JPS60107649A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To eliminate light absorption in the green wavelength region hindering cyan color development, to sharpen spectral absorption, and to reduce loss of color development due to a fatigued processing soln. by forming a silver halide emulsion layer contg. a specified phenol type cyan coupler on a support. CONSTITUTION:At least one layer of silver halide emulsion layers formed on a support contains a phenol type cyan coupler having at the 2-position of the phenol ring a phenylureido group having -SO2R (R being a cyclic hydrocarbon group); at the 4-position, H or a group releasable by the coupling reaction with the oxidized product of a color developing agent; and at the 5-position, a group represented by the shown formula in which R1, R2 are each H or branched alkyl, and they are not H at the same time, R3 is alkylene, and J is O or S. The incorporation of such a cyan coupler gives good sensitivity, and good max. density in spite of the presence or absence of benzyl alcohol, further, max. absorption in a comparatively long part in the red wavelength region, small absorption in the short wavelength region, and excellent color purity, and it can form an image superior in resistances to light, heat, humidity, etc., and good color fastness.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material containing a novel cyan dye image-forming coupler.

(Prior art) Color images are usually produced by the aromatic primary amine color developing agent reducing exposed silver halide grains.
It is formed by oxidative coupling between the oxidation product of the color developing agent and the couplers forming yellow, magenta, and cyan dyes in a silver halide emulsion.

Couplers typically used to form cyan dyes are phenols and naphthols.

In particular, for phenols, the basic properties required in terms of the photographic performance of conventional couplers are that the dye has good spectral absorption characteristics, that is, there is no absorption in the edge region of the spectrum;
Sharp things. The pigment formed has sufficient fastness against light, heat, moisture, etc. Good color development.

That is, it must have sufficient color development sensitivity and color density. Further ED
It is required that a bleaching bath or a bleach-fixing bath containing TA ferric salt as a main component does not cause loss of color even when fatigued by running.

Also, from the standpoint of depollution, the removal of Hensyl alcohol added to color developing solutions has been taken up as a serious problem. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added. The decrease in coloring properties due to the removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view, a novel phenolic cyan coupler that contains a cyanide that can produce cyan dyes with high coloring properties even without benzyl alcohol. There is a demand for the development of silver halide photographic materials.

Research has been conducted so far to satisfy the above requirements, but to the best of the present inventors' knowledge, there is no silver halide photographic photosensitive material containing cyan coupler that satisfies all of the above required properties. The material has not yet been discovered.

For example, 6-[α-(2,4-di-t-amylphenoxy)butanamide)-2,4-di-chloro-described in U.S. Pat. In addition, dye loss in a tired manufactured fixer is also significant. Furthermore, color development is dependent on benzyl alcohol, and it is difficult to remove benzyl alcohol from a color developer.

2-Hebutafluorobutanamide-5-[α-(2,4-di-t-amylphenoxy)hexanamide]phenol described in U.S. Pat. No. 2,815,826 is heat resistant.

It is superior in terms of dye loss in a tired bleach-fixing bath, but inferior in terms of light fastness and color development. Also, JP-A-53
The coupler described in No. 109630 also has problems in terms of benzyl alcohol removal and light resistance. Furthermore, U.S. Patent No. 3,839°044,
-37425, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. Sho F
iO-1013! 'i No. 50-117422, No. 50-130441, No. 50-108841, No. 5
The phenolic cyan couplers described in No. 0-120334 and the like are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol. Silver halide photographic materials containing a phenolic coupler having a ureido group at the 2-position are disclosed in British Patent No. 1,011°940 and US Patent No. 3,446,622.
No. 3996.253, No. 3,758,303
No. 8 and No. 3 880.661, etc., the cyan dyes formed from silver halide photographic materials containing these couplers have broad spectral absorption, and furthermore, the thickest absorption is in the red region. Due to its relatively short wavelength range, it has considerable absorption in the edge region of the spectrum, which is unfavorable for color reproduction. Although the phenolic coupler having a ureido group at the 2-position described in JP-A No. 56-65134 has considerably improved green absorption in the spectral region, other properties are still unsatisfactory.

(Objective of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material which has sharp spectral absorption (i.e., sharp spectral absorption) and which does not have any harmful absorption in the edge region during cyan color development.

Another object of the present invention is to provide a silver halide color photographic material that exhibits good cyan color development, exhibits little color loss even when processed with a fatigue processing solution, and is less dependent on benzyl alcohol color development.

Another object of the present invention is to provide a silver halide photographic material in which the cyan-colored dye is fast. a phenylureido group having (R is a cyclic hydrocarbon group), 4
In this position, a hydrogen atom or a group that can be removed by force with an oxidized product of a color developing agent or a pulling reaction, each represents a hydrogen atom or a branched alkyl group, and the crow represents an alkylene group;
J represents an oxygen atom or a sulfur atom. However, R,
and R2 are never hydrogen atoms at the same time. ) (hereinafter referred to as the phenolic cyan coupler according to the present invention) with a silver halide photographic material having at least one silver halide emulsion layer on a support.

The phenolic cyankabra according to the present invention is preferably represented by the following general formula CD.

The R is preferably a cyclic hydrocarbon group having 3 to 10 carbon atoms. The sulfonyl group to which R is bonded is preferably one substituted at the p-position or m-position of the ureido group in the phenyl ring.

Examples of the cyclic hydrocarbon group represented by R include a cycloalkyl group and a bicycloalkyl group, which may have a substituent.

Examples of the cycloalkyl group include a cycloprobimantanyl group.

The branched alkyl group represented by R1 and R1 is preferably a secondary or tertiary alkyl group having 3 to 20 carbon atoms, such as t-butyl group, t-pentyl group, t-octyl M, 5ee-pentyl group; 5ee
-dodecyl group and the like. Further, these branched alkyl groups may have a substituent.

In the general formula, it is preferable that R1 and R2 are both tertiary alkyl groups.

R4 represents a halogen atom such as chlorine, or a -valent organic group, such as an alkyl group (preferably a linear or branched substituted or non-hexasubstituted alkyl group having 1 to 4 carbon atoms (particularly preferably methyl, tert- butyl)), aryl group (
(preferably a substituted or unsubstituted 7-nyl group), a heterocyclic group (preferably a substituted or unsubstituted 7-nyl group);

Plain elemental ring (especially preferably pyrrolidine, piperidine) L
Hydroxy group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms (particularly preferably methoxy tert-butyloxy, methoxycarbonylmethoxy group)), aryloxy group (preferably substituted or unsubstituted alkoxy group) funoxy group), acyloxy group (preferably substituted or unsubstituted alkylcarbonyloxy group,
arylcarbonyloxy group), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 8 carbon atoms (especially preferably a methylthio group))
, a nitro group, an acyl group (preferably an alkylcarbonyl group having 1 to 8 carbon atoms (particularly preferably an acetyl group, a pivaloyl group)), an amino group, an alkylamino group (preferably a linear or branched group having 1 to 4 carbon atoms) Alkylamino group (particularly preferably methylamino group, ethylamino group, t
(6rt-butylamino group)), dialkylamino group (preferably dimethylamino group, diethylamino group).

m represents an integer from 0 to 3, preferably m is 0.

R6 represents a hydrogen atom or an alkyl group, and the alkyl group is preferably a straight chain or branched chain having 1 to 18 carbon atoms.
an alkyl group (for example, a methyl group, an ethyl group, a l-propyl group, a propyl group, a dodecyl group, an octadecyl group), and this alkyl group may have a substituent.

J represents an enzyme atom or a sulfur atom, preferably an oxygen atom.

X represents a hydrogen atom or a group capable of being eliminated by a coupling reaction with a destroyed product of the color-forming main mulberry.

Examples of this removable group include: ), rogene atom (e.g., chlorine, bromine, fluorine, etc. atoms) [aryloxy group, carbamoyloxy group, in which the enzyme atom or nitrogen atom is directly bonded to the force or pulling position. , carbamoylmethoxy group, acyloxy group, sulfonamide group, co/reflection imide group, etc. More specific examples include U.S. Pat. No. 3,471,563, JP-A-47-37425,
JP 48-36894, JP 50-10135, JP 50-117422, JP 50-130441,
No. 51-108841, No. 50-120334, No. 52-18315, No. 53-52423, No. 53-
Examples include those described in No. 105226 and the like.

Preferred examples of X include a hydrogen atom or a ) chlorogen atom.

More preferably, the phenolic cyanide duller according to the present invention is represented by the following general formula (II).

General formula [■] Here, R, R, and X have the same meanings as in the above general formula [■], but both R3 and R2 are branched alkyl groups (t-
propyl group, t-butyl group, t-pentyl group, etc.).

Typical specific examples of the phenolic cyan couplers according to the present invention are shown below, but the present invention is not limited to these.

Hereinafter, a typical synthesis process and synthesis example of the phenolic cyan coupler used as the pressure body of the present invention will be shown.

Synthesis Example 2 - Synthesis of (4-cyclohexylsulfonylphenyl)ureido-5-(α-(2,4-di-t-pentylphenoxy)hexaneacidophenol (Exemplary Compound 2).

15.4 g 2-amino-5-nitrophenol, 35
, '1(7)phenyl-4-cyclohexylsulfonylphenyl carbamate and a mixture of 68011I9 imidazole, 200μ toluene was refluxed for 8 hours. After reflux, the precipitated crystals were collected and washed with toluene. (mp 192-194°C yellow solid 28.
I got 39. Obtained 2-(4-cyclohexylsulfonylphenyl)ureido-5-nitrophenol 20.
2 g was dissolved in 200 ml of tetrahydrone, and catalytic reduction was performed using a palladium-carbon catalyst.

After consuming the theoretical amount of hydrogen, pyridine 7.9I was added to the reaction solution.
, 18.3 g of 2-(2,4-di-t-pentylphenoxy)hexyl chloride was added, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was added to ice water and extracted with ethyl acetate. After washing with water, the ethyl acetate layer was separated, dried over sodium sulfate, and concentrated to obtain an extract. This reaction crude product was isolated and purified using silica gel column chromatography to obtain 10.5 g of light brown caramel.

The structures of the intermediate and cyan coupler synthesized above were confirmed to match the target product by IR, NMR, etc. Other cyan couplers of the present invention can be synthesized in a similar manner.

The cyan dye-forming coupler contained in the silver halide emulsion layer according to the present invention can be similarly applied to the method techniques used for conventional cyan dye-forming couplers. Typically, they are incorporated into a silver halide emulsion, such as a coupler, and the emulsion is coated onto a base to form a photographic element.

Photographic elements can be single color or multicolor elements. In multicolor elements, the cyan dye-forming couplers of this invention are generally incorporated into red-sensitive silver halide emulsions.

Each structural unit constituting each photosensitive silver halide emulsion layer is
It can consist of a single emulsion layer or multiple emulsion layers that are sensitive to a certain region of the spectrum.

The silver halide photographic material according to the present invention comprises at least one red-sensitive silver halide emulsion layer containing at least one cyan dye-forming coupler. at least one magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer, at least one magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer; A yellow dye image-forming unit consisting of at least one blue-sensitive) silver halide emulsion layer having two yellow dye-forming couplers is supported on a base. It can have layers, intermediate layers, retention layers, undercoat layers, etc.

To be incorporated into the coupler red-sensitive silver halide emulsion according to the present invention, tricresyl phosphate, dibutyl phthalate F'49, a high boiling point organic solvent with a boiling point of 175°C or higher, butyl acetate, globion powder, etc. The coupler according to the present invention is dissolved in a low-boiling point solvent such as butyl alone or in a mixture thereof as necessary, and then mixed with an aqueous gelatin solution containing a surfactant,
The silver halide emulsion emulsified in a high-speed rotary mixer or colloid mill can then be added to the red-sensitive silver halide emulsion to prepare the silver halide emulsion used in the present invention.

When the coupler according to the present invention is added to the red-sensitive silver halide emulsion according to the present invention, usually silver halide 1
Approximately 0.07 per mole ■α7 mole, preferably 0.1~
The Kabra of the present invention is added in an amount of 0.4 mol.

Silver halide used in the silver halide emulsion that can be used in the silver halide photographic light-sensitive material trap of the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Any of those used in conventional silver halide emulsions are included.

The silver halide emulsion constituting the silver halide emulsion according to 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. 46-7772, i.e., the solubility is higher than that of silver bromide. A process for producing a so-called conversion emulsion, in which an emulsion of silver salt grains consisting of at least a portion of silver salt, which is large in size, is formed, and then at least a portion of the grains is converted into silver bromide or silver iodobromide salt, or O
In addition, the silver halide emulsion according to the present invention can be prepared by any method such as the method of manufacturing a Lippmann emulsion comprising fine-grained silver halide having an average grain size of 21 μm or less. active or inactive selenium sensitizers, reduction sensitizers such as il tin salts, polyamines, precious metal layer sensitizers such as gold sensitizers, specifically Potassium aurithiocyanate, potassium chloroaurate, 2-ourosulfobenzthiazole methyl chloride, etc. (・k'i
For example, sensitizers of water-soluble salts such as ruthenium, rhodium, iridium, etc., specifically ammonium chloronochlorate, potassium chlorooleate, and sodium chloropalladide (* are used as appropriate) When used in combination, it can be chemically sensitized.

Furthermore, the silver 10-genide emulsion according to the present invention can contain various known photographic additives.

For example, Research Disclosure December 1978 Item 1
7643.

The silver halogenide according to the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart sensitivity to the wavelength range necessary for red-sensitive emulsions. . Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral wavelength three-sensitive dyes advantageously used in the present invention include, for example, U.S. Pat.
No. 9,234, No. 2,270,378, No. 2,442
, No. 710, No. 2゜454.620, No. 2,776
．． Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 280.

The color developing solution that can be used in the silver halide photographic light-sensitive material of the present invention preferably contains as a main component an aromatic primary amine color-forming fJ image herbal medicine. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-
5-(N-ethyl-N-dodecylamino)-toluene,
2-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoludiene sulfur salt, 4-(N-
ethyl-N-β-methanesulfonamidoethylamino)
Aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-
N-β-methoxyethyl)aminotoluene and the like.

After storage, the conventional steps of bleaching, fixing or bleach-fixing, washing and drying are carried out to remove silver and silver chlorides.

(Examples) The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited to those described above.

Example 1 A phenolic cyan coupler according to the present invention as shown in Table 1 below and a comparative Kabra (5) below.

Take 0.01 mol of each of (B) and tq, add them to a mixture of dibutyl phthalate with the same fat and jλ, and 3 times the amount of ethyl acetate, and heat to 60°C to completely dissolve. . This solution was added to an aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill to prepare each Kabra dispersion. Next, this dispersion was used as silver.
．． Silver iodobromide emulsion containing 1 mole (5 mole % of silver iodide) is added to a silver iodobromide emulsion (5 mole % is silver iodide), coated on a cellulose acetate film base, and dried to form a stable coating film. Photographic g'yt materials (sample numbers 1 to 6) were obtained.

Comparative coupler (A) 0 ■ Comparative coupler (B) H Comparative coupler (C) u 4H9 These samples were subjected to nine edge exposures according to a conventional method, and then subjected to the following processing.

Processing step (30°C) Processing time [Color developing solution composition] [Bleaching solution composition] [Constant M solution composition] [Ammonium thiosulfate 175.0. ! i' [Stabilizing liquid composition] The photographic characteristics of the cyan dye image obtained by the above processing were measured. The results are shown in Table 1 below.

(The relative sensitivity in the table is the sensitivity ratio when the comparative coupler (A) is taken as 100.) As is clear from the results in Table 1 above, the samples used as couplers according to the present invention (samples IG 1 to It can be seen that sample 3) is superior to the comparative couplers in both sensitivity and color development. Furthermore, as a result of measuring the spectroscopic spectrum of the sample according to the present invention,
It was also found that the dye has a maximum absorption wavelength in the long wavelength region of the red region, shows a sharp cut in the short wavelength region, and provides a dye image that is favorable in terms of color basis.

Example 2 Samples 7 to 12 obtained in the same manner as in Example 1 were subjected to wedge exposure, and then subjected to the color development treatment in Example 1. On the other hand, development was carried out using a bleach-fix solution with the composition shown below, and the fading resistance of the cyan dye image due to the fatigued bleach solution was investigated.

(Bleach solution composition) The maximum reflection density of the cyan dye of the sample obtained by image processing was measured.

The results are shown in Table 2 below. Incidentally, the dye residual rate at the maximum density portion was determined as follows.

From the results in Table 2 above, it was understood that in the samples using the coupler according to the present invention (Samples 7a 7 to 9), the fading of the cyan dye was small in the fatigue bleaching solution treatment.

Example 3 Using samples obtained in the same manner as in Example 1, the light resistance, heat resistance, and moisture resistance of colored thread images were investigated.

The results obtained are shown in Table 3.

(Table 3) The light resistance in the table is expressed by the residual density of each image obtained after exposure for 400 hours using a xenon fade meter, with the density before exposure being 100. Moisture resistance was expressed as the residual concentration after storage for 4 weeks under moxibustion conditions at 60° C. and 70% relative humidity, with the concentration before the test being 100. Furthermore, the heat resistance is 7
The residual concentration after storage for 4 weeks under yarn production at 7° C. was expressed with the concentration before the test as 100. (However, the initial concentration was 1.0) From Table 3, it can be seen that the samples using the cyan coupler according to the present invention had excellent performance in terms of light resistance, heat resistance, and moisture resistance.

Example 4 0.03 mol each of the couplers of the present invention as shown in Table 4 and the following comparative couplers (9) and (8, (t)) were taken, and the same amount of dibutyl phthalate and three times the weight of of ethyl acetate and completely dissolved by heating to 60°C.This solution was added to an aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill. Then, a silver chlorobromide emulsion containing 0.1 mol of silver (30 mol% silver bromide) and VCFz were added to this coupler dispersion, and the mixture was coated on polyethylene laminate paper and dried. Six types of silver halide color photographic materials (sample numbers 19 to 24) having stable coating films were obtained.

Comparative coupler (D) (e Comparative coupler (E) Comparative coupler (F) These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing. Two types of compositions were tested: one (color development (1)) and one added (color development f?121).

〔process〕

Treatment process (28℃) 111 hours Color development 3 minutes 30 seconds Bleach fixing 1 minute seconds Wash with water for 2 minutes The composition of each treatment is shown below.

[Color developer composition l]

[Color developing solution composition 2] [Bleach-fixing solution composition] Characteristics of each of the obtained samples were measured.

The results are shown in Table 4 below. -i: (Medium, relative sensitivity value is the maximum sensitivity value when processed with color developer [1]
It was expressed as

As is clear from Table 4 above, the samples obtained using the coupler according to the present invention exhibited excellent sensitivity and maximum concentration regardless of the presence or absence of benzyl alcohol. As a result of the measurement, it was understood that the dye using the coupler of the present invention has the maximum absorption in a relatively long part of the red region, and has little absorption on the short wavelength side, exhibiting degraded color purity.

Agent Yoshimi Kuwahara

Claims (1)

[Claims] A phenylureido group (R) having R at the 2nd position of the phenol ring (a cyclic hydrocarbon group), a hydrogen atom at the 4th position -1
: represents a coupling atom or a branched alkyl group with an oxidized product of a color developing agent, R3 represents an alkylene group, and J represents an oxygen atom or a sulfur atom. However, R
1 and R2 are never hydrogen atoms at the same time. ) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a phenolic cyan coupler on a support.