JPS5833252A - Silver halide color photographic cyan coupler - Google Patents

Abstract

PURPOSE:To obtain a novel phenolic cyan dye image forming coupler good in spectral absorption characteristics of the formed dye, high in resistance to light, heat, humidity, etc., good in color developability, sufficient in color developing sensitivity and density, small in loss of the dye even in an exhausted bleaching bath, and retained high in color developability even when benzyl alcohol is not added to a color developing soln. CONSTITUTION:The purposes are attained by a phenolic cyan dye forming coupler having the shown general formula in which Y is a monovalent group; p is an integer of 0-5; when p>=2, Y may be same or different; R1 is a ballasting group; and Z is H or a group releasable upon coupling reaction with the oxidized product of a color developing agent. Said coupler has a naphthyl ureido group at the 2-position, and an acylamino group at the 5-position.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cyan dye image-forming coupler and a silver halide photographic material containing the same. Cyan is formed by the main agent reducing the exposed silver halogen grains19, and oxidative coupling with the couplers that form each dye in the silver halogen emulsion. Couplers typically used to form dyes are phenols and naphthols. In particular, for Phenol II, the basic properties required in terms of the photographic performance of conventional couplers are that the spectral absorption characteristics of the dye are good, that is, there is no absorption in the edge region of the spectrum and that the formed dye is sharp. It must have sufficient fastness to light, heat, moisture, etc., it must have good color development, that is, it must have sufficient color development sensitivity and color density, and it must also have 11DT.
A. It is required that a bleaching bath or a bleach-fixing bath containing ferric salt as a main component does not lose color even if it is fatigued by running.

From the standpoint of eliminating Te pollution, the removal of benzyl alcohol added to color developing solutions has been taken up as a major problem. However, the current situation is that sufficient color development cannot generally be obtained without the addition of pendyl alcohol. The decrease in color development due to the removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view, there is a demand for phenolic cyan couplers that have high color development even without benzyl alcohol. Although research has been carried out in order to achieve this, to the best of the present inventor's knowledge, a cyan coupler that satisfies all of the above-mentioned required properties has not yet been found.

For example, 6-[α-(2,4-di-t-alumiphenoxy) described in U.S. Pat. No. 2,801,171
Although 2,4-di-chloro-3-methylphenol (butanamide) has good light resistance, it has drawbacks in heat resistance and also suffers from large dye losses in tired bleach-fix solutions. Furthermore, it is highly dependent on benzyl alcohol, and it is difficult to remove benzyl alcohol from the color developing solution. 2-Heptafluoro-butaneido-5-[α-(2,4-di-t-amylphenoxy)hexanamide]phenol, described in U.S. Patent #I 2,815.826, is heat resistant and resistant to fatigue in tired bleach-fix solutions. It is excellent in terms of dye loss, but inferior in terms of light fastness and color development. Also, JP-A-53-10
Problems remain in terms of the removal of Kab 5-4 benzyl alcohol described in Japanese Patent No. 9630, and also in light resistance. Furthermore, U.S. Patent No. 3,839,044, Japanese Patent Application Publication No. 4
7-37425, JP 48-36894, JP 50-10135, JP 50-117422, JP 50-130441, JP 50-108841,
Phenol-type cyan couplers described in Publication No. 50-120334 are also unsatisfactory in terms of removal of heat-resistant benzyl alcohol. Phenol couplers having a ureido group at the 02-position are disclosed in British Patent No. 1,011,940 and US Pat. No. 3,446,622, No. 3,996,25
No. 3, No. 3,758,308 and No. 3,880,66
No. 1, etc., the cyan dyes formed by these couplers have broad spectral absorption, and furthermore, the absorption maximum is in the relatively short wavelength region of the red region, so there is considerable absorption in the edge region of the spectrum. This is unfavorable in terms of color reproduction. Although the phenol coupler having a ureido group at the 2-position described in JP-A-56-65134 has considerably improved green absorption in the spectral region, other properties are still unsatisfactory. As a result of extensive research into this prior art, the present inventors have discovered that the coupler described below fully satisfies the various properties required of the above-mentioned phenolic cyan coupler.

That is, the object could be achieved by using a phenolic cyan dye-forming coupler having a 7-tylureido group represented by the following general formula (1) at the 2-position and an acylamino group at the 5-position.

General Formula [I] [In the formula, Y represents a monovalent n group, p represents an integer of 0 to 5, and when p is 2 or more, Y may be the same or 5-different. ] The 7a/coupler in the present invention is more preferably represented by the following general formula (1).

In the formula, Y represents a monovalent U group, for example, the substituted 2te is an unsubstituted alkyl group (preferably an alkyl group having 1 to 4 carbon atoms (e.g. methyl, t/rt-butyl, etc.)), an aryl group, (preferably substituted or unsubstituted phenyl group), heterocyclic group (preferably nitrogen-containing heterocyclic ring (e.g. pyrrolidine, piperidine, etc.), hydroxy group, alkoxy group (preferably from 1 to 1 carbon atom) 8 substituted or unsubstituted alkoxy groups (e.g., methoxy tert
-butyloxy, methoxycarbonylmethoxy group, etc.), aryloxy group, (preferably substituted or unsubstituted phenoxy group), acyloxy group, (preferably substituted or unsubstituted alkylcarbonyloxy group, arylcarbonyl) oxyZ group), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 8 carbon atoms, (for example, methylthio group, etc.)), 2) tetragroup, acyl group, (preferably , an alkylcarbonyl group having 1 to 8 carbon atoms (e.g., acetyl group, pivaloyl group, etc.)), an amino group, an alkylamino group (preferably a linear or branched alkylamino group having 1 to 4 carbon atoms), (e.g. , methylamino group, methylamino group, t@rt-butylamino group)), dialkylamino group (e.g. dimethylamino group, -soμ・
, -so, oa', -80,N(R'), ,
-5oa group (ari substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aryl group, i9 represents a heterocyclic group, B/ represents an atom or a group represented by B) , may be the same or different, f
(9) O which may form a 5- or 6-membered ring together (e.g., methanesulfonyl group, carbamoyl group, methanesulfinyl group, ethoxycarbonyl group, isopropylsulfamoyl group, methoxysulfonyl group, etc.); , rd represents a ballast group, preferably having 4 to 4 carbon atoms.
30 straight chain or branched alkyl groups, aralkyl groups,
General formula (1) representing an alkenyl group, an aralkenyl group, an alkoxyalkyl group, a substituted or unsubstituted cycloalkyl group, a 5-membered or 6-membered heterocyclic group, or a group represented by the general formula CI] , J is an oxygen atom or a sulfur atom, R1 is a carbon number of 1
~200 A straight or branched alkyl group is a straight or branched alkyloxy group having 1 to I carbon atoms (e.g.
methoxy, ethoxy, t@rt-preferably, a substituted or unsubstituted alkylcarbonyl group, alkoxycarbonyl group, (preferably a substituted or unsubstituted alkyloxycarbonyl group from 1 to 1 branched alkyloxycarbonyl group) ), a carbonyl group (preferably a substituted or unsubstituted phenoxycarbonyl), a mercapto group, an alkylthio group (preferably a linear or branched substituted or unsubstituted benzenesulfonyl having 1 to 1 carbon atoms), Acyl group (preferably a straight or branched alkyl group having 1 to 200 carbon atoms, substituted or unsubstituted benzenesphonyl, acylamino group (preferably tL 9-) is a straight or branched alkyl group having 1 to 200 carbon atoms; pore, mido, substituted or unsubstituted benzene carbamide), sulfo/amide i (preferably linear or branched substituted or unsubstituted purkylsulfone azdo group with 1 to 1 carbon atoms, substituted or unsubstituted benzene) sulfonamide group), carbamoyl group (preferably a linear or branched alkylaminocarbonyl with 1 to 1 carbon atoms, substituted or unsubstituted phenylaminocarbonyl), sulfamoyl group (preferably a straight chain with 1 to 1 carbon atoms or branched alkylaminocarbonyl, substituted or unsubstituted phenylaminocarbonyl), represents an arbitrarily selected group such as chain or branched alkylaminosulfonyl, substituted or unsubstituted phenylannosulfonyl;

zri, a group that can be eliminated during a coupling reaction with hydrogen or an oxidation product of a color developing agent (for example, a halogen atom (e.g., each atom of chlorine, bromine, fluorine, etc.), an oxygen atom or a nitrogen atom directly coupled Examples include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfo/amide group, a succinimide 10- group, and more specifically, US Pat.
, 471.563, JP 47-37425, JP 48-36894, JP 50-10135, JP 50-117422, JP 50-130441, JP 5
No. 1-108841, No. 50-120334, No. 52
-18315, 53-52423, 53-10
P represents an integer from 0 to 5, m represents an integer from 1 to 4, and / represents an integer from 0 to 91.

Seven uncouplers defined in the claims of the present invention are illustrated below, but are not limited thereto.

Oh.

(5) 13- (12) OH (13)? H 14- (14) (15) I (16) H (17) 0 (19) IJ (21) (23) I (24) IJ Typical synthesis routes and synthesis examples of the coupler of the present invention are shown below. .

17- Synthesis Example 1 (Synthesis of Exemplary Coupler 1) A Synthesis of 2-naphthylureido-5-nitrophenol 15.41 2-amino-5-nitrophenol was added to 50
Suspended in 0 m/m of toluene and heated to 80°C with stirring.
16.91 of naphthyl inocyanate was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was further carried out under reflux for 2 hours. The reaction solution was cooled to room temperature, and the resulting precipitate tF was separated, washed with toluene and then with n-hexane, and dried to obtain a pale yellowish brown powder 30.6f.

Synthesis of Exemplary Coupler 1 6Sf 2-naphthylureido-5-nitrophenol was dissolved in 300 m/m tetrahydrofuran and catalytic reduction was carried out using 1f palladium-carbon as a catalyst.

After the theoretical amount of hydrogen has been absorbed, the catalyst is quickly separated from P,
Add 4 m/ml of pyridine to the P solution, and dropwise add a solution of 8.11 F 2-(2-nitrophenoxy)tetradecanoyl chloride dissolved in 50 m/ml of tetrahydrofuran over 9 minutes while cooling with ice water. The resulting 0 reaction solution was further stirred at room temperature for 2 hours, then added to ice water containing 1Qm/ml of hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained crude reaction product was separated and purified using silica gel column chromatography.0 Among the isolated nitro compounds, 6. Of was dissolved in 100 m/m of tetrahydrofuran, and catalytic reduction was performed using 1 f of palladium-carbon as a catalyst. After 0 theoretical amount of hydrogen was absorbed, the catalyst was separated from the furnace, and the F solution was concentrated under reduced pressure. 90 Add 100ml of acetonitrile and 1ml of pyridine to the resulting residue!
was added, and while stirring at room temperature, 1.61 of butanesulfonyl chloride was added dropwise over (9) minutes, and the reaction was continued for an additional 2 hours. The reaction solution was concentrated under reduced pressure, dissolved in ethyl acetate, and washed with water. After dehydration with magnesium sulfate, it was concentrated under reduced pressure, and the resulting crude product was separated and purified using silica gel column chromatography.
Crystallization was performed using a mixed solution of ethyl acetate and n-hexane to obtain a white powder of 3.2 f. It was confirmed that the product obtained by nuclear magnetic resonance spectrum and mass spectrometry was the desired product.

Synthesis Example 2 (Synthesis of Exemplary Coupler 16) A 2-(4-chloro-1-naphthyl)ureido-4-
Synthesis of chloro-5-ditrophenol 18.91 2-
Amino-4-chloro-5-nitrophenol,! =29
．． 8F phenyl 4-10-1-1-phthylcarbamate and 1.5f imidazole were suspended in 250 m/ml of xylene, and the mixture was reacted under reflux with stirring for 7 hours.

The reaction solution was cooled to room temperature, and the formed precipitate was separated, washed with xylene and then with n-hexane, and dried to obtain a light tan powder of 37.71. , 1f palladium-carbon was used as a catalyst to carry out catalytic reduction. After the theoretical amount of hydrogen has been absorbed, the catalyst is quickly separated, 4 m/m of pyridine is added to the p liquid, and while cooling with ice water, 7.3 f of 2- (2,
4-di-t@rt-pentylphenoxy)hexanoyl chloride was added dropwise over (9) minutes. After stirring the reaction solution for another 2 hours at room temperature, 11 containing hydrochloric acid of IQm/
The mixture was added to ice water, extracted with ethyl acetate, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained crude product was solidified using a mixture of 9-ethyl acetate and n-hexane, which had been separated and purified using silica gel column chromatography.
White powder crystals of f were obtained. Nuclear magnetic resonance spectroscopy and mass spectrometry analysis confirmed that the obtained product had the desired structure.

The cyan dye-forming couplers used in this invention can be prepared using similar process techniques used for conventional cyan dye-forming couplers. Typically, the couplers are incorporated into a silver halide emulsion and this emulsion is coated onto the paste. to form photographic elements.

Photographic elements can be single color or multicolor elements. In multicolor elements, the cyan dye-forming couplers of this invention are normally included in red-sensitive emulsions, but also in unsensitized emulsions or dye-sensitive dyes sensitive to each of the three primary regions of the spectrum. It has constituent units. Each building block may consist of a single layer of a single emulsion or a multilayer emulsion layer sensitive to a certain region of the spectrum. A typical multicolor photographic element consists of at least one red-sensitive silver halide emulsion layer with at least one cyan dye-forming coupler, which can be arranged in various orders as is known. Formative unit (
(at least one of the cyan dye-forming couplers is a coupler of the present invention), a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler is maintained in the base. consists of things. The element may have additional layers such as a filter layer, an intermediate protective layer, a lower MA layer, etc.

The K to be incorporated into the emulsion with the coupler of the present invention can be prepared by a conventionally known method, such as 98414-98414 - a high boiling point organic solvent of 75°C or higher, butyl acetate, globion, etc. The coupler of the present invention is dissolved in a low boiling point solvent such as butyl chloride alone or in a mixture thereof as necessary, and then mixed with an aqueous gelatin solution containing a surfactant. After emulsification in a high-speed rotary mixer or colloid mill, it can be added to silver halide to prepare the silver halide emulsion used in the present invention. When the coupler of the present invention is also added to the silver halide emulsion of the present invention, it is usually about 0.0% per mole of silver halide.
The coupler of the invention is added in an amount ranging from 0.7 to 0.7 mole, preferably from 0.1 mole to 0.4 mole.

The silver halide used in the silver halide emulsion of the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Anything is included.

The silver halide emulsion constituting the silver halide emulsion of the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, for example, the method described in Japanese Patent Publication No. 7772/1983, i.e., silver bromide emulsion having a solubility of silver bromide. A process for producing a so-called conversion emulsion, which involves forming an emulsion of silver salt grains that are larger than the size of the silver salt, and then converting at least a part of the grains into silver bromide or silver iodobromide salt, or It can be produced by any production method such as the production method of Lippmann emulsion consisting of fine grain silver halide having an average grain size of 0.1 μm or less.

Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers such as allylthiocarbazide, thiourea, cystine, active or inactive selenium sensitizers, reduction sensitizers, etc.
For example, stannous salts, ceriamine, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazolemethyl chloride, etc., or, for example, ruthenium, rhodium, etc. Chemical sensitization can be achieved by using water-soluble salt sensitizers such as iridium, specifically ammonium chlorovaradite, potassium chloroaurate, and sodium chlorovaradite alone or in combination as appropriate. can.

Further, the silver halogenide emulsion of the present invention can be prepared using various known silver 643 emulsions.
The silver halide of the present invention is a photographic additive such as that described in 1. The silver halide of the present invention can be used by selecting an appropriate sensitizing dye to impart photosensitivity in the wavelength range required for red-sensitive emulsions. Spectral sensitization is performed. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. 4IIIf No. 2,889.23;
．． Cyanine dye, melonanine dye or complex cyanine as described in No. 270.378, No. 2.442,710, No. 2,454,629, No. 2,776,280, each specification, etc. Dyes can be cited as a representative example.

The color developing solution that can be used in the present invention is preferably
The main ingredient is an aromatic primary amine coloring agent. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine fJ [acid m], dimethyl-p-phenylenediamine hydrochloride, salt, 2-amino-5-dinithylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dode7)
νa))-Toluene, 2-amino-5-(N-ethyl-N-B-methanesulfonamidoethyl)aminotoluene sulfur 12[,4-(N-ethyl-N-B-methanesulfonamidoethylamino) ) Aniline, 4-(N-ethyl-
Examples thereof include N-B-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-N-B-methoxyethyl)aminotoluene, and the like.

Bleaching to remove silver and silver halides after development;
The usual steps of fixing or bleaching, washing and drying are carried out.

Hereinafter, the present invention will be described in a formal manner with reference to Examples, but the embodiments of the present invention are not limited thereto.Example (1) Couplers of the present invention as shown in Table 1 and comparative couplers below. (A), CB), (c) are o and 0, respectively.
Take 3 malts, add to a mixture of the same amount of diptyl 7-talate and 3 times the amount of ethyl acetate, add 6°.
- I was completely happy with the temperature. Add this solution to Alkanol B (alkylnaphthalene/sulfonate, manufactured by DuPont).
and an aqueous solution of gelatin and emulsified using a colloid mill to create respective coupler dispersions. Next, this coupler dispersion was added to a packed silver emulsion containing 0.1 mol of silver (20 mol of silver bromide), coated on polyethylene laminated paper, and dried to form six types of stable coating films. silver halide color photographic light-sensitive material (sample number (1)
~ [6] was obtained.

Comparative coupler (B) I C11H fin one by one - Comparative coupler CC) H These samples were subjected to wedge exposure according to the usual method and then processed as described below.However, in the color development process, P/D alcohol was added. Two compositions were tested: ([Color developer composition 1]) and one without additive ([Color developer composition 2]).

〔process〕

Processing process (30℃) Processing time The treatment composition is shown below. [Color developer composition 1] 28- [Color developer composition 2] [Bleach-fix solution composition] −41 Photographic properties were measured for each of the obtained samples.

The results are shown in Table 1. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with [color developer composition 1] as 100. As is clear from Table 1 above, the samples obtained with the coupler according to the present invention are It can be seen that good sensitivity and maximum concentration can be obtained regardless of the presence or absence of benzyl alcohol.

In addition, as a result of measuring the color spectrum, it was found that the dye using the coupler of the present invention has the maximum absorption in a relatively long part of the red region, and shows excellent color purity with little absorption on the short wavelength side. .

Example (2) Using a sample obtained in the same manner as in Example (1) above, the light resistance, heat resistance, and moisture resistance of one dye were investigated.

The obtained results are shown in Table 2. Note that the light resistance in the table is the residual density after exposing each image to a xenon fade meter for 300 hours, and the density before exposure is 100 It was expressed as Moisture resistance was expressed as the residual concentration after storage for 3 weeks at 60° C. and relative humidity of 70 −, with the concentration before the test being 100. Furthermore, the heat resistance is 7
The residual concentration after storage for 3 weeks at 7°C was expressed with the concentration before the test as 100. (However, the initial concentration is 1-0) As is clear from Table 2, Comparative coupler 1 (4) has excellent light resistance, but there is a gap in heat and humidity resistance, and Comparative couplers [B) and Cc) , has excellent heat and humidity resistance, but has a problem with light resistance in color development [2]. On the other hand, exemplary couplers (2), (6) and [7] according to the present invention have excellent performance with any fish. It can be seen that the coupler has the following properties.

Example (3) Take 0.01 mole each of the couplers of the present invention as shown in Table 3, the comparative couplers (A), (B), and the comparative coupler (D) shown below, and add the same amount of trifluoride as their weight. It was added to a mixture of cresyl phosphate and 3 times the amount of ethyl acetate and heated to 60°C to completely dissolve. This solution was added to an aqueous solution of Alkanol B and gelatin and emulsified using a colloidal bar to prepare respective coupler dispersions.

Next, this coupler dispersion is added to a silver iodobromide emulsion containing 0.1 mole of silver (6 moles of silver iodide), coated on a cellulose acetate film base, and dried to form a stable coating film. Six types of silver halide color photographic materials (sample numbers [13] to [18]) were obtained.

Comparative coupler CD) H These materials were subjected to wedge exposure according to a conventional method and then subjected to fire treatment.

〔process〕

Processing step (33°C) Processing time [Color developer composition] 36- [Bleaching solution composition] [Fixer composition] [Stabilizing solution composition] n- The photographic properties of the obtained cyan color developer were measured.

The results are shown in Table 3.

As is clear from Table 3, the samples using the coupler according to the present invention were found to be excellent in sensitivity and color development.

Furthermore, as a result of measuring the spectroscopic spectrum, the Nishina according to the present invention has a long-length sK maximum absorption wavelength in the red region, and a sharp cut in the short wavelength region, and has improved color reproduction in the edge region compared to comparative couplers. Preferred Dye Example-4 Samples (1) to (6) obtained in Example-1 are subjected to wedge exposure and then subjected to the development treatment of (1) of Example-1. The fading properties of the cyan dye due to the fatigue bleach-fix solution were investigated by developing with the fixer having the following composition. The results of the concentration measurements are shown in Table 4.

The dye residual rate at the thickest density part was determined as follows.9.

Hata Br = bleach-fix solution From Table 4, it is understood that the sample using the coupler according to the present invention has less fading power of cyan dye when treated with fatigue bleach-fix solution. 30, 1957 (I Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Display of the case Patent Application No. 131314 of 1981 2 Title of the invention Cyan coupler for silver halide color photography 3 Relationship with the Seri case for supplementary IE Patent applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Konishi Roku Photo Industry Co., Ltd. Representative Nobuhiko Moto 4 Agent Address 191 Address Konishi, 1 Sakuracho, 1411F City, Tokyo 6, "Detailed Description of the Invention" column 7, "Detailed Description of the Invention" of the Ill Positive Target Specification, Contents of the Amendment (1) The detailed description of the invention is amended as follows.

Claims (1)

[Scope of Claims] At the 2-position, a 7-thylureido group represented by the following general formula is substituted with 5
A phenolic silver halide cyan coupler for color photography, characterized by having an acylamino group in the position. General formula [Nioki, Y represents a monovalent group, p represents an integer from 0 to 5], when p is 2 or more, Y may be the same or different. )