JPH0784348A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To provide silver halide color photosensitive material excellent in sharpness and improved in preservation stability by containing a specific compound in at least one photo-forming layer. CONSTITUTION:In silver halide color photographic material having at least one silver halide emulsion layer on base material, at least one photo-forming layer contains at least one compound expressed by a formula so as to desorb a development restrainer by the reaction to the oxidant of a developing agent. In the formula, R1, R2 represent hydrogen atoms or substituents, and R1 and R2, may be mutually condensed to form a ring. DI represents a restrainer group, TIME represents a timing group, and (n) represents 0, 1 or 2. As silver halide emulsion used for this photographic material, optional one of normal silver halide emulsion can be used, and this emulsion can be chemically sensitized by a normal method and optically sensitized into a desired wavelength area using sensitizing pigments.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having improved sharpness and storage stability.

[0002]

2. Description of the Related Art In recent years, it has been strongly desired to develop a color photographic light-sensitive material having high sensitivity, sharpness and color reproducibility.

As a means for improving the sharpness, it is known to use a compound (hereinafter referred to as DIR coupler) which reacts with an oxidant of a color developing agent to release a development inhibitor.

It is also well known that by incorporating the compound in a silver halide emulsion layer, the color reproduction is improved by the IIE effect. However, when these DIR couplers are used, the development inhibitor, which is released during color development, diffuses and accumulates in the processing solution from the light-sensitive material, and as a result, the processing solution exhibits a development-inhibiting effect, and in the method of running processing of the light-sensitive material. There is a defect that it is difficult to always obtain a constant gradation.

JP-A-57-151944, 58-205150, 60
-218644, 60-221750, 61-11743 and U.S. patents
No. 4,782,012 proposes a method for solving such a problem.

These are DIR couplers having a group at the coupling position which has a property of decomposing into a compound that does not affect the photographic characteristics after the compound having the development inhibiting property separated from the coupling position flows out into the processing solution. Is.

With these DIR couplers, it is certain that even when a large amount of light-sensitive material was subjected to running processing, the decrease in sensitivity was small, and the contamination of the color developing solution due to the accumulation of development inhibitors was considerably reduced. is there.

However, the light-sensitive materials containing these DIR couplers have insufficient sharpness, and there is a drawback that fog is increased or sensitivity is lowered particularly during aging storage at high temperature. In addition, the multi-layer effect is insufficient as the performance of the DIR coupler itself, and the γ of the emulsion layer containing the coupler is
It cannot be said that the level has reached a satisfactory level such as a decrease in.

[0009]

As described above, by using the known DIR coupler, the sharpness is good, and the sensitivity does not decrease and the fog does not increase even if the DIR coupler is stored at a high temperature over time. At present, no silver halide color photographic light-sensitive material has been obtained.

Therefore, the object of the present invention is to provide good sharpness,
It is intended to provide a silver halide color photographic light-sensitive material having improved storage stability.

[0011]

As a result of intensive studies, the inventors of the present invention have found that the object of the present invention can be achieved by the following, and have accomplished the present invention.

That is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one photographic constituent layer is represented by the following general formula [I]. It was achieved by a silver halide color photographic light-sensitive material characterized by containing at least one compound capable of leaving a development inhibitor upon reaction with an oxidized product of a developing agent.

[0013]

[Chemical 2]

In the formula, R ₁ and R ₂ represent a hydrogen atom or a substituent, and R ₁ and R ₂ may be condensed with each other to form a ring. DI represents an inhibitor group, TIME represents a timing group, and n represents 0, 1 or 2.

The present invention will be specifically described below.

The substituent represented by R ₁ and R ₂ in the general formula [I] is not particularly limited, but typical examples thereof include alkyl, aryl, alkenyl and cycloalkyl groups. In addition, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, aryloxycarbonylamino, alkoxycarbonyl,
Each group such as aryloxycarbonyl, carboxy and sulfonic acid, as well as a spiro compound residue, a bridged hydrocarbon compound residue and the like can be mentioned.

Of the substituents represented by R ₁ and R ₂ , the alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 carbon atoms.
The alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred. Alkylsulfonyl group, arylsulfonyl group, etc. as sulfonyl group; alkylsulfinyl group, arylsulfinyl group, etc. as sulfinyl group; alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group as phosphonyl group Etc .; as the acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .;
The carbamoyl group is preferably an alkylcarbamoyl group, an arylcarbonyl group, or the like; the sulfamoyl group is an alkylsulfamoyl group, an arylsulfamoyl group, or the like; the heterocyclic group is preferably a 5- to 7-membered group, and specifically,
2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group and the like;
Spiro [3,3] heptan-1-yl etc. are used as spiro compound residues; 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-
Ill and the like.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

The timing group represented by TIME is based on the intramolecular nucleophilic substitution reaction disclosed in US Pat. No. 4,248,962 and JP-A-57-56837, and JP-A-56-11494.
No. 6, JP-A-57-154234, and the like, which release a development inhibitor by an electron transfer reaction along a conjugated chain, can be cited. In addition, JP-A-57-188035 and 58-
98728, 59-206834, 60-7429, 60-214358
No. 50, No. 50-225844, No. 60-229030, No. 60-233649,
The linking groups disclosed in Nos. 60-237446 and 60-237447 are also included.

The TIME useful in the present invention includes, but is not limited to, those represented by the following general formulas [II], [III] and [IV].

[0023]

[Chemical 3]

In the formula, Q represents an atomic group necessary for completing a benzene ring or a naphthalene ring which may be a substituent. Y is -O -, - S -, - N (R 23) - represents, is bound to the coupling position of the pyrazolidinedione residues in the general formula [I], R _21, R ₂₂ and R ₂₃ Is a hydrogen atom,
Represents an alkyl group or an aryl group. Also, −C (R ₂₁ ) (R
_{The 22} )-group is substituted in the ortho or para position relative to Y and is bonded to the sulfur atom of the development inhibitor group.

[0025]

[Chemical 4]

In the formula, Y, R ₂₁ and R ₂₂ are each represented by the general formula [II].
R ₂₁ and R ₂₂ have the same meaning. R ₂₄ is, for example, a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group or a heterocyclic residue, and R ₂₅ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, An amino group, an acid amide group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group are shown. Further, this timing group is represented by the general formula [I
As in I], Y is bonded to the coupling position of the pyrazolidinedione residue in the general formula [I] with -C
(R ₂₁ ) (R ₂₂ ) — is bonded to the sulfur atom of the development inhibitor group.

Next, an example of a timing group that releases a development inhibitor group by an intramolecular nucleophilic substitution reaction is shown by the general formula [IV].

Formula [IV] -Nu-BE-In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and is pyrazolidine in the formula [I]. It is attached to the coupling position of the dione residue. E
Is an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group or thiophosphinyl group, and is bonded to the sulfur atom of the development inhibitor group.
B is sterically related to Nu and E, and in the general formula [I], after the release of Nu from the pyrazolidinedione residue, intramolecular nucleophilic nucleophilic formation involving formation of a 3- to 7-membered ring. A linking group capable of undergoing a reaction and thereby releasing a development inhibitor.

The group represented by DI in the general formula [I] is a group exhibiting a development inhibitory action, and is preferably a mercaptotetrazole, a selenotetrazole, a mercaptotriazole, a mercaptothiadiazole, a mercaptooxadiazole, a mercapto. It represents imidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptobenzthiazoles, triazoles, benztriazoles and tetrazoles.
Particularly preferred are mercaptothiadiazoles, mercaptotriazoles, mercaptotetrazoles and mercaptobenzthiazoles.

Specific examples of the compound according to the present invention are shown below, but the invention is not limited thereto.

Exemplified Compound

[0032]

[Chemical 5]

[0033]

[Chemical 6]

[0034]

[Chemical 7]

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

Synthetic Examples The compounds of the present invention can be prepared by known methods in the organic synthetic art. A specific synthesis example is shown below.

Synthesis of Exemplified Compound 13

[0044]

[Chemical 15]

(I) Synthesis of intermediate (3) 12.0 g of intermediate (2) and 18.8 g of dicyclohexylcarbodiimide (DCC) were dissolved in 200 ml of tetrahydrofuran, and intermediate (1) was added little by little under ice cooling, followed by ice cooling. Stirred below for 1 hour. The reaction solution was filtered to remove solids, and the filtrate was concentrated under reduced pressure to leave an oily substance (intermediate (3)).

(Ii) Synthesis of Exemplified Compound 13 The obtained oily product (intermediate (3)) was treated with 150 m of acetonitrile.
Dissolve in l, triethylamine 7g, intermediate (4) 16.
5 g was added and stirred at room temperature for 4 hours. The reaction solution is ethyl acetate 350
It was dissolved in ml, 1% hydrochloric acid was added to adjust the pH to about 3, and the layers were separated.
The ethyl acetate layer was further washed with water, and the solvent was distilled off under reduced pressure. The obtained oily substance was separated and purified by silica gel column chromatography to obtain 10.7 g of Exemplified Compound 13. The structure was confirmed by nuclear magnetic resonance spectrum, mass spectrum and infrared absorption spectrum.

The other exemplified compounds can be synthesized by the same method.

The DIR coupler according to the present invention is a photographic material containing
It can be contained in any layer, for example, a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer, but it is preferably used in the silver halide emulsion layer. More preferably, it is used for a red-sensitive silver halide emulsion layer and / or a blue-sensitive silver halide emulsion layer.

In order to incorporate the DIR coupler of the present invention into the hydrophilic colloid layer of a color light-sensitive material, for example, a known high-boiling solvent such as dibutyl phthalate, tricresyl phosphate, dinonylphenol and butyl acetate, propionic acid, etc. The DIR coupler according to the present invention is dissolved in a mixed solution with a low boiling point solvent such as the above, alone or in combination, and then mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotary mixer or a colloid mill. Alternatively, it may be emulsified and dispersed by using an ultrasonic disperser and then added directly into the emulsion, or after the above emulsified dispersion is set, it may be shredded and washed with water and then added to the emulsion.

The amount of the DIR coupler used in the present invention is preferably 0.005 to 10 mol% per mol of silver halide,
More preferably, it is in the range of 0.01 to 5 mol%.

The DIR couplers according to the present invention may be used alone or in combination of two or more.

As the silver halide emulsion used in the light-sensitive material of the present invention, any of ordinary silver halide emulsions can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Further, by coupling with a colored coupler having a color correcting effect, a competing coupler and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener and a hardener. Compounds that release photographically useful fragments can be used, such as film agents, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development process may be contained.

Matting agents, lubricants, image stabilizers, surfactants, anti-foggants, development accelerators, development retarders and bleaching accelerators can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image by using the light-sensitive material of the present invention, a commonly known color photographic process can be carried out after exposure.

[0061]

EXAMPLES The present invention will now be specifically described with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 The amounts of various additives added to the silver halide color photographic light-sensitive material are shown in mol per mol of silver unless otherwise specified.

Samples of a multilayer color photographic light-sensitive material were prepared by sequentially coating each layer having the following composition from the support side on a triacetyl cellulose film support.

First Layer: Antihalation Layer (HC) A gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL) Monodisperse emulsion consisting of AgBrI containing 0.30 μm average grain size and 6.0 mol% AgI (Emulsion 1) ... Silver coating amount 1.8 g / m ² Sensitizing dye I 6 × 10 ⁻⁵ Sensitizing dye II 1.0 × 10 ⁻⁵ Cyan coupler (C-1) 0.06 Colored cyan coupler (CC-1) 0.003 DIR compound (D-1) 0.0035 DIR compound (D-2 ) 0.002 Layer 4: High-sensitivity red-sensitive silver halide emulsion layer (RH) Monodisperse emulsion consisting of AgBrI containing 0.5 μm average grain size and 7.0 mol% AgI (Emulsion II) ... Silver coating amount 1.3 g / m ² Sensitizing dye I 3 × 10 ^-5 Sensitizing dye II 1.0 × 10 ^-5 Cyan coupler (C-1) 0.02 Colored cyan coupler (CC-1) 0.0015 DIR compound (D-1) 0.001 Fifth layer: intermediate layer ( IL) A gelatin layer having the same composition as the second layer.

Sixth layer: Low-sensitivity green-sensitive silver halide emulsion layer (GL) (Emulsion I) ... Silver coating amount 1.5 g / m ² Sensitizing dye III 2.5 × 10 ^-5 Sensitizing dye IV 1.2 × 10 ^-5 Magenta coupler (M-1) 0.050 Colored magenta coupler (CM-1) 0.009 DIR compound (D-1) 0.0010 DIR compound (D-3) 0.0030 7th layer: high-sensitivity green-sensitive silver halide emulsion layer (GH) ( Emulsion II) Silver coating amount 1.4 g / m ² Sensitizing dye III 1.5 × 10 ^-5 Sensitizing dye IV 1.0 × 10 ^-5 Magenta coupler (M-1) 0.020 Colored magenta coupler (CM-1) 0.002 DIR compound ( D-3) 0.0010 Eighth layer: Yellow filter layer (YC) Gelatin layer containing yellow colloidal silver and emulsified dispersion of 2,5-di-t-octylhydroquinone Ninth layer: Low-sensitivity blue-sensitive silver halide emulsion Layer (BL) Monodisperse milk consisting of AgBrI containing 0.48 μm average particle size and 6 mol% AgI Agent (Emulsion III) ... Silver coating amount 0.9 g / m ² Sensitizing dye V 1.3 × 10 ^-5 Yellow coupler (Y-1) 0.29 10th layer: High-sensitivity blue-sensitive emulsion layer (BH) Average particle size 0.8 μm, Monodisperse emulsion consisting of AgBrI containing 15 mol% AgI (Emulsion IV) ... Silver coating amount 0.5 g / m ² Sensitizing dye V 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.08 DIR compound (D-2) 0.0015 11th layer: First protective layer (Pro-1) Silver iodobromide (AgI 1 mol%, average particle size 0.7 μm) ... Silver coating amount 0.5 g / m ² UV absorber UV-1, UV-2 (1: 1 ) Containing a gelatin layer.

Twelfth layer: Second protective layer (Pro-2) A gelatin layer containing polymethylmethacrylate particles (average particle size: 1.5 μm) and formalin scavenger (hydantoin).

In addition to the above components, a gelatin hardening agent (sodium salt of 2,4-dichloro-6-hydroxy-s-triazine) and a surfactant were added to each layer.

Further, Sample 2 to Sample 7 were prepared in the same manner as Sample 1 except that the DIR compound (D-1) contained in the third and fourth layers of Sample 1 was changed to the DIR compound shown in Table 1. did.

The compounds contained in each layer of each sample are as follows.

Sensitizing Dye I: Anhydro-5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II: Anhydro-9-ethyl-3,3'-di- (3-sulfopropyl) -4,5, 4 ', 5'-Dibenzothiacarbocyanine hydroxide Sensitizing dye III: Anhydro-5,5'-diphenyl-9-ethyl-
3,3′-Di- (3-sulfopropyl) -oxacarbocyanine hydroxide Sensitizing dye IV: Anhydro-9-ethyl-3,3′-di- (3-sulfopropyl) -5,6,5 ′ , 6'-Dibenzooxacarbocyanine hydroxide Sensitizing dye V: Anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxythiacyanine hydroxide

[0073]

[Chemical 16]

[0074]

[Chemical 17]

[0075]

[Chemical 18]

[0076]

[Chemical 19]

Samples 1 to 7 obtained in this way were partially for 7 days at 55 ° C. and 20% RH (referred to as 55 ° C. treatment),
After storing each for 7 days under normal indoor conditions,
After wedge exposure using white light, the following development processing was performed.

[0078] The composition of the processing liquid used in each processing step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous carbonic acid Calcium 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter and adjust to pH 10.20 with potassium hydroxide or 20% sulfuric acid.

[Bleach] Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water is added to make 1 liter and pH is adjusted to 6.0 using aqueous ammonia.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter and pH was adjusted to 6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica) 7.5 ml Water is added to make 1 liter.

The sensitivity and fog of the red photosensitive layer of each of the developed samples were measured using an optical densitometer PDA-65 (manufactured by Konica Corporation). In addition, the image sharpness was also measured. The sharpness was determined by determining the MTF of the dye image and showing the relative value of the MTF at 30 lines / mm. Table 1 shows specific sensitivity, fog, and sharpness.

[0084]

[Table 1]

The specific sensitivities in Table 1 are the relative values of the reciprocal of the exposure amount that gives the fog density + 0.10 density, and are shown as values with sample 1 being 100.

From Table 1, Samples 3 to 12 containing the DIR coupler of the present invention have significantly improved sharpness as compared with Comparative Samples 1 and 2 and have low fog generation during storage. It is clear that the decrease in sensitivity is small.

Even when the sample according to the present invention was subjected to a running development treatment, the sensitivity was hardly decreased.

Example 2 A basic sample was prepared by applying a multilayer coating on the triacetate base in the following order.

(1) C-2 0.5 as a cyan coupler
g, 2.4 g of gelatin and 1.6 g of silver halide, a red-sensitive silver iodobromide emulsion layer.

(2) A gelatin intermediate layer containing 0.5 g of gelatin and 0.1 g of 2,5-di-t-octylhydroquinone.

(3) Y-1 1.7 as a yellow coupler
Blue-sensitive silver iodobromide emulsion layer containing 0 g, gelatin 2.4 g, and silver halide 1.6 g.

(4) A protective layer consisting of 0.8 g of gelatin.

Of the constituent layers of the multilayer coating light-sensitive material described above, the following DIR coupler D is contained in the third layer containing a yellow coupler.
-5, D-6 and the DIR coupler according to the present invention were added according to the addition amount as shown in Table 2 to prepare eight kinds of materials 13 to 20.

Each sample was divided into two, one sample was subjected to wedge exposure with white light, and the other sample was subjected to wedge exposure with red light.

Then, the same treatment as in Example 1 was performed.

For each sample, the gamma value was obtained from the characteristic curve of the cyan dye image obtained by color development, and the value obtained by dividing the gamma by the red exposure (γ _R ) by the gamma by the white exposure (γ _W ) is shown in Table 2. Show.

[0097]

[Table 2]

As is clear from Table 2, Samples 15 to 20 containing the DIR coupler of the present invention have a larger γ _R / γ _W value than Comparative Samples 13 and 14 and exhibit an excellent layering effect. I understand.

[0099]

By using the novel DIR coupler of the present invention, a silver halide color photographic light-sensitive material having good sharpness and excellent storage stability can be provided.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one photographic constituent layer is represented by the following general formula [I]: A silver halide color photographic light-sensitive material comprising at least one compound capable of leaving a development inhibitor upon reaction with an oxidized product of a developing agent. [Chemical 1] [Wherein R ₁ and R ₂ represent a hydrogen atom or a substituent,
₁ and R ₂ may be condensed with each other to form a ring. DI represents an inhibitor group, TIME represents a timing group, n is 0,
Represents 1 or 2. ]