JPH0362030A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material giving an image having low fog density and high max. density by incorporating at least one kind of specified coupler. CONSTITUTION:At least one kind of coupler represented by formula I (where Z is a group of atoms required to form a 6-membered hetero ring, Y is aryl, alkyl or a heterocyclic group and Cp is a residue of a coupler) is incorporated. The amt. of the coupler added is preferably 10-300g per 1mol silver halide but may be properly changed as required. Two or more kinds of couplers may be used in combination and the coupler may be combined with other kinds of coupler forming an image having the same hue. A silver halide photographic sensitive material giving an image having low fog density and high max. density can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material that provides images with low fog density and high maximum density.

[Prior Art] Various studies have been conducted to obtain high-density images. For example, efforts have been made to increase the coupling speed of couplers and to search for couplers that provide dyes with high ε (molecular extinction coefficient). Research has also begun on couplers designed so that the "off group" (sometimes referred to as "off group") functions as a dye.

There are reports about it, for example, in US Patent No. 4.248.96.
No. 2, JP-A-61-184541, JP-A-1-134
It is described in No. 454, etc.

These coupling-off groups are bound directly or indirectly to the active site of the coupler in the form of a blocked auxochrome, and when the auxochrome is unblocked during coupling-off, thereby Functions as a dye with sufficient wavelength.

As mentioned above, such couplers block the auxochrome, so they shift the spectral absorption wavelength that the dye originally has to the shorter wavelength side, so that no color develops in the areas that are not developed, that is, the unexposed areas. Designed. however,
These conventional couplers suffer from fog11 in unexposed areas.
There were still many problems left unsolved.

[Problems to be solved by the invention] The present invention has been made to solve the above problems,
An object of the present invention is to provide a silver halide photographic light-sensitive material that provides images with a low fog of 11 degrees and a high fog of up to 81 degrees.

[Means for Solving the Problems J] The present invention is achieved by a silver halide photographic material containing at least one kind of coupler represented by the following general formula [I].

General formula [I] (wherein, Z represents an atomic group necessary to form a 6-membered heterocycle, and Y represents an aryl group, an alkyl group, or a heterocyclic group;
[Represents a group. Cp represents a coupler residue. 〉 Below, the present invention! ! I will explain in detail.

The silver halide photographic material of the present invention has the following general formula [I
] Contains at least one coupler represented by the following.

A group of atoms necessary to form the general formula [I]. For example, it may consist only of carbon chains, or it may contain a nitrogen atom. The heterocycle may further have a substituent, and the substituents may bond to each other to form a condensed ring.

Examples of this substituent include a halogen atom, an alkoxy group, an alkyl group, an alkylthio group, an aminocarbonyl group,
Preferred examples include alkoxycarbonyl groups, such as aryl groups such as phenyl groups, and cyano groups.

Y represents an aryl group such as a phenyl group or a naphthyl group, or an alkyl group such as a hetero group such as thiophene.

These groups include alkyl groups (e.g. methyl, ethyl, propyl, n-butyl, t-butyl, tetradecyl, etc.), halogen atoms, nitro groups, carbamyl groups, acylamino groups, and sulfonamino groups as substituents. , a sulfamyl group, a sulfo group, a carboxyl group, a cyano group, an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), an acyl group, a sulfonyl group, a hydroxy group, an aryloxy group, an alkoxycarbonyl group, etc. Further, Cp represents a coupler residue, and preferable coupler residues include cyan coupler residues such as phenol type and naphthol type, magenta coupler residues such as pyrazolone type and pyrazolotriazole type, benzoylacetanilide type, bivallylacetanilide type, etc. Examples include yellow coupler residues and coupler residues that do not form a color M image.

Next, specific examples of couplers used in the present invention are shown, The present invention is not limited to these.

Exemplary compound () to l(s 14 Next, a synthesis example of the nJ coupler included in the present invention will be shown.

Synthesis Example: Synthesis of Exemplified Compound 4 (1) (2)
Then, 2.8o of raw material compound (1) was added and heated to reflux. After 1 hour, the solvent was distilled off and the intermediate compound (
A white powder of 2) was obtained.

(4) Raw material compound (3) 5g of 300i12 chloroform 5.1 g of 8rz was added dropwise at room temperature.

After reacting with v'fA for 4 hours, the reaction solution was washed with water, the chloroform layer was dried over magnesium sulfate, and the solvent was distilled off. The obtained curved residue was mixed with hexane:ethyl acetate (9:
A rib-like intermediate compound (4) was obtained by column chromatography using the developing solvent of 1).

3゜(5) Intermediate compound < 4) 11.9 (7 and Intermediate compound (2) 4.10 were dissolved in ahitonitrile 250112 and heated to reflux. After 2o1, the precipitated KBr was filtered. After separation, the solvent was distilled off and the residue was separated into toluene:ethyl acetate (
The curved compound 8.2 of intermediate compound (5) was purified by column chromatography using a developing solvent of 7:3).
I got g.

(6) (7) (8) Intermediate compound <5) s, og to ethyl acetate 1501
Dissolved in p, palladium/carbon Dk'A 0.51
J was added and hydrogen gas was introduced for reduction. After the reaction, the catalyst was filtered off and the solvent was distilled off. The obtained (6) was immediately dissolved in 100 d of acetone, and then dissolved in 25 n/ml of water.
With l? 2.5 t of 11MA acid, 12 was added, and the mixture was cooled to -5°C. To this solution, 21,0 liter of NaNO dissolved in 151 g of water was added dropwise.Stirred for 30 minutes under cooling, and then the intermediate compound was added. (7) was obtained.

To a solution of raw material compound (8) 3.5(+ dissolved in pyridine 501Q and cooled to below 0°C, a solution of intermediate compound (7) dissolved in acetone was added dropwise with stirring. Dropwise. After the completion of the reaction, stirring was continued for an additional hour, and then the reaction solution was diluted with 5,001 l of water, extracted with ethyl acetate, washed with water, and dried. The solid obtained by distilling off the solvent was diluted with hexane:acetone. By column chromatography using a developing solvent of (4:1), 11! of the target compound, Exemplary Compound 4, was separated.

Intermediate compounds (4) and (5) and the final target compound, Exemplified Compound 4, were all confirmed by NMR and MaSS spectra.

In the silver halide photographic light-sensitive material of the present invention, the coupler used in the present invention is contained in an amount of 10 to 10% per mole of silver halide.
It is preferable to add 300 (J), but it can be changed as necessary.

The couplers related to the present invention can be used in combination of two or more types, and can also be used in combination with other types of couplers that can form images of the same hue.

The coupler of the present invention can be added to a silver halide photographic material using various methods such as a solid dispersion method, a latex dispersion method, and an in-water & I+ FF4 emulsion dispersion method. For example, in the emulsion dispersion method of 1 d 1 drop in water, a hydrophobic additive such as a coupler is usually added to a high-boiling Ishibashi solvent with a boiling point of about 150°C or higher, such as tricresyl phosphate or dibutyl phthalate, and ethyl acetate, propionate, etc. as necessary. Dissolve it in combination with a low boiling point and/or water-soluble organic solvent such as butyl acid, emulsify and disperse it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then add it to the desired hydrophilic colloid layer. do it. The hydrophilic colloid used in the present invention includes a binder, but other hydrophilic colloids can also be used.

When the silver halide photographic light-sensitive material of the present invention is used for natural color photography, a green-sensitive photographic material containing a magenta coupler, a cyan coupler, and a yellow coupler, respectively, as photographic colors for subtractive color reproduction; It has a structure in which red-sensitive and blue-sensitive emulsion layers and non-light-sensitive layers are layered on a support in an appropriate number and order of layers, but the number and order of layers may be changed as appropriate depending on the purpose of use. You can.

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

Silver halide emulsions are chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, negative metal sensitization, or the like. Further, optical sensitization can be performed to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

The silver halide photographic material of the present invention includes a color antifoggant, a hardening agent, a plasticizer, a polymer latex, an ultraviolet absorber, an antioxidant, an antifading agent, a formalin bender, a mordant, a development accelerator, Development retardants, optical brighteners, matting agents, lubricants, antistatic agents, surfactants, and the like can be optionally used.

The support used in the silver halide photographic material of the present invention may be appropriately selected from paper, glass, cellulose acetate, polyester, polyamide, borisdylene, etc. depending on the purpose.

In the present invention, any treatment used in the art can be performed, such as color development treatment, bleaching, fixing, bleach-fixing, stabilization, washing with water, and stopping. However, when the silver halide photographic light-sensitive material of the present invention is used as a color material, it is preferable to use a developer containing a required amount of an aromatic primary amine as a developing agent.

The silver halide photographic material of the present invention can be used, for example, as a color negative, positive or reversal film [Example] Yellow coupler (Y-1) 6! A mixed solution in which 3 g of tricresyl phosphate and 18 g of ethyl acetate were added to I+ was heated to 60°C to dissolve it, and then mixed with 5% aqueous solution of Alkanol B (manufactured by DuPont) containing 10- % geladine aqueous solution and emulsified and dispersed using an ultrasonic disperser to prepare a dispersion liquid.

Next, the dispersion was mixed into a silver iodobromide emulsion (containing 6 mol% silver iodide) so that the yellow coupler was 10 mol% based on silver.
After adding 1°2-bis(vinylsulfonyl)ethane as a hardening agent at a ratio of 1211 (+) per gram of gelatin, the amount of silver coated on a subbed transparent cellulose triacetate film support was is 181!II/100Cf
Sample 1 was prepared by coating the sample to give the following properties.

Next, Samples 2 to 6 were prepared in the same manner as Sample 1 except that the yellow coupler (Y-1) was replaced with an equimolar coupler as shown in Table 1.

Samples 1 to 6 were each subjected to wedge exposure and then processed according to the processing steps shown below.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds constant n
Stabilization for 6 minutes and 30 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer J 4-amino-3-methyl-N=ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75Q pyrohydrous sodium sulfite 4.259 hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.59 Sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0 (7 Add water to make 1i, use potassium hydroxide to make pi-110
, adjust to 0.

[Bleach solution]

Ethylenediaminetetraacetic acid iron (III) ammonium salt ioo a ethylenediaminetetraacetic acid 2 ammonium salt 1o, og ammonium bromide 150.0 (1 ice vinegar R
10,0n12 Add water to make 12, and use ammonia water to make 9 mouths 6.0
Adjust to.

[Fixer] Ammonium acetate (50% aqueous solution) 1621
1 Add 12.4 g of anhydrous sodium sulfite to bring the volume to 111, and adjust to 6.5 with acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution> 1.5d Konidax (manufactured by Konica Corporation) γ, 51 (add water to make 1j2).

The R height of the thus obtained yellow dye image is 8ia! I
.

and the blue density of the unexposed area was measured. Table 1 shows the results.
Shown below.

Table 1 (Compounds described in U.S. Pat. No. 4,248,962) (Compounds described in JP-A-61-184541) As is clear from Table 1, although the compounds of the present invention were found at high concentrations, An excellent image with little coloring in unexposed areas was obtained.

Further, a sample was prepared in the same manner as in sample 1 except that the yellow coupler in sample 1 was replaced with exemplified compound 16.17, and the same treatment and evaluation were performed, and the effects of the present invention were obtained.

[Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material that provides images with low fog density and high maximum density.

Claims (1)

[Scope of Claims] A silver halide photographic material containing at least one kind of coupler represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. (Cp represents a coupler residue.)