JPH01955A - Silver halide color photographic material containing a new cyan coupler - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan coupler. The present invention relates to a silver halide color photographic light-sensitive material from which dye images with good quality can be obtained.

(Prior art) The subtractive color method, which is generally used as a color reproduction method for color photography, reduces silver halide in each of the imagewise exposed blue-, green-, and red-sensitive emulsion layers using a color developing solution. Yellow, magenta, and cyan dyes are formed by the coupling reaction between the oxidized product of the color developing agent and the coupler, and a color image is obtained.

Phenol-based cyan couplers and naphthol-based cyan couplers are generally used as couplers that form dyes by reacting with oxidized products of color developing agents such as those mentioned above, especially couplers that form cyan dyes. Various studies have been conducted on cyan couplers in order to satisfy the following basic properties. That is, (1) good dispersion stability in a system using a high boiling point solvent as a coupler solvent;

(2) The spectral absorption characteristics of the dye formed are good, that is, there is little absorption in the blue and edge regions of the dye's spectrum, and the absorption wave edge is sharp.

(2) It has good color development, that is, it has sufficient sensitivity and maximum density, and even if benzyl alcohol, which is undesirable from a pollution standpoint, is removed, the color development is good.

(2) Even when processed with a bleach or bleach-fix solution that has become fatigued due to running or the like, there is no loss of coloring pigment, ie, a decrease in coloring efficiency (hereinafter referred to as "poor color recovery").

■ The dye image formed has sufficient fastness to light, heat and moisture.

etc.

Various studies have been conducted to develop cyan couplers that meet the above-mentioned problems. For example, the coupler described in U.S. Pat. No. 2,801,171 has excellent color forming properties, but has a lot of asymmetric absorption in the blue and edge regions of the spectrum of the dye formed, and has poor color reproducing properties and Poor heat resistance.

Also, U.S. Patent Nos. 2,895,826 and 2,77
No. 2,162, No. 3,758,308, No. 3,8
Specifications of No. 39,044, Japanese Patent Publication No. 47-37425,
No. 48-36894, JP-A-50-130441,
5G-117422, 5G-130441, 50-108841, 50-120334, 5
No. 3-109630, No. 56-65134, No. 59-
Some of the couplers described in various publications such as No. 46644 are excellent in terms of color development or color restoration, but there are many such asymmetric absorptions as described above, and there are no couplers that can satisfy all of the above properties.

Couplers described in JP-A-56-104333, JP-A-58-105229, JP-A-60-159851, etc. also have good storage stability, but are still unsatisfactory in reducing the asymmetric absorption.

Furthermore, U.S. Patent Nos. 2,324,832 and 2,72
No. 8,660, No. 3,858,537, No. 3,6
No. 32,347, No. 3,762,921 si
, the phenolic cyan coupler having a carbamoyl group at the 2-position described in Japanese Patent Publication No. 39-1031 does not have the above-mentioned asymmetric absorption and has a sharp absorption wave edge, but
It has the drawbacks of poor dispersibility due to low solubility in organic solvents, and poor color reversibility and dye image storage stability, especially heat resistance.

As mentioned above, a cyan coupler excellent in all of the above basic properties has not yet been found.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material that has high sensitivity and processing suitability, particularly excellent color reversibility.

Another object of the present invention is to provide a silver halide color photographic material in which the formed dye image is robust, the spectral absorption characteristics of the dye image are improved, and, as a result, the color reproducibility is excellent.

A further object of the present invention is to provide a silver halide color photographic material containing a novel cyan coupler with excellent dispersibility.

(Means for Solving the Problems) The above objects of the present invention have been achieved by a silver halide color photographic light-sensitive material characterized by containing at least one cyan coupler represented by the following formula [I].

General formula [I] [wherein R represents an acylamimum L alkylsulfonamide group, arylsulfonamide group, carbamoyl group or sulfamoyl group, R' represents 1[1's i group, X represents a halogen atom, 2, which represents an alkoxy group or a hydroxy group, represents a hydrogen atom or a group capable of being 1lliVl by a coupling reaction with an oxidation product of an aromatic primary amine developing agent.

l represents 1 or 2, yaku represents 0 or 1, and n represents 1 or 2. ] In the general formula [I], the group represented by R is an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, a carbamoyl group or a sulfamoyl group,
An acylamino group, an alkylsulfonamide group, or a phenylsulfonamide group is preferable, and a group having a total number of carbon atoms of 1 to 32 is more preferable.

For the purpose of the present invention, it is particularly preferable that the substitution position of R in the general formula [I] be at the ortho position with respect to the amide.

In the general formula [I], the monovalent organic group represented by R' is preferably an electron-donating group, and examples of such electron-donating groups include, for example, "Structure-Activity Relationships of Drugs" (Nankodo, No. 96-103). Examples include groups having a Hammett's σp value of a negative number, as described in J. P., 1979), and more preferably a group having a Hammett's σρ value of -0.3 or less.

Preferred examples of the organic group represented by R' include an amino group, an alkyl group, an alkoxy group, a ureido group, and a benzamide group, including those having substituents.

More preferred are amino groups, branched alkoxy groups, and benzyloxy groups having substituents.

The group represented by X in general formula [I] is a halogen atom, an alkoxy group or a hydroxy group, preferably a chlorine atom or an alkoxy group.

In the general formula [I], 1 is preferably 1, 1 is preferably O, and n is 1 or 2. When n is 1, the substitution position of R/ is preferably at the 5th position relative to the phenol. Further, when the number is 2, the two R's may be the same or different.

In addition, in the general formula [1], the group represented by 2 that can be eliminated by a coupling reaction is, for example, a halogen atom (specifically, each atom such as chlorine, odor, fluorine, etc.), an oxygen atom, a sulfur atom, or a nitrogen atom. A removable group attached directly to the coupling position, such as an alkoxy group, an aryloxy group, a sulfonylalkoxy group, a carbamoyloxyylmethoxy group, an acyloxy group, a sulfonamide.

Examples include a do group, a triazolylthio group, a tetrazolylthio group, a tetrazolyl group, a carbonyloxy group, and a succinimide group.

Furthermore, specific examples of these groups include, for example, U.S. Pat. No. 3,476,563, U.S. Pat.
No. 6894, JP-A-50-10135, JP-A No. 50-11
No. 7422, No. 50-130441, No. 51-10
No. 8841, No. 50-120334, No. 52-18
No. 315, No. 53-52423, No. 53-1052
No. 26, No. 54-14736, No. 54-48237, No. 55-32071, No. 55-65957, No. 5
No. 6-1938, No. 56-12643, No. 56-27
It is described in various publications such as No. 147.

The group represented by Z is preferably a hydrogen atom, a halogen atom, an alkoxy group having a substituent, an aryloxy group having a substituent, etc., and more preferably a chlorine atom or a carbamoylmethoxy group having each substituent,
These include sulfonylalkoxy groups and phenoxy groups.

Specific compounds of the cyan coupler represented by the general formula [I] are illustrated below, but the present invention is not limited to the following compounds.

The coupler represented by the above general formula [I] can be synthesized by various methods depending on the structure, but generally, it can be synthesized by the following reaction.

The above reaction (1) is a reaction to synthesize a carbamoyl group, in which a dehydrating agent is added to a carboxylic acid and an amine, such as N,N'-disycOhexylcarbodiimide (hereinafter referred to as rDccJ).
or by reacting an acid chloride or phenyl ester with an amine.

Reaction (2) is a reaction to introduce R', where Y is a nucleophilic group such as a hydroxy group or an amine group, and an active reagent such as an alkyl halide, acid chloride, or urethane is reacted in the presence of a base. It can be obtained by letting

Reaction (3) is a reaction for introducing Z, and can be performed by halogenation or by introducing a hydroxy group or a halogen atom into the 4-position of the phenol, and by a substitution reaction, a substituted or unsubstituted alkoxy group, phenoxy group, etc. can be introduced. At that time, the hydroxy group of the phenol may be protected if necessary. Introduction of other leaving groups can be carried out with reference to the above-mentioned patent publications.

Hereinafter, a specific synthesis example of the cyan coupler represented by the general formula [I] of the present invention will be shown.

Synthesis Example 1 (Synthesis Reaction Scheme of Exemplary Coupler 1 (a) (b) (Exemplary Coupler 1) Synthesis of Intermediate (b) 50o starting material (a) and 920 2-dodecylamide aniline were dissolved in 40011 dioxane. , 6 in the solution
A solution of 20 DCC in 1001R dioxane was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, the precipitated urea was filtered, the solvent was distilled off, and hexane was added to solidify to obtain 109 g of medium solid (b).

Synthesis of Exemplary Coupler 1 Intermediate (b) of 50o was dissolved in 250 ml of chloroform, and 169 sulfuryl chloride was dissolved in 50112 of chloroform and added dropwise under water cooling. After stirring at air temperature for 2 hours,
Chloroborum was distilled off, and white crystals of 410 were obtained by recrystallization from ethyl acetate and hexane.

NMR, IR, FD-Mass 1. : The structure of the white crystal obtained was confirmed.

To! (Exemplary coupler 5) Synthesis of intermediate (d) Dissolve 50 g of 2,4-dihydroxybenzoic acid and 150 (1 of 2-(4-dodecyloxyphenylsulfonamido)benzoyl chloride in 500 i of dioxane,
670 DCC was added to the solution at room temperature with stirring and dioxane 1
001g was added dropwise. After removing the urea precipitated after repulsion with Wl for 3 hours, the product was purified by column chromatography to obtain 87 g of intermediate (d).

Synthesis of Exemplary Coupler 5 80 g of intermediate (d) and 18 g of isopropyl bromide were dissolved in 200112 N,N-dimethylformamide and 6 g of sodium hydroxide was added to 80.degree.
The reaction was carried out at 0°C for 5 hours. After draining the water and extracting with ethyl acetate, the obtained 65 g of caramel was purified by columnar mudgraphy and dissolved in 2001 g of ethyl acetate.
After adding 15 g of N-chlorosuccinimide and heating under reflux for 3 hours, it was washed with water and recrystallized from hexane to give 4
4 g of exemplary coupler 5 was obtained.

The structure was confirmed by NMR, IR, and FD-Mass.

The amount of the cyan coupler represented by the general formula [I] used in the silver halide color photographic light-sensitive material of the present invention is preferably 1 to 0.5 mol of O,OO per mol of silver halide.

Further, as the cyan coupler of the present invention, the above compound can be used alone, but it can also be used in combination with another phenol-based or naphthol-based cyan coupler. In such a case, the amount of the other phenol-based or naphthol-based cyan coupler used is preferably 0.1 to 10 mol per 1 mol of the cyan coupler of the present invention.

Although the cyan coupler of the present invention can be used in both the emulsion layer and the non-emulsion layer in the silver halide photographic light-sensitive material, it is particularly preferable to use it in the red-sensitive emulsion layer.

The cyan 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 oil-in-water emulsion dispersion method. For example, in the oil-in-water emulsion dispersion method, the cyan coupler is usually dissolved in a high-boiling organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low-boiling point and/or water-soluble organic solvent, such as an aqueous gelatin solution, etc. After emulsifying and dispersing it in a hydrophilic binder using a surfactant, it may be added to the desired hydrophilic colloid layer.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but the present invention particularly applies when applied to color photographic paper used for direct viewing. The effect is effectively strengthened.

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

Examples of the yellow coupler used in the photographic light-sensitive material of the present invention include penzoylacetanilide-based and pivaloylacetanilide-based compounds, and specific examples thereof include U.S. Pat. Nos. 2,875,057 and 3,265.
, No. 506, No. 3.408.194, No. 3.55
No. 1,155, No. 3,582,322, No. 3.7
25.072, West German Patent No. 3,891,445, West German Patent No. 1,547,868, West German Application Publication No. 2,219,
No. 917, No. 2,261,361, No. 2,414
,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, 4
No. 8-73147, No. 51-102636, No. 50-
No. 6341, No. 50-123342, No. 50-13
No. 0442, No. 51-21827, No. 50-8765
No. 0, No. 52-82424, No. 52-115219, etc.

As the magenta coupler used in the photographic material of the present invention, for example, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers can be used. Specific examples of such magenta couplers include Japanese Patent Publications No. 4G-6031 and No. 40-6035.
No. 45-40757, No. 47-27411, No. 49-37854, JP-A-50-13041, No. 5
No. 1-26541, No. 51-37646, No. 51-
No. 105820, No. 52-42121, No. 53-1
No. 23129, No. 53-125835, No. 53-1
No. 29035, No. 54-48540, No. 56-292
No. 36, No. 56'-75648, No. 57-17950
No. 57-35858, No. 57-146251,
Publication No. 59-99437, British patent cylinder 1.252,
No. 418, U.S. Pat. No. 2,600.788, U.S. Patent No. 3.
No. 005,712, No. 3.062.653, No. 3
, No. 127,269, No. 3,214,437, No. 3.253.924, No. 3,311,476, No. 3,419,391, No. 3,519.429 ,
3.558.319, 3,582,322, 3,615,506, 3,658,544
No. 3,705, 896, No. 3,725,0
No. 67, No. 3,758,309, No. 3,823.
No. 156, No. 3,834,908, No. 3.891
．． No. 445, No. 3,907,571, No. 3,92
No. 6,631, No. 3,928,044, No. 3.9
No. 35,015, No. 3,960.571, No. 4.
No. 076, 533, No. 4.133.686, No. 4
, No. 237,217, No. 4,241,168, No. 4,264, 723, No. 4,301,235, No. 4,310,623. can be mentioned.

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 of the present invention is chemically sensitized by a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method, or the like.

The silver halide emulsion of the present invention can be optically sensitized 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, a formalin scavenger 1 mordant, a development accelerator,
Development retardants, optical brighteners, matting agents, lubricants, antistatic agents, surfactants, and the like can be optionally used.

The silver halide photographic light-sensitive material of the present invention can form images by performing various color development processes similar to those of ordinary silver halide photographic light-sensitive materials.

(Examples) Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Preparation of silver halide emulsions Six types of silver halide emulsions shown in Table 1 were prepared by a neutral method and a simultaneous mixing method.

Table 1 After completion of chemical sensitization, 5TB-1 shown below was added as an emulsion stabilizer to each silver halide emulsion in an amount of 5×10 −3 mol per mol of silver halide.

S 03N H(C-Hs)i [5D-3] Preparation of silver halide color photographic light-sensitive material sample Next, the following layers 1 to 7 were sequentially coated on a paper support whose both sides were coated with polyethylene (simultaneous coating) Silver halide color photographic light-sensitive material samples 1 to 8 were prepared. (In the following examples, the addition port is indicated per 1f of light-sensitive material.) Layer 1: Gelatin (1,2CI) and 0.2
A blue-sensitive silver halide emulsion (Em-1> of 9a (in terms of silver, the same applies hereinafter) and a yellow coupler (Y
-1), 0.3 (l of light stabilizer 5T-1 and 0. ot
sg 2,5-dioctylhydroquinone (HQ-1)
A layer containing 0.3 g of dinonyl phthalate (DNP) dissolved therein.

Layer 2... Gelatin (0.9g) and 0.041;
A layer containing 0.2 g of DOP (dioctyl phthalate) in which 1 of HQ-1 was dissolved.

Layer 3: gelatin (1,40), 0.2 g of green-sensitive silver halide emulsion (EI5-2), 0.66
g of magenta coupler (M-1), 0.5 g of DOP in which 0.25 CI of light stabilizer ST-2' and 0.011;l of HQ-1 were dissolved, and 6.9 of the following filter dye Al. -1.

Layer 4... Gelatin (1,20) and the following 0.6
g of ultraviolet absorber (JV-1 and Hi0.05o(7)HQ
A layer containing 0,31;l of DNP, which is understood from -1.

Layer 5... Gelatin (1,4!) and 0.20
(J's red-sensitive silver halide emulsion (E--3) and Table 2
1.06 mmol of each cyan coupler shown in 0.0
A layer containing DOP of 0, 3(J) in which HQ-1 of 1(] and 5T-1 of 0.3CI were dissolved.

16...gelatin (1.1g) and 0.20 U
A layer containing 0.2 g of DOP in which V-1 was dissolved and 5 mo of the following filter dye Al-2.

Layer 7... Gelatin (i, oa >, 0.05
A layer containing 2°4-dichloro-6-hydroxytriazine sodium of TJ.

(ST-1) UV-I I-I I-2 (Y-1) (M-1) The obtained sample was subjected to wedge exposure using a sensitometer KS-7 model (manufactured by Konishiroku Photo Industry Co., Ltd.). After processing according to the following color development processing steps, the specific sensitivity and layer high density ([) Wa .

Also, when the density of the cyan dye image is 1.0, 420r
The concentrations at v and 550 nm, namely DB and DG, were measured.

Further, the obtained sample was stored for 20 days under conditions of 85° C. and 60% relative humidity, and the dark fading property was evaluated by determining the residual rate (%) of the dye image at an initial density of 1°0.

Further, the specific sensitivity was expressed as a relative value with the sensitivity of sample No. 1 as 100.

The above results are shown in Table-2.

[Processing process] Temperature Time Development color development 34.7±0.3℃ 45 seconds Bleach fixing 34.7±0.5℃ 50 seconds stabilization 3
0~34℃ 90 seconds drying 60~
80℃ 60 seconds [Color developer] Pure water 80G triethanolamine 8 (IN, N-diethylhydroxyamine 5g Potassium chloride
2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30 g potassium sulfite
0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 10 Add pure water to bring the total volume to 12 and adjust to pi-110.2.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100 Ammonium sulfite (40%)
% solution > 27.5d p with potassium carbonate or glacial acetic acid
Adjust to H5.7 and add water to bring the total volume to 11.

[Stabilizing liquid] 5-chloro-2-methyl-4-inthiazolin-3-one 1g 1-hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make 1t, and adjust pH with ti*m or potassium hydroxide. 7,
Adjust to 0.

As is clear from the results of comparative coupler Table 2, sample 1 using the conventionally used coupler (C-1) has high sensitivity and maximum density, but has large asymmetric absorption in both Da s Da and poor bright color fading. Samples 2 and 4, which have good light fading properties, also have large asymmetric absorption and do not have sufficient sensitivity.

In addition, sample No. 003 has considerably improved asymmetric absorption, but is inferior in dispersion stability, color development, and bright color fading. -6 Samples 5 to 8 using the couplers of the present invention exhibited high levels of color development, asymmetric absorption, and dark fading properties, and were found to be excellent color light-sensitive materials.

Example 2 The blue-sensitive silver halide emulsion of layer 1 of the silver halide color photographic light-sensitive material prepared in Example 1 was used as Em-4 in Table 1.
The green-sensitive silver halide emulsion of W3 was added to El- in Table-1.
5, the red-sensitive silver halide emulsion of layer 5 was added to Ic of Table 1.
Silver halide color photographic materials Nos. 009 to 13 were prepared in the same manner as in Example 1 except that the cyan couplers shown in Table 3 were used in layer 5 in place of e-6.

The obtained sample was passed through a photosensitive needle KS-7 type (manufactured by Konishiroku Photo Industry).
After wedge exposure using the following method, the film was processed according to the following color development processing steps.

[Processing process] Color development 3 minutes 30 seconds Bleach fixing at 33℃
1 minute 30 seconds Temperature: 33°C Water washing 3 minutes Temperature: 33°C Color developer formulation N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.9g Hydroxylamine sulfate 2. 0g potassium carbonate 25.0 (sodium monobromide 0.69 anhydrous sodium sulfite 2.0g benzyl alcohol
13112 polyethylene glycol (average degree of polymerization 40G) 3.0t
Add j2 water and make 1j! Bind and adjust pH to 1 with sodium hydroxide.
Adjust to 0,0.

Bleach-fix solution formulation Ethylenediaminetetraacetic acid sodium salt 6.0 g Ammonium thiosulfate 100 i; 1 Sodium bisulfite io g Sodium metabisulfite 3 g Add water to make 11, and adjust DH to 7.0 with aqueous ammonia.

On the other hand, 5 g of sodium hydrosulfide was added to the bleach-fix solution to reduce the bleaching edge, and the bleach-fix solution was used as a fatigue bleach-fix solution (hereinafter referred to as "fatigue BFJ") to examine color recovery properties.

That is, after color development, a new bleach-fix solution (hereinafter "New BFJ"
It is called. ) and fatigue bleach-fix solution, the maximum density of the cyan dye obtained was compared, and the color reversibility (%) was calculated using the following formula. Table 3 shows the results.

Fatigue BF Maximum Density Comparison Couplers Table 3 As is clear from Table 3, Samples 9 and 10 using comparative couplers were found to have insufficient color restoration properties. Especially sample 1
0 has a low absolute value of maximum density and is not practical.

On the other hand, it can be seen that Samples 11 to 13 using the couplers of the present invention have excellent color development and color recovery properties.

(Effects of the Invention) As described in detail above, silver halide color photographic sensitizers with high sensitivity and processing suitability, particularly excellent color restoration properties, are produced by containing the novel cyan coupler represented by -Isen [I]. Materials are obtained.

Furthermore, by containing the cyan coupler, the dye image formed is robust and has improved spectral absorption characteristics,
As a result, a silver halide color photographic material having excellent color reproducibility was obtained.

Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Scope of Claims] A silver halide color photographic material containing at least one cyan coupler represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R represents an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, a carbamoyl group, or a sulfamoyl group, and R' is a monovalent organic group. , and X represents a halogen atom, an alkoxy group or a hydroxy group. Z represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. l represents 1 or 2, m represents 0 or 1, and n represents 1 or 2. ]