthalate in which 8 mg of yellow coupler and 0.1a+H of 2.5-di-t-octylhydroquinone were dissolved. Sensitive emulsion layer.

(2) 12B gelatin, 0.5 mg 2.5-di-
Interlayer containing 21 g of dibutyl phthalate dissolved in t-octylhydroquinone and 4B UV absorber.

(3) 1g of 18I gelatin, 4mg of silver as green-sensitive silver chlorobromide emulsion, 2.5mg of dioctyl in which 5o+H magenta coupler and 0.2mg of 2,5-di-t-octylhydroquinone were dissolved. Green-sensitive emulsion layer containing phthalates.

(4) An intermediate layer containing the same composition as (2).

(5) 16 mg of gelatin, 4 mg of silver as a red-sensitive silver chlorobromide emulsion, and 2.0 mg of trichloride in which 3.5 mg of cyan coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Red-sensitive emulsion layer containing cresyl phosphate.

(6) Gelatin protective layer containing 9 mg gelatin.

Coating aids are added to each layer (1) to (6), and (
A hardener was added to layers 4) and (6).

As the ultraviolet absorbers (2) and (4), a mixture of UV-1 and UV-2 having the structures described below was used.

The above multilayer photosensitive material was treated in the same manner as in Example-2. The coupler is yellow coupler (Y-1).

Y-2), cyan coupler (c-1-c-4), and magenta coupler (1), (2) according to the present invention,
Comparative coupler 1 used in (3) and Example-1 was used. The composition of the sample and the test results are shown in Table 3.

Each sample was measured for magenta density after white exposure.

Further, measurements of specific sensitivity, maximum density, and light resistance were carried out in the same manner as in Example-1.

From Table 3, it is clear that the couplers according to the present invention have excellent light fastness of dye images, and it is also clear that the light fastness of dye images can be further improved by using an ultraviolet absorber.

The following margins include UV absorber UV-1 IV-2 Y coupler Ci! P C coupler and I! [Effects of the Invention] As described above, the silver halide photographic material using the magenta coupler of the present invention has significantly improved light fastness and formalin resistance of magenta images, and has high color development.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Miki Nakajima Eloquent buried earth Kuramochi
Written amendment (spontaneous) June 16, 1988 Commissioner of the Patent Office Black 1) Mr. Yu Aki 1, Indication of the case 1988 Patent Application No. 8109 2, Name of the invention Silver halide photographic light-sensitive material 3, Amendment Relationship with the case of a person who does Column 7, Contents of amendment 1) In the table on page 13 of the specification, R1 is listed for coupler (11).

2) In the table on page 15, in coupler (35), “
"correct.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains 1H-pyrazolo[5,1
-c] - A silver halide photographic light-sensitive material characterized by containing a magenta coupler in which the 6th position of the -1,2,4-triazole type magenta coupler is substituted with a substituent represented by the following general formula [I] . General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Both Y_2 are not hydrogen atoms. Also, Y_1 and Y_2 may be bonded to each other to form a 5- or 6-membered heterocycle with a nitrogen atom.)