JPS60108846A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photosensitive material having no absorption hindering cyan color formation in the green region, sharp in spectral absorption, good in cyan color formation, small in color formation loss when processed with a fatigued processing soln., and small in dependence on benzyl alcohol color formation, by incorporating a specified phenolic cyan coupler in a silver halide emulsion layer. CONSTITUTION:A silver halide emulsion layer formed on a support contains a phenolic cyan coupler represented by the shown formula and having at the 2-position of the phenol ring an arylureido group having a hetero ring formed by condensing a 5- or 6-membered ring having -S- or -SO2- directly combined with the phenyl ring, with this phenyl ring, at the 4-position, H or a group releaseable by the coupling reaction with the oxidized product of a color developing agent, and at the 5-position an acylamino group. A red-sensitive silver halide emulsion contg. said coupler is prepared by dissolving the coupler in a solvent, mixing it with an aq. soln. of gelatin contg. a surfactant, emulsifying it in a colloid mill or te like, and adding it to said silver halide emulsion in the range of 0.07-0.7mol per mole of silver halide. In the formula, R<1> is a ballasting group; X is H or a group releasable in the coupling reaction with the oxidized product of the color developing agent; Z is a nonmetallic atomic group having -S- or -SO2- directly combined with a phenyl ring and completing a 5- or 6-membered ring; R<5> is halogen, such as chlorine, or a univalent org. group; and p is 0, 1, 2, or 3.

Description

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

(Prior art) Color images are usually produced by using an aromatic primary amine color developing agent to reduce exposed silver halide grains.
It is formed by oxidative coupling between the resulting oxidation product of the color developing agent and 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 Kabra 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 levelness against light, heat, moisture, etc. Good color development.

That is, it must have sufficient color development sensitivity and color density. Further ED
A bleach bath or a bleach-fix bath containing TA ferric salt as a main component is required to have good dye loss even when fatigued by running.

Also, from the standpoint of depollution, the removal of benzyl alcohol, which is added under pressure to a color developing solution, has been taken up as a major problem. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added.

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, the product contains a novel phenolic cyan coupler that can generate cyan dyes with high color development even without benzyl alcohol. There is a demand for the development of silver halide photographic materials.

Until now, research has been carried out that satisfies the above requirements, but to the best of the inventors' knowledge, there is no silver halide photograph containing a cyan coupler that satisfies all of the above required properties. A photosensitive material has not yet been discovered.

For example, 6-[α-(2,4-di-t-amylphenoxy)butanamide)-2,4-di-chloro-3-methylphenol described in U.S. Pat. No. 2,801,171 has a light-fast Although it has good properties, it has shortcomings in heat resistance and also suffers from large loss of dye in a tired bleach-fix solution. 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 US Pat. Although it is superior in terms of dye loss in bath, it is inferior in terms of light fastness and color development. Also, JP-A-5
The coupler described in 3-109630@K also has problems in terms of removal of benzyl alcohol and light resistance. Furthermore, U.S. Pat. No. 5
Phenolic shea described in No. 0-120334 etc.
Coupler is also unsatisfactory in terms of heat resistance and removal of benzyl alcohol. Silver halide photographic materials containing a phenolic coupler having a zeta-ureido group at the 2-position are disclosed in British Patent No. 1, 011°940 and U.S. Patent No. 3,446,62.
No. 2, No. 3996.253, No. 3.7fi8,3
No. 08 and No. 3゜880.661, etc., but these (cyan dyes formed from silver halide photographic materials containing recoupler) have broad spectral absorption, and furthermore, the absorption maximum is in the red region. Because it is in the relatively short wave region of the spectrum, it has considerable absorption in the edge region of the spectrum, which is not favorable for color reproduction. Green absorption has been considerably improved, but other properties are still insufficient.

(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 without any absorption that would be a hindrance to the edge region during cyan color development.

Another object of the present invention is to provide a halogen and silver oxide color photographic light-sensitive material that exhibits good cyan color development, exhibits little loss of color development even when processed with a fatigue processing solution, and has less dependence on benzyl alcohol color development.

Still another object is to provide a silver halide color photographic light-sensitive material in which cyan-colored dyes are uniform. As a result of repeated efforts, it has been found that the coupler described below fully satisfies the various physical properties required for the above-mentioned phenolic cyan coupler as a coupler contained in a silver halide emulsion layer.

-8- directly bonded to the phenyl ring at the 2-position of the phenol ring
Or -8O! an aryl ureido group having a fused heterocycle formed by a 5- to 6-membered ring containing - and the phenyl ring, a force with hydrogen or an oxidation product of a color developing agent at the 4-position, a group that can be removed during a pulling reaction, This is achieved by a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a phenolic cyan coupler having an acylamino group at the 5-position on a support.

The cyan coupler contained in the silver halide emulsion layer in the present invention is preferably represented by the following general formula [I] general formula CI
) In the formula, R1 is a palust group and is a substituted alkyl group, preferably a substituted 7. It is a phenylthioalkyl group or a phenylthioalkyl group.

X is a hydrogen atom or a group that can be separated by a force or bling reaction with an oxidized product of a color developing agent.

2 is -S- or etc. directly bonded to the phenyl group,
These atoms may have a substituent.

-S- or -SO, - directly bonded to the phenyl group
The position relative to the ureido group is preferably #, the 2-position or the m-position on the phenyl group.

In addition, examples of the substituent on the heterocycle include an alkyl group having 8 or less carbon atoms.

Furthermore, K R' represents a halogen atom such as chlorine or a -valent organic group. p is an integer from 0 to 3.

Examples of the monovalent organic group represented by R5 include an alkyl group (
Preferably, a straight chain or branched substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (particularly preferably methyl, tar
(t-butyl)), an aryl group (preferably a substituted or unsubstituted 7., nyl group), a heterocyclic group (preferably a
Heterocycle (especially preferred f, L < is pyrrolidine, piperidine)
), hydroxy group, alkoxy group (preferably 1 carbon number)
to 8 substituted or unsubstituted alkoxy groups (particularly preferably me) #'/, tart-7' thyloxy, methoxycarbonylmethoxy groups), aryloxy groups (
(preferably substituted or unsubstituted phenoxy group), acyloxy group (preferably substituted or unsubstituted alkylcarbonyloxy group, carbonyloxy group), mercapto group, alkylthio group (preferably substituted!
il-replaced a#*ruthio group (particularly preferably a methylthio group) l, 2)4 group, an acyl group (preferably an alkylamino group having 1 to 8 carbon atoms/14 (eK
Preferably an acetyl group, a pivaloyl group)), an amino group,
Alkylamino group (preferably a linear or branched alkylamino group having 1 to 4 carbon atoms (particularly preferably a methylamine group, ethylamino group, tert-butylamino group)
), dialkylamino group (preferably dimethylamino group, diethylamino group), and the like. Further, p is preferably 0.

In addition, the force represented by Examples include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, and a succinimide group.

Note that X is preferably a hydrogen atom or a halogen atom.

Furthermore, as specific examples of these groups, see, for example, US Pat. No. 3,471. Fi No. 63, JP-A-47-37425,
Japanese Patent Publication No. 4B-36894, Japanese Patent Publication No. 1') 0-1013
No.5, fi0-117422, fi50-13044
No. 1, No. 51-108841, No. 150-12033
No. 4, No. 52-1831F), No. 53-52423, No. F) 3-105226, etc.

Furthermore, the fumer cyan coupler represented by the general formula [I] is preferably one represented by the following general formula [■].

General formula [■] In the formula, 2 and X have the same meanings as above.

R1 is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a hydroxy group,
Acyloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, alkylsulfonyl group,
It represents an arylsulfonyl group, an acyl group, an acylamino group, a sulfonamide group, a carbamoyl group or a sulfamoyl group.

R3 represents a linear or branched alkylene group.

Further, Y is an 112 elementary atom or a sulfur atom, preferably an oxygen atom.

l represents 0 or 1, and m represents an integer of 0 to 4.

When m is 2 or more, R2 may be the same or different.

The nitrogen atom represented by R2 is preferably chlorine or bromine, and the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, particularly preferably methyl, t
The aryl group is preferably a phenyl group, and the heterocyclic group is preferably a nitrogen-containing heterocyclic group. The alkoxy group represented by R2 is preferably a linear or branched alkyloxy group having 11 to 20 carbon atoms, particularly preferably methoxy, ethoxy,
t6rt-butyloxy, octyloxy, decyloxy, and dodecyloxy groups, the aryloxy group is preferably a phenoxy group, and the acyloxy group is preferably an alkylcarbonyloxy group or an arylcarbonyloxy group, particularly preferably acetoxy or benzoyloxy. The alkoxycarbonyl group is preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms, and the aryloxycarbonyl group is preferably a phenoxycarbonyl group. Further, the alkylthio group represented by R2 is preferably a straight-chain or branched alkylthio group having 1 or more carbon atoms, and the acyl group is preferably a straight-chain or branched alkylcarbonyl group having 1 or more carbon atoms. The acylamino group is preferably a linear or branched alkylcarboxamide or benzenecarboxamide group having 1 or more carbon atoms, and the sulfonamide group is preferably a linear or branched alkylsulfonamide group having 1 or more carbon atoms, It is a benzenesulfonamide group, and the carbamoyl group is preferably a linear or branched alkylaminocarbonyl or phenylaminocarbonyl group having 1 carbon atom, and the sulfamoyl group is preferably a 1-carbon alkyl group.
- A base layer of linear or branched alkylaminosulfonyl or phenylaminosulfonyl, and each of these groups may have a substituent.

Next, the linear or branched alkylene group represented by R3 is preferably an alkylene group having 1 to 2 carbon atoms.

Further, the phenolic cyan coupler represented by the general formula [n) is more preferably one represented by the following general formula [III].

General ceremony [town In the formula, 2 and X have the same meanings as above.

R4 represents a hydrogen atom or an alkyl group, and the alkyl group is preferably a straight chain or terminally branched alkyl group having 1 to 18 carbon atoms, such as a methyl group, a propyl group, a dodecyl group, an octadodecyl group, etc. These alkyl groups may have a substituent.1 B11 and R6 are branched alkyl groups, preferably tertiary alkyl groups, particularly preferably t-C
,H,, - group.

n is an integer from 1 to 3.

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 ('!, etc.).

Compound example C,H.

13 4 0CH.

Next, a typical method for synthesizing phenolic cyankagura according to the present invention will be described.

It can be easily synthesized by following the above route.

(Synthesis example) Exemplary compound (1) was synthesized by the following route.

H Compound (A) 1.5. ! i', compound (B) 3.9, and imidazole 7Qq are heated under reflux for 6 hours in 50°C of toluene. After the reaction, the precipitated crystals are collected by filtration. The produced intermediate (C) is washed with Pd-C in 10% aqueous tetrahydrofuran (50%).

The calculated amount of hydrogen was absorbed. Compound CD) is poured into 5001 water. The crystals were dissolved in 100 WL of ethyl acetate, and an aqueous alkaline solution containing 5607F potassium hydroxide was added.
The mixture was stirred vigorously with 0d and 13.3g of compound (g) was added.

After reacting for 2 hours, the ethyl acetate layer was washed with water and dried.

It was concentrated under reduced pressure and separated on a silica gel column.

1.5g of Exemplified Compound (1) was obtained. It was confirmed by NMR and mass spectrometry that it was the desired product.

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

The cyan dye-forming ability graph contained in the silver halide emulsion layer according to the present invention can be similarly applied using the method techniques used for conventional cyan dye-forming couplers. A typical process involves formulating, for example, a coupler silver halide emulsion and coating this emulsion onto a base to form a photographic element.

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

Each structural unit constituting each photosensitivity/%Q silver fumide layer can be a single emulsion layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

The silver halide photographic light-sensitive material of the present invention comprises a cyan dye image-forming unit (a cyan dye-forming coupler) consisting of at least one small red-sensitive silver halide emulsion layer containing at least one cyan dye-forming coupler. at least one of which is a coupler according to the invention), a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler, at least one having at least one yellow dye-forming coupler. It consists of a yellow dye image-forming structural unit consisting of one evening-sensitive silver halide emulsion layer supported on a base. The silver halide photographic material may have additional layers such as a filter layer, an intermediate layer, a protective layer, and an undercoat layer.

When incorporating the coupler according to the present invention into a red-sensitive silver halide emulsion, for example, a high boiling point solvent having a boiling point of 175° C. or higher such as dilphosphate or dibutyl phthalate or a low boiling point solvent such as butyl acetate or butyl propionate can be used. The coupler according to the present invention is dissolved in K alone or in a mixture thereof as necessary, alone or in combination, and then mixed with an aqueous gelatin solution containing a surfactant. Alternatively, it can be emulsified in a colloid mill and added to a 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, it is usually about 0.07 to 0.7 mol per mol of silver halide, preferably 0.1 mol - 0. The couplers of the invention are added in the range of 4 gels.

The a-halogenide solution used in the a-a silver emulsion that can be used in the silver halide photographic light-sensitive material of the present invention includes:
Any of those used in conventional halide emulsions, such as silver bromide, silver halide, silver iodobromide, and silver bromide chloride iodobromide, etc., are included.

The silver halide emulsion constituting the silver halide emulsion of the present invention can be produced by various manufacturing methods, including the usual manufacturing method.
For example, a method such as that described in Japanese Patent Publication No. 7772/1982, ie, at least some Iji! A method for producing a so-called convergilon emulsion, such as forming an emulsion of silver-based grains consisting of 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 1 μm or less.

Furthermore, the silver halide emulsion according to the present invention includes a sulfur sensitizer,
For example, luciocarpamide, thiourea, cystine, etc.
In addition, active or inactive selenium sensitizing lithiocyanate, potassium chloroaurate, 2-oresulfopenzthiazole methyl chloride, etc., or water-soluble sensitizers such as rutheniuno 1, rhodium, iridium, etc., specifically, Chemical sensitization can be carried out using ammonium chloroparatate, potassium chlorooleate, sodium chlorovaradite, etc. alone or in appropriate combinations.

Further, the silver halide emulsion according to the present invention can contain various known photographic additives.

For example, the silver halide according to the present invention is a photographic additive as described in Raaeareh Disclosure (Research Disclosure) December 1978 Item 17643 K. Spectral sensitization is achieved by selection of suitable sensitizing dyes for imparting. Various types of spectral sensitizing dyes are used, and these can be used alone or in combination.Spectral sensitizing dyes that are advantageously used in the present invention include, for example, U.S. Pat. 23
No. 4, No. 2,270,378, No. 2.442,710
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 1, No. 2.454,620, and No. 2.776.280. Silver halide of the present invention The color developing solution that can be used for photographic light-sensitive materials is preferably one containing an aromatic FF11-class amine color developing agent as a main component. Typical examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine Nawam salt, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-7enylenediamine. Hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N-β-methanesulfone amidoethyl)aminotoluene sulfate, 4-(N
-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aryniline, 2-amino-5-(N-ethyl-N-β-methoxyethyl) Examples include aminotoluene.

Development is followed by the usual steps of bleaching, fixing or bleach-fixing, washing and drying to remove silver and silver halides.

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

Example (1) Phenolic cyan couplers according to the present invention as shown in Table 1 and the following comparative couplers (A), (B), (
Take 1 mole of each of C), add it to a mixture of dibutyl 7-talate in the same amount as its weight, and 3 times the amount of ethyl acetate, and warm to 0°C to completely dissolve the vinegar. The solution was added to an aqueous solution of Alkanol B (alkylnaphtha I/nsul 7 tonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill to prepare respective coupler dispersions. Next, this coupler dispersion was added to a silver iodobromide emulsion containing 0.1 mol of silver (5 mol of silver iodide), coated on polyethylene laminate paper and dried, resulting in six types of stable coating films. Halogenated steel color photographic materials (sample numbers 1 to 6) were obtained.

Comparative coupler (5) Comparative coupler (Bl OTI Comparative coupler (C) 4H9 These samples were subjected to conventional wedge exposure and then subjected to the following processing.

Processing step (30°C) Processing time [Color developing solution composition] [Bleaching solution composition] [Stabilizing solution composition] [Stabilizing solution composition] Photographic properties were measured. The results are used for the first pregnancy (first pregnancy) mentioned above.
Table) (The relative sensitivity in the table is the sensitivity ratio when the comparison coupler (A) is taken as 100.) As is clear from the results in Table 1 above, the sample using the coupler according to the present invention (sample A1 It can be seen that items 3) to 3) are superior to the comparison Kabra in sensitivity and color development. Furthermore, as a result of measuring the spectroscopic spectrum, it was found that the sample according to the present invention 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 pigment image that is preferable in terms of color reproduction. .

Example 2 Samples 7 to 12 obtained in the same manner as in Example 1 were subjected to wedge exposure, and then subjected to Example 10 color development treatment. On the other hand, the bleach-fixed 1v sample was developed with the following composition, and the fading property of the cyan dye image due to the fatigue bleaching 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.

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

Example 3 Using a sample obtained in the same manner as in Example 1, the light resistance, heat resistance, and moisture resistance of the dye image were examined.

The obtained results are shown in Table 3. (Table 3) In addition, the light resistance in the table is the residual density after exposing each image to a xenon fade meter for 400 hours, with the density before exposure being 100. expressed. Moisture resistance was expressed as the concentration after storage for 4 weeks at ω° C. and 70% relative humidity, with the concentration before the test being 100. Furthermore, the heat resistance is
The residual concentration after storage for 4 weeks at 77° C. was expressed with the concentration before the test as 100. (However, the initial concentration is 1.0) From Table 3, it can be seen that the samples using Shea/Cub 2 according to the present invention have excellent performance in terms of light resistance, heat resistance, and humidity resistance. I understand.

Example 4 0.03 mol each of the couplers of the present invention as shown in Table 4 and the following comparative couplers (D), (E), and (F) were taken, and the same amount of diptyl heptatalate and It was added to a mixture with 3 times the amount of ethyl acetate and heated to ω°C to completely dissolve. This solution was added to an aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dujo) and gelatin, and emulsified using a colloid mill to prepare each coupler dispersion. Next, this coupler dispersion was added to a silver chlorobromide emulsion containing 0.1 mol of silver (30 mol % silver bromide), coated on polyethylene laminate paper and dried to form a stable coating film. What kind of silver halide color photographic light-sensitive materials (sample numbers 19 to 27K)? Star.

Comparative coupler (D) LJ Comparative coupler (E) Comparative coupler (F) Added benzyl alcohol (color development [1]
) Two types of compositions were tested: one without additives (color development [2]) and one without additives (color development [2]).

〔process〕

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

[Color developer composition 1] [Color developer composition 2] [Bleach-fix solution composition] Established.

The results are shown in Table 4 below. In the table, the relative sensitivity values are expressed with the maximum sensitivity value when processed with color developer [ ] as 100.

(No. 4) As is clear from Table 4 above, the samples obtained with the coupler according to the present invention have excellent sensitivity and maximum concentration regardless of the presence or absence of benzyl alcohol. In addition, as a result of measuring the color spectrum, it was found that the color i of the present invention has a maximum absorption in a relatively long part of the red region, and the absorption on the short wavelength side is small (excellent color). I understand that it indicates purity.

Agent Yoshimi Kuwahara

Claims (1)

[Claims] -S directly bonded to the 7L nyl ring at the 2-position of the phenol ring
An arylureido group having a fused heterocycle formed by a 5- to 6-membered ring containing - or -802- and the phenyl ring, 4
At least one silver halide emulsion layer containing a phenolic cyan coupler having an acylamino group at the 5-position, a group that can be eliminated during a pulling reaction, and a force with potential hydrogen or an oxidation product of a color developing agent is used as a support. A silver halide photographic light-sensitive material having the above.