JPH09146234A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the sensitive material superior in color reproducibility and not exert adverse influence of a discharged inhibitor on processing liquid by incorporating at least one kind of specific compound. SOLUTION: This material contains at least one kind of compound shown by formula I or II. Formula I is Cp-(Time)n-DI-NR1 COOR2 . In the formula, Cp is a group which reacts on a developing base oxidant and discharges (Time) n-DI-NR1 COOR2 , 'Time' is a timing group, and (n) is 0, 1, or 2; when n=0, it means that DI is combined directly with Cp. Further, DI is a nitrogen containing heterocycle group or nitrogen containing heterocycle thio group, R1 is a substituent, R2 is an optional substituable alkyl group or aryl group. The formula II is Cp-(Time)n-DI-SCONR3 R4 . In the formula Cp, Time, (n), and DI are the same with the formula I and R3 and R4 are a hydrogen atom or optional substituable alkyl group or aryl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material, a light-sensitive material or a color light-sensitive material). The present invention relates to a light-sensitive material that does not adversely affect the liquid.

[0002]

2. Description of the Related Art In the field of silver halide color photographic light-sensitive materials, inhibitor releasing compounds (hereinafter referred to as DIR compounds) are widely used for the purpose of improving image quality such as color reproducibility, sharpness and graininess. When a DIR compound is used in a light-sensitive material, the released inhibitor accumulates in the processing solution, which causes a problem in the processing level. In order to solve this problem, for example, Japanese Patent Publication No. 63-27701 discloses a so-called inactivated DIR compound in which the released inhibitor reacts in the treatment liquid and does not exhibit the inhibitory effect. However, since the deactivation rate of these compounds is not appropriate, they have drawbacks such as insufficient deactivation, insufficient storage stability, and color turbidity. It wasn't done. On the other hand, the DIR compound is generally an oxidized product of a developing agent (hereinafter referred to as Q
It is desirable that the reaction with DI) be fast, and a compound having a naphthol mother nucleus is preferably used. However, since the naphthol-based compound develops a cyan color, it causes color turbidity when used in areas other than the red-sensitive layer, which is not preferable for color reproduction.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material which is excellent in color reproducibility and which does not adversely affect the processing liquid due to the released inhibitor.

[0004]

The above object of the present invention is achieved by the following constitution.

[0005] 1. A silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula (I) or (II).

General Formula (I) Cp- (Time) n-DI-NR ₁ COOR ₂ Cp: Reacts with an oxidized product of a developing agent to give (Time) n-DI
-NR ₁ COOR ₂ releasing group Time: Timing group n: 0, 1, 2. When n = 0, it means that DI is directly bonded to Cp. DI: Nitrogen-containing heterocyclic group or nitrogen-containing heterocyclic thio group R ₁ : Substituent R ₂ : Substituted or unsubstituted alkyl group or aryl group.

[0007] Formula (II) Cp- (Time) n -DI-SCONR 3 R 4 in formula Cp, Time, synonymous n, DI is the general formula (I).
R ₃ and R ₄ represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.

[0008] 2. 2. The silver halide color photographic light-sensitive material as described in 1 above, which contains at least one compound represented by the following general formula (III) or (IV).

[0009]

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In the formula, R ₅ represents a substituent and R ₆ represents a substituted or unsubstituted phenyl group. Time, n, DI, R ₁ ,
R ₂ , R ₃ and R ₄ have the same meanings as in the general formula (I) and general formula (II).

3. 3. The silver halide color photographic light-sensitive material as described in 1 or 2 above, wherein the compound represented by the general formula (III) or the general formula (IV) is contained in a blue-sensitive emulsion layer.

Hereinafter, the present invention will be described in detail.

Cp in the general formula (I) represents a group which releases (Time) n-DI- upon reaction with QDI,
Those by a coupling reaction and those by an oxidation-reduction reaction can be used. Examples of the one by a coupling reaction include compounds having an active methylene group such as acylacetanilides and pyrazolones, pyrazolotriazoles, phenols or naphthols. And so on. Examples of the redox reaction include hydroquinones. Preferred is a coupling reaction type, more preferred is pivaloyl acetanilide,
Examples thereof include acylacetanilides such as benzoylacetanilide and malondiamide.

As the Time in the general formula (I), it is possible to use one by intramolecular nucleophilicity or one by electron transfer. An example of the former is, for example, JP-A-57-56.
No. 837, and examples of the latter include those described in JP-A-56-114946. When n is 0, it means that DI is directly bonded to Cp.

DI in the general formula (I) represents a nitrogen-containing heterocyclic group or a nitrogen-containing heterocyclic thio group. Specific examples include triazoles, tetrazoles, mercaptotriazoles, mercaptotetrazoles, oxadiazoles,
Thiadiazoles, mercaptooxadiazoles, mercaptothiadiazoles and the like can be mentioned.

Examples of R ₁ in the general formula (I) include an alkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group. An alkyl group is preferred.

R ₂ in the general formula (I) represents a substituted or unsubstituted alkyl group or aryl group.

R ₃ and R ₄ in the general formula (II) each represent a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group.

R ₅ in the general formulas (III) and (IV) represents alkyl, aryl, arylamino, alkoxy or aryloxy, preferably tertiary alkyl, aryl,
Represents an arylamino group. Moreover, these may have a substituent. R ₆ represents a substituted or unsubstituted aryl group, preferably a substituted aryl group. Time, DI, n, R
₁ , R ₂ , R ₃ and R ₄ have the same meanings as in the general formula (I) and the general formula (II).

As the substituents in the above general formula (I), general formula (II), general formula (III) and general formula (IV), for example, the groups mentioned as examples of R ₁ in the general formula (I) can be mentioned. Can be mentioned.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the present invention is not limited to the following compounds.

[0022]

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[0023]

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[0024]

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[0025]

[Chemical 6]

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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Synthetic Examples Synthetic examples of representative compounds of the present invention are shown below. The method of synthesizing the exemplified compounds is as follows.

[0032]

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Synthesis of compound (4) 12.3 g of compound (1), 7.3 g of compound (2) and 10 g of triethylamine were added to compound (3) 9.9 in toluene.
The reaction with g gave 19.3 g of compound (4).

Synthesis of Exemplified Compound (II-19) 19.3 g of Compound (4) and 76.2 g of Compound (5) were heated and refluxed in ethyl acetate for 4 hours in the presence of pyridine to give Exemplified Compound (II-19). 85.0 g was obtained.

The compound of the present invention can be contained in any layer in the silver halide photographic material, for example, a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer.
It is preferably used for a silver halide emulsion layer. More preferably, or when used in a blue-sensitive silver halide emulsion layer.

In order to incorporate the compound 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 and dinonylphenol and butyl acetate, propionic acid and the like are used. The compound of the present invention is dissolved in a mixed solution with a low-boiling solvent as described above, either alone or in combination, and then dissolved with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotary mixer or a colloid mill or After emulsifying and dispersing using an ultrasonic disperser, directly added to the emulsion, or after setting the emulsified dispersion, after shredding and washing with water,
This may be added to the emulsion.

The amount of the compound of the present invention to be used is preferably 0.005 to 10 mol%, more preferably 0.01 to 5 mol%, per mol of silver halide.

The compound of the present invention may be used alone, or
Two or more kinds may be used in combination.

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 a binder for 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 compound is used in the emulsion layer of the color photographic light-sensitive material. Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, by coupling with a colored compound having a color correction effect, a competing compound and an oxidized product of a developing agent, Antifoggant, antifoggant,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

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 may be bleached or bleached from the light-sensitive material during development processing may be contained.

Matting agents, lubricants, image stabilizers, surfactants, color fog inhibitors, 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.

[0047]

EXAMPLES Specific examples of the present invention will be given below, but the present invention is not limited thereto.

The following multilayer samples were prepared.

(Multilayer Samples) In all the following examples, the addition amount in the silver halide color photographic light-sensitive material is per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver.

Example 1 A multilayer color light-sensitive material sample 1 (comparative sample) was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

First Layer: Antihalation Layer (HC) Gelatin (1.6) containing black colloidal silver (0.15 g).
g) Layer.

Second layer: intermediate layer (IL) 2,5-di-t-octylhydroquinone (0.12)
A gelatin (1.3 g) layer containing the emulsified dispersion of g).

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL) AgBr containing 0.30 μm average grain size and 6 mol% AgI.
Monodisperse emulsion consisting of I (emulsion I) 1.8 g Sensitizing dye I 6 × 10 ⁻⁵ mol / silver 1 mol Sensitizing dye II 1 × 10 ⁻⁵ mol / silver 1 mol Cyan compound (C-1) 06 mol / silver 1 mol Colored cyan coupler (CC-1) 0.003 mol / silver 1 mol DIR compound (D-4) 0.0035 mol / silver 1 mol Fourth layer: high-sensitivity red-sensitive silver halide emulsion layer (RH) AgB containing an average particle size of 0.5 μm and AgI of 7.0 mol%.
Monodisperse emulsion consisting of rI (emulsion II) 1.3 g Sensitizing dye I 3 × 10 ⁻⁵ mol / silver 1 mol Sensitizing dye II 1 × 10 ⁻⁵ mol / silver 1 mol Cyan coupler (C-1) 0.1. 02 mol / silver 1 mol Colored cyan coupler (CC-1) 0.0015 mol / silver 1 mol DIR compound (D-4) 0.001 mol / silver 1 mol Fifth layer: intermediate layer (IL) Second layer Same, gelatin layer.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion I 1.5 g Sensitizing dye III 2.5 × 10 ⁻⁵ mol / silver 1 mol Sensitizing dye IV 1.2 × 10 ^{− 5} mol / silver 1 mol Magenta coupler (M-1) 0.050 mol / silver 1 mol Colored magenta coupler (CM-1) 0.009 mol / silver 1 mol DIR compound (D-5) 0.0010 mol / silver 1 mol DIR compound (D-2) 0.0030 mol / silver 1 mol 7th layer: High-sensitivity green-sensitive silver halide emulsion layer (GH) Emulsion II 1.4 g Sensitizing dye III 1.5 × 10 ^-5 mol / Silver 1 mol Sensitizing dye IV 1.0 × 10 ^-5 mol / silver 1 mol Magenta coupler (M-1) 0.020 mol / silver 1 mol Colored magenta coupler (CM-1) 0.002 mol / silver 1 Mol DIR compound (D-2) 0.0010 mol / silver 1 mol Eighth Layer: Yellow filter layer (YC) A gelatin (1.0 g) layer containing yellow colloidal silver (0.1 g) and an emulsified dispersion of 2,5-di-t-octylhydroquinone (0.14 g).

Ninth layer: low-sensitivity blue-sensitive silver halide emulsion layer (BL) AgBr containing 0.48 μm average grain size and 6 mol% AgI.
Monodisperse Emulsion (Emulsion III) 0.9 g Sensitizing dye V 1.3 × 10 ⁻⁵ mol / silver 1 mol Yellow coupler (Y-1) 0.29 mol / silver 1 mol 10th layer: high sensitivity Blue-sensitive silver halide emulsion layer (BH) AgBr containing an average grain size of 0.8 μm and AgI of 15 mol%.
I Monodisperse emulsion (Emulsion IV) 0.5 g Sensitizing dye V 1 × 10 ⁻⁵ mol / silver 1 mol Yellow coupler (Y-1) 0.08 mol / silver 1 mol DIR compound (D-1) 0 .0015 mol / silver 1 mol 11th layer: First protective layer (Pro-1) Silver iodobromide (AgI 1 mol%, average particle size 0.07 μm) 0.3 g Ultraviolet absorber (UV-1) (0. 07g), (UV-
2) A gelatin (0.8 g) layer containing (0.1 g).

Twelfth layer: Second protective layer (Pro-2) Polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) (0.5)
A gelatin (0.5 g) layer containing g).

In addition to the above composition, a gelatin hardening agent (H-1) and a surfactant were added to each layer.

The compounds contained in each layer of the 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 (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

[0060]

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[0061]

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[0062]

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HS-1: Hydantoin H-1: 2,4-dichloro-6-hydroxy-s-triazine.sodium Samples 2 to 10 in which the compound D-1 in the 10th layer of the above sample was replaced with the compound shown below. It was created. The following treatments were performed on the samples that were subjected to white exposure and monochromatic separation exposure to these samples through a wedge.

[0064]

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Processing step (38 ° C.) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Each processing step The composition of the treatment liquid used in 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 Potassium 37.5 g Sodium bromide 1.3 g Nitriloacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and pH is adjusted to 10.0 using potassium hydroxide. adjust.

Bleaching solution Iron (III) diaminetetraacetate ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Water was added to make 1 liter, and pH was adjusted with ammonia water. Adjust to 6.0.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

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

Next, each sample was evaluated as follows. The results are shown below.

IIE: Gamma (γG) of the green-sensitive layer in the green separation exposure and gamma (γ) of the green-sensitive layer in the white exposure.
W) ratio (γG / γW), the larger this value, the greater IIE Color turbidity: Cyan color density difference (ΔDR) between the fog part and the maximum density part of blue separation exposure. The larger this value, the greater the color turbidity. Processing level fluctuation: 135 to 24 white-exposed samples were taken, and a running process equivalent to 200 shots was performed. The difference in sensitivity of the green layer between the top (new processing solution) and the tail (at equilibrium) (fog +0.2, Δ
log E). The smaller this value is, the more preferable.

IIE Color turbidity Treatment level fluctuation Sample No. Compound γW / γG ΔDR ΔlogE 1 D-1 (Comparative) 1.27 0.01 0.11 2 D-3 (Comparative) 1.22 0.07 0.03 3 D-4 (Comparative) 1. 08 0.07 0.09 4 I-1 (invention) 1.30 0.01 0.02 5 I-2 (invention) 1.28 0.00 0.02 6 I-5 (invention) 1 .29 0.01 0.01 7 I-8 (invention) 1.30 0.01 0.02 8 II-2 (invention) 1.27 0.00 0.01 9 II-5 (invention) 1.25 0.01 0.02 10 II-7 (Invention) 1.26 0.01 0.00 As is apparent from the above, according to the present invention, the photosensitivity which is excellent in color reproducibility and does not adversely affect the processing liquid. It turns out that we can provide the material.

[0073]

The light-sensitive material of the present invention has excellent color reproducibility and has an excellent effect that the released inhibitor does not adversely affect the processing solution.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula (I) or (II). General formula (I) Cp- (Time) n -DI-NR 1 COOR 2 Cp: reacts with oxidized developer, (Time) n-DI
A group that releases —NR ₁ COOR ₂ . Time: Timing base. n: 0, 1, 2. When n = 0, it means that DI is directly bonded to Cp. DI: nitrogen-containing heterocyclic group or nitrogen-containing heterocyclic thio group. R ₁ : Substituent R ₂ : A substituted or unsubstituted alkyl group or aryl group. Formula (II) Cp- (Time) in n-DI-SCONR ₃ R ₄ [wherein, Cp, Time, n, DI is synonymous with the general formula (I). R ₃ and R ₄ represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group. ] 2. The silver halide color photographic light-sensitive material according to claim 1, which contains at least one compound represented by the following general formula (III) or (IV). Embedded image [In the formula, R ₅ represents a substituent, and R ₆ represents a substituted or unsubstituted phenyl group. Time, n, DI, R ₁ , R ₂ , R ₃ ,
R ₄ has the same meaning as in the general formula (I) and the general formula (II). ] 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (III) or the general formula (IV) is contained in a blue-sensitive emulsion layer. material.