JPS6115423B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel coupler used in photographic technology, particularly a silver halide color photographic light-sensitive material containing a novel coupler used in photographic technology using silver halide as a light-sensitive component. More specifically, the present invention relates to a silver halide color photographic light-sensitive material (hereinafter referred to as "silver halide color photographic light-sensitive material") which has undergone internal color correction by incorporating a so-called colored coupler capable of correcting undesirable secondary absorption (particularly from 550 to 57 nm) of a cyan-forming coupler. (referred to as color photosensitive materials). The use of color-forming couplers that react with aromatic amine developing agents to form color photographic images is well known. The absorption spectra of conventional dyes formed by color-forming couplers are by no means simple; cyan dyes obtained from cyan-forming couplers always exhibit undesirable absorptions (secondary absorptions) in the short wavelength region (fringes and blue portion) of the spectrum. ). This secondary absorption is extremely problematic in terms of color reproduction. It is known that one effective method for correcting this undesirable secondary absorption is to mix colored couplers into color photosensitive materials. This colored coupler is required to have a maximum absorption wavelength region around 550 to 570 nm if undesirable secondary absorption in the cyan dye is to be corrected. This colored coupler is capable of reacting with the oxidized color developing agent during the color development processing step, yielding a useful cyan dye and, upon development, simultaneously increasing its absorption capacity in the 550-570 nm region of the spectrum. This compensates for the undesirable absorption of cyan dye derived from the primary cyan dye-forming coupler in the photographic material. (In addition,
As used herein, the term "undesirable absorption" refers to measurable absorption in the green and blue regions of the visible spectrum for cyan couplers. ) However, conventional colored couplers such as those described in British Patent No. 1446728, etc.
There are colored couplers that do not have a maximum absorption wavelength region in m, and such colored couplers have the disadvantage that color reproduction is inaccurate because the absorption wavelength does not match that of the cyan dye. On the other hand, even with conventional colored couplers that have a maximum absorption wavelength region of 550 to 570 nm, the coupling speed is slow, fogging occurs easily, or the absorption wavelength is affected by the high pH of the processing solution, especially the developer. It has the disadvantage that the area may fluctuate. For this reason, there is a strong desire for a colored coupler that has a maximum absorption wavelength region of 550 to 570 nm, has a fast coupling speed, does not cause fog, and whose absorption wavelength region does not change depending on the pH of the processing solution. The current situation is that A first object of the present invention is to provide a color photosensitive material using a colored coupler that solves the above-mentioned conventional problems at once and exhibits the above-mentioned desired effects. A second object of the present invention is to provide a color photosensitive material using a colored coupler that has a maximum absorption wavelength region of 550 to 570 nm, has an excellent absorption wavelength of a mask, and can obtain a dye image with high clarity. That's true. A third object of the present invention is to provide a color photosensitive material having high sensitivity, excellent light fastness and moisture resistance, and less fogging. A fourth object of the present invention is to provide a color photosensitive material which has excellent cyan coloring properties and whose absorption wavelength region (mask density) hardly changes depending on the pH of a processing solution such as a whitening solution. It is. The above objects of the present invention and other objects described below are achieved by a color photosensitive material containing a compound represented by the following general formula [] (hereinafter referred to as the colored coupler of the present invention). General formula [] In the formula, Cp is a residue of a naphthol-based cyan coupler excluding the hydrogen atom at the active site, R ₁ is a hydrogen atom, an alkyl group or acyl group having 1 to 4 carbon atoms, and R ₂ is a residue having 1 to 4 carbon atoms. 4 alkyl group or an alkenyl group having 2 to 4 carbon atoms. M ₁ and M ₂ are a hydrogen atom, an alkali metal or ammonium, X represents an alkylene group having 1 to 4 carbon atoms or an alkenylene group having 2 to 4 carbon atoms, and A represents the following structural formula. or

[Example coupler]

(1) 1-hydroxy-4{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)-phenoxyacetamide]anilinocarbonyloxy}-N-[δ −
(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide disodium salt (2) 1-hydroxy-4{3-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)-phenoxyacetamide]anilinocarbonyloxy}-N-[δ −
(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide disodium salt (3) 1-hydroxy-4{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)-phenoxyacetamide]benzylaminocarbonyloxy}-N-
{δ-(2,4-di-tert-amylphenoxy)
Butyl]-2-naphthamide disodium salt (4) 1-hydroxy-4[2-methoxy-5-
(1-Hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)-benzyl[aminocarbonyloxy]-N-{δ-(2,4
-di-tert-amylphenoxy)butyl]-2
−Naphthamide} disodium salt (5) 1-Hydroxy-4-{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxyacetamide]anilinocarbonyloxy}-n-dodecyl- 2-Naphthamide disodium salt (6) 1-hydroxy-4{2-methyl-4-[4
-(1-hydroxy-3,6-disulfo-8-
acetylamino-2-naphthylazo)phenoxyacetamide]anilinocarbonyloxy}
-N-(δ-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide disodium salt (7) 1-hydroxy-4{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxyacetamide]N-acetylanilinocarbonyloxy}
-2-Naphthanilide disodium salt (8) 1-hydroxy-4{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxyacetamide]phenethylaminocarbonyloxy}-N
-[δ-(2,4-c-tert-amylphenoxy)butyl]-2-naphthamide disodium salt (9) 1-hydroxy-4-{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxypropionylamide]anilinocarbonyloxy}-N-
[δ-(2,4-di-tert-amylphenoxy)
Butyl]-2-naphthamide disodium salt (10) 1-hydroxy-4-{4-[4-(1-hydroxy-3,6-disulfo-8-propionylamino-2-naphthylazo)phenoxyacetamide]anilinocarbonyloxy}-N-(2
-n-tetradecyloxyphenyl)-2-naphthamide disodium salt (11) 1-hydroxy-4-{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxyacetamide]anilinocarbonyloxy}-N-[δ −
(2,4-di-tert-amylphenoxy)butyl]-N-[δ-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide dipotassium salt The colored coupler of the present invention is a naphthol type coupler having a hydroxyl group at the 4-position of 1-naphthol (for example, 1,4-dihydroxy-2-naphthanilide, 2,4-di-tert-amylphenoxybutyl-1, 4-dihydroxy-2-naphthamide, 1,4-dihydroxy-2-tetradecyloxyphenyl-2-naphthamide, etc.) in a sufficiently dried appropriate solvent (e.g., toluene, xylene, dioxane, benzene, etc.). The corresponding 4-nitrophenylcarbonyloxy substituted product is obtained by boiling under reflux with an appropriate amount of nitrophenyl isocyanate. Next, this nitro form is reduced with zinc-hydrochloric acid or tin-hydrochloric acid, etc. to give an amino form, and the corresponding nitrophenoxyalkylcarboxylic acid is converted into an acyl form by a conventional method in the presence of N・N'-dicyclohexylcarbodiimide. The nitro compound is reduced again by the above-mentioned method to give an amino compound, which is diazotized with sodium nitrite and hydrochloric acid, and the N-acylated H acid is coupled with an alkali to synthesize the amino compound. Next, a typical synthesis example of the colored coupler of the present invention will be specifically explained. Synthesis Example 1 [Synthesis Example of Exemplary Coupler (1)] [Step 1] 1-Hydroxy-4-[4-nitroanilinocarbonyloxy)N-[δ-(2,4-di-tert
Synthesis of -amylphenoxy)butyl]-2-naphthamide 4.9 g of 1,4-dihydroxy-N-[δ-
(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide and 1.64 g of p-nitrophenyl isocyanate in 100 ml of dehydrated toluene.
and add 1.6g of pyridine to it to make 1~
It was refluxed for 2 hours. After the reaction, remove the solvent under reduced pressure and
- Hexane was added to filter out the crystals. The crystals were recrystallized from benzene-petroleum benzene. The above compound with a melting point of 136-138°C was obtained (yield 80
%). The results of elemental analysis were as follows.

[Table] [Step 2] 1-Hydroxy-4-(4-aminoanilinocarbonyloxy)N-[δ-(2,4-di-tert
-amylphenoxy)butyl]-2-naphthamide Synthesis of 25 g of 1-hydroxy-4-(4-nitroanilinocarbonyloxy)N-[δ-(2,4-di-
After dissolving tert-amylphenoxy)butyl]-2-naphthamide in 300ml of ethanol, zinc powder 10.4
Suspend g, add 30 ml of concentrated hydrochloric acid to 10 to 20 ml of ethanol.
Add the diluted solution at 15±5°C, react for about 1 hour, concentrate under reduced pressure, make alkaline with 7-8% aqueous sodium carbonate solution, extract with ethyl acetate, wash the organic solvent layer with water, and add anhydrous sodium sulfate. After drying, the solvent was removed under reduced pressure, n-hexane was added, and the crystals were filtered. The crystals were recrystallized from acetonitrile. The above compound with a melting point of 191-194°C was obtained (yield 80
%). The results of elemental analysis were as follows.

[Step 3]

Synthesis of 1-hydroxy-4-[4-(4-nitrophenoxyacetamide)anilinocarbonyloxy]-N-[δ-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide 36 g 1-Hydroxy-4-(4-aminoanilinocarbonyloxy)-N-[δ-2・4-di-
After heating and completely dissolving tert-amylphenoxy)butyl]-2-naphthamide in 600 ml of dioxane, 12.6 g of p-nitrophenoxyacetic acid was added, and N.N'-
A solution of 13 g of dicyclohexylcarbodiimide dissolved in 70 ml of dioxane is added. At 50℃±5℃
After reacting for 3.5 to 4 hours, the precipitate was filtered, the liquid was concentrated under reduced pressure, n-hexane was added, and the crystals were filtered.
These crystals were recrystallized from a mixed solvent of acetone-ethanol-n-hexane. The above compound with a melting point of 170-173°C was obtained (yield 80
%). The results of elemental analysis were as follows.

[Step 4]

Synthesis of 1-hydroxy-4-[4-(4-aminophenoxyacetamide)anilinocarbonyloxy]-N-[δ-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide 22 g 1-Hydroxy-4-[4-(4-nitrophenoxyacetamide)anilinocarbonyloxy]-N-[δ-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide in 450 ml of acetone. After dissolving, add 250ml of ethanol, then suspend 16.2g of tin powder, and add 75~80ml of concentrated hydrochloric acid at 15±2°C.
ml was added dropwise, and after reacting for about 30 minutes, it was concentrated under reduced pressure.
8% sodium carbonate aqueous solution (or caustic soda aqueous solution)
The organic solvent layer was washed with water, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, petroleum benzine was added, and the crystals were filtered. These crystals were recrystallized from an acetone-petroleum benzine mixed solvent. The above compound with a melting point of 153-155°C was obtained (yield 78
%). The results of elemental analysis were as follows.

[Step 5]

1-Hydroxy-4-{4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxyacetamide]anilinocarbonylsulfoxy}-N-[δ
Synthesis of -(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide disodium salt 7 g of 1-hydroxy-4-[4-aminophenoxyacetamido)anilinocarbonyloxy]-N- δ-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide in acetone
Next, add 6.3 ml of concentrated hydrochloric acid, cool to below 0°C, and add a solution of 0.82 g of sodium nitrite dissolved in 3 ml of water. At this time, dissolve the precipitated crystals in 120 ml of acetone-water mixed solvent (2:1) and
The reaction was continued for 30 minutes to complete diazotization. Separately 8-
Pour the above diazotized solution into a mixture of 24 to 25 ml of acetamido-3,6-disulfonaphthol (disodium salt), 105 ml of 10% aqueous sodium carbonate solution, and 70 ml of acetone at 15±2°C, and stir at room temperature for 40 minutes. After the reaction, the precipitated magenta precipitate was poured into 1.5 to 2 liters of water, filtered, washed with water, dried, and washed with acetonitrile.
400 ml was added, heated to 60°C, and purified to obtain the desired product (yield 70%). In this way, various colored couplers of the present invention can be synthesized according to the above synthesis method, but among the colored couplers of the present invention synthesized in this way, the elemental analysis values and λmax of the above-mentioned exemplary couplers are measured. The results are shown below.

[Color developer]

4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.00g Anhydrous potassium carbonate 37.50g Sodium bromide 1.30g Nitrilotriacetic acid trisodium salt (monohydrate)
2.50g urium hydroxide 1.00g Add water to 1 and use potassium hydroxide to pH
Adjust to 10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to 1 and use ammonia water to pH
Adjust to 6.0. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162 ml Anhydrous sodium sulfite 12.4 g Add water to bring the solution to 1, and adjust the pH to 6.5 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Table 1 shows the results of measuring the photographic properties of the samples treated in this way.

[Bleach solution composition]

Ethylenediaminetetraacetate iron ammonium salt
100g Ethylenediaminetetraacetic acid diammonium salt
10g ammonium bromide 150g Water was added to 1 and the pH was adjusted using sulfuric acid or aqueous ammonia, and three types of bleaching solutions with pH = 6.0, 7.5, and 9.0 were used. After immersion in this bleach solution, the concentration was measured again to examine the change in mask concentration, and the second mask was determined to have the same rate of change as in Example 1.
Shown in the table.

[Cyan coupler dispersion-1]

As a cyan coupler, 1-hydroxy-2[α
-(2,4-di-tert-amylphenoxy)-n-
tricresyl phosphate, 39 g of exemplified compound (2) as a colored coupler of the present invention, and 2.5 g of 2-(1-phenyl-5-tetrazolylthio)-4-octadecylsuccinimide-1-indanone as a DIR compound. 22g
The mixture was dissolved in a mixed solution of 140 g of ethyl acetate and added to 450 ml of a 7.5% gelatin solution containing 1.5 g of alkanol B, and emulsified and dispersed using a colloid mill. [Cyan coupler dispersion-2] 45 g of the cyan coupler of the above cyan coupler dispersion-1, 2 g of exemplified compound (2) as a colored coupler of the present invention, and 2.5 g of the DIR compound of the above dispersion-1.
and 0.5 g of gallic acid lauryl ester were dissolved in a mixed solution of 25 g of tricresyl phosphate and 150 g of ethyl acetate to form a 7.5% solution containing 1.7 g of alkanol B.
It was added to 480 ml of gelatin solution and emulsified and dispersed using a colloid mill. The obtained multilayer color photosensitive materials (7) and (8) were prepared in Example 1 using blue, green and red filters.
The same color development process was performed. The result is the third
Shown in the table.

[Table] The mask effect ΔD was measured by passing a cyan image through a green filter, and was expressed as the difference between the unexposed density and the maximum density. That is, the smaller this value is, the better the color reproducibility is. In addition, the sensitivity was expressed as a relative value, with the sensitivity of sample number (8) being 100. As is clear from Table 3, the color photosensitive material according to the present invention is excellent in cyan color development (sensitivity, etc.) and masking properties.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material characterized by containing a compound represented by the following general formula []. General formula [] [In the formula, Cp is a residue obtained by removing the hydrogen atom at the active site of the naphthol cyan coupler; _R1 is a hydrogen atom, an alkyl group or an acyl group having 1 to 4 carbon atoms;
R ₂ is an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms; M ₁ and M ₂ are hydrogen atoms, alkali metals, or ammonium; X is an alkylene group having 1 to 4 carbon atoms or carbon Alkenylene group having 2 to 4 atoms; A is or [Formula] (where X ₁ is an alkylene group having 1 to 4 carbon atoms, R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ is an alkyl group having 1 to 4 carbon atoms, or represents an alkenyl group having 2 to 4 carbon atoms. ]