JPS60108845A - 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 a phenylureido group having -SO2R (R being a cation), 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 an acylamino group. The emulsion contg. said coupler is prepared by dissolving the coupler in a solvent, mixing it with n aq. soln. of gelatin contg. a surfactant, emulsifying it in a colloid mill or the like, and adding it to the 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; R is cation, such as alkali metal or quaternary ammonium cation; R<5> is halogen 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 material containing a novel cyan dye image-forming coupler.

(Prior art) Color images are usually produced by an aromatic primary amine color developing agent reducing exposed halogenated particles.
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.

Considering the photographic performance of conventional couplers, the basic properties required for Ic phenols are that the dye has good spectral absorption characteristics, that is, there is no absorption in the edge region of the spectrum.
Kuyap thing. 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 there is no dye loss even if a bleaching bath or a nickel silver fixing bath containing TA ferric salt as a main component is fatigued by washing.

Furthermore, from the viewpoint of depollution, 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 benzyl alcohol. The decrease in color development when pendyl alcohol is removed is particularly noticeable in phenolic cyan couplers, and from this point of view, we have developed a new tubonol cyan coupler that can generate cyan dyes with high color development even when benzyl alcohol is strong. There is a desire to develop silver halide photographic materials containing silver halide.

Research has been conducted to satisfy the above requirements, but to the best of the present 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 in addition, there is a large loss of dye in a tired bleach-fix solution. In addition, color development is highly 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. Although it is superior in terms of dye loss, it is inferior in terms of light resistance and color development. Also, JP-A-53-109
The coupler described in No. 630 also has problems in terms of removal of benzyl alcohol and light resistance. Furthermore, U.S. Patent No. 3゜839.044, Japanese Patent Application Publication No. 1983-374
No. 25, Japanese Patent Publication No. 1983-36894, Japanese Patent Publication No. 1983-10
No. 135, No. 50-117422, No. 50-1304
No. 41, No. 50-108841, No. 50-12033
The phenolic cyan couplers described in No. 4 and the like are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol.

A silver halide photographic material containing a phenolic coupler having a ureido group at the 2-position is a British patent]・011.9
No. 40 and U.S. Pat. No. 3,446,622, U.S. Pat. No. 3,99
No. 6,253, No. 3,758,308 and No. 3,88
0.661, etc., the cyan dyes formed from silver halide photographic materials containing these couplers have broad spectral absorption, and furthermore, the absorption maximum is in the relatively short wavelength region of the red region. For this reason, it has considerable absorption in the edge region of the spectrum, which is unfavorable in terms of 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 and is free from harmful absorption in the edge region during cyan color development.

Another object of the present invention is to provide a silver chloride color photographic light-sensitive material which 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 halogenide color photographic light-sensitive material in which the cyan-colored dye is fast.

(Structure of the Invention) As a result of extensive research into these conventional techniques, the present inventors found that the following couplers are required as the above-mentioned phenolic cyan couplers to be incorporated into the silver halide emulsion layer. The inventors have found that the material fully satisfies the above characteristics.

A phenylureido group having 18o and R at the 2-position of the phenol ring (R is a cation), a group that can be removed during a coupling reaction with hydrogen or an oxidation product of a color developing agent at the 4-position, and an acylamino group at the 5-position. At least one of the silver halogenide emulsion layers containing a phenolic cyan coupler having
This is achieved by a silver halide photographic material having a layer on a support.

The cyan coupler contained in the silver halide emulsion layer in the present invention is more preferably represented by the following general formula CI).

General formula [I] In the formula, Bl is a ballast group, X is a hydrogen atom or a group that can be separated by a coupling reaction of the oxidized product of a color developing agent, and R is a cation such as an alkali metal or a quaternary ammonium compound. represent.

The present invention will be explained in more detail below.

In the general formula [[I], the substitution position of -8O,H is the 2-position, m-position or 0-position of the ureido group, preferably tt,
< is in second place. Further, R is preferably a quaternary ammonium ion obtained from an alkali metal such as lithium, potassium, or sodium, methylamine, ethylamine, benzylamine, triethylamine, etc., and particularly preferably potassium or sodium.

Further, R5 is a halogen atom or a monovalent organic group, and p
is an integer from O to 3. Furthermore, the monovalent organic group represented by R5 includes, for example, an alkyl group (preferably a linear or branched substituted or substituted alkyl group having 1 to 4 carbon atoms (particularly preferably methyl, tart-butyl, aryl group) (preferably a substituted or unsubstituted phenyl group), a heterocyclic group (preferably a nitrogen-containing heterocyclic ring (particularly preferably a pyrrolidine, piperidine, hydroxy group, an alkoxy group (preferably a substituted or unsubstituted carbon 1115!1 to 8 carbon group) aryloxy group (preferably substituted or unsubstituted phenoxy group), acyloxy group (preferably substituted or unsubstituted phenoxy group), substituted alkylcarbonyloxy group, arylcarbonyloxy group), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 8 carbon atoms (
Particularly preferred are methylthio base layer, nitro group, acyl group,
(Preferably an alkylcarbonyl group having 1 to 8 carbon atoms (
Particularly preferred are an acetyl group, a pivaloyl group, an amine group, and an alkylamino group (especially a straight-chain or branched alkylamino group having 1 to 4 carbon atoms) (particularly preferably a methylamino group, an ethylamino group, a tert- It represents a butylamino base layer and a dialkylamino group (preferably a dimethylamino group or a diethylamino group).

Note that the value of p is preferably 0.

Further, the group represented by the above-mentioned X which can be removed during the coupling reaction is a parogen atom (specifically, each atom such as chlorine, bromine, fluorine, etc.). Examples include aryloxy groups, carbamoyloxy groups, carbamoylmethoxy groups, acyloxy groups, sulfonamide groups, and succinimide groups in which an oxygen or nitrogen atom is directly bonded to a coupling position.

Furthermore, specific examples of these groups include 1, for example, U.S. Pat.
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-
105226 etc.

X is preferably a hydrogen atom or a halogen atom.

Further, the phenolic cyanide compound represented by the general formula CI) can be expressed by the general formula rII].

General formula [II] In the formula, R and group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group,
represents an arylthio group, an alkylsulfonyl group, 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.

Y is an oxygen atom or a t/'i sulfur atom, preferably an oxygen atom. l is 0 or 1. m is θ~4 (however, m
is 2 or more, Bl represents an integer (which may be the same or different).

The halogen atom represented by R1 is preferably chlorine or bromine, and the alkyl group is preferably a linear or branched alkyl group having 1 to 2 carbon atoms, particularly methyl, ts
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 a linear or branched alkyloxy group having 1-carbon number, particularly preferably methoxy, ethoxy, or
ert-butyloxy, octyloxy, decyloxy, and dodecyloxy groups, the aryloxy group is preferably a phenoxy group, and the acyloxy group is preferably an alkylcarbonyloxy group, an arylcarbonyloxy group, and particularly preferably an acetoxy group. , 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. Bearing pressure is R3 above
The alkylthio group represented by is preferably a straight chain or branched alkylthio group having 1 to 2 carbon atoms, the acyl group is preferably a straight chain or branched alkylcarbonyl group having 1 carbon number, and the acylamino group is preferably Carbon number 1
- straight-chain or branched alkylcarboxamide, penzenecarboxamide groups, and the sulfonamide group is preferably a straight-chain or branched a/I/dr sulfonamide group having 1 to 1 carbon atoms, benzene It is a sulfonamide group,
The carbamoyl group is preferably a linear or branched alkylaminocarbonyl group having 1 to 1 carbon atoms, or a phenylaminocarbonyl group, and the sulfamoyl group is preferably a linear or branched alkylaminocarbonyl group having 1 to 20 carbon atoms. These are alkylaminesulfonyl and phenylaminosulfonyl groups, and each of these groups may have a substituent.

Next, the linear or branched alkylene group represented by R8 is preferably an alkylene group having 1 to 20 carbon atoms.

More preferably, the phenolic cyan coupler represented by the general formula (n) can be represented by the general formula [■].

4 In the formula, R and X have the same meanings as in general formula [I], and R4n represents an integer of 1 to 3.

Examples of the alkyl group represented by R4 include methyl,
Examples include groups such as propyl, dodecyl, octadecyl, etc.
These alkyl groups may have a substituent.

R3 and R8 are branched alkyl groups, preferably tertiary alkyl groups, particularly preferably t-C5
It is H+1 group.

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.

Compound example' Zugami C, H Kasumi C, H, - amount 4dk'1mHRI X R (3shi!, p Re (:
.

I bite 11! l' X R is ti, t, knee), R'(
C4H9 Next, typical synthesis steps and synthesis examples of the phenolic cyan coupler according to the present invention will be shown.

0,N O,N Fusion Synthesis Example (Exemplary Compound 3) 15.4g of 2-amino-5-ditrophenol, 29
．． A mixture of 9% p-phenoxycarbonyl, sodium aminophenylsulfinate, and 680% imidazole, 300d toluene, and 50d DMF was added to 8%
Refluxed for an hour. After reflux, the precipitated crystals were collected and washed with toluene. Thus yellow solid 20I (melting point 300
℃ or higher). This compound 28.5# was dissolved in 300 WLIK of 8θ% water-containing methanol, and catalytic reduction was performed using a radium-carbon catalyst.

After consuming the theoretical amount of hydrogen, the catalyst was removed by filtration, and the resulting solution was dried under reduced pressure. The brown solid thus obtained was dissolved in 501 L of DMF, 15.8 g of pyridine, 2
33.8 g of -(2,4-di-t-pentylphenoxy)butanoyl chloride was added and 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 recrystallized from acetonitrile to obtain 29.4 g of a penta-red brown solid with a decomposition point of 180°C.

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 method techniques used in conventional cyan dye-forming couplers can be similarly applied to the cyan dye-forming coupler used in the present invention. Typically, the coupler is incorporated into a silver halide emulsion and the emulsion is seeded onto a base to form a photographic element.

Photographic elements can be single color elements or multicolor elements. In multicolor elements, the cyan dye-forming power of the present invention is
It is usually contained in red-sensitive emulsions, but may also be contained in non-sensitized emulsions or emulsion layers sensitive to the three primary color regions of the spectrum other than red-sensitivity. Each structural unit can consist of a single emulsion layer or multiple emulsion layers sensitive to a certain region of the spectrum. The layers of the element, including the layers of imaging units, can be arranged in various orders as is known in the art.

A typical multicolor photographic element consists of a cyan dye image-forming building block consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers is a compound of the present invention). at least one green-sensitive silver halide emulsion layer with at least one magenta dye-forming coupler; at least one blue-sensitive magenta dye image-forming unit with at least one yellow dye-forming coupler;・・・
It consists of a base supporting a yellow dye image-forming structural unit consisting of a silver gonide emulsion layer. Elements can be added to additional layers such as filter layers, intermediate J fields, and protection! ! It can have a layer, an undercoat layer, etc.

In order to incorporate the coupler according to the present invention into an emulsion, a conventionally known method may be followed. For example, the coupler of the present invention may be added to a high boiling point organic solvent having a boiling point of 175° C. or higher such as tricresyl phosphate or dibutyl phthalate, or to a low boiling point solvent such as butyl acetate or butyl propionate, or a mixture thereof as necessary. After dissolving them alone or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, and then emulsified using a high-speed rotary mixer, ultrasonic disperser, or colloid mill, and then added to silver halide to form the main material. Silver halide emulsions used in the invention can be prepared. When the coupler according to the present invention is added to a silver halide emulsion, it is usually 0.07 to 0 per mole of silver halide.
．． 7 mol, preferably in the range 0.1 mol to 0.4 mol, of the coupler according to the invention are added.

The silver halide used in the silver halide emulsion in the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. used in ordinary silver halide emulsions. is included.

The silver halide emulsion constituting the silver halide emulsion used in 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., the solubility is low. An emulsion of silver salt grains made of at least a part of silver salt, which is thicker than silver oxide, is formed, and then at least part of the grains is treated with silver bromide or iodobromide@
It can be prepared by any method such as a method for producing a fragmented conversion emulsion such as converting it into a salt, or a method for producing a Lippmann emulsion consisting of finely divided I silver halide having an average grain size of 0.1 μm or less.

Furthermore, the above silver halide emulsions may contain sulfur:V sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts, polyamines, etc. etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-olosulfobenzthiazole methyl chloride, etc., or water-soluble salts such as rutinium, rhodium, iridium, etc. Sensitization can be achieved by using a sensitizing agent, specifically ammonium chloroparadate, potassium chlorooleate, sodium chloroparadite, etc. alone or in combination as appropriate (hygrochemically).

The silver halide emulsion described above can contain various known photographic additives. For example, Re5earc
h Disclosure December 1978 Item 17
A photographic additive such as that described in TI43.

The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range required for red-sensitive emulsions.

Various types of spectral sensitizing dyes can be used, and these can be used alone or in combination of two or more Fi types. Spectral sensitizing dyes advantageously used in the present invention include:
For example, U.S. Patent Nos. 2,269,233 and 2,270,
No. 378, No. 2.442.710, No. 2.454, 6
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 29 and No. 2,776.280.

The color developing solution that can be used in the present invention is preferably
The main component is an aromatic primary amine color developing agent. Typical examples of this color developing agent include those based on p-7 enylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. salt, 2-amino-5-diethylaminotoluene sulfate, 2-amino-5-(N-ethyl-N-dodenylamino)-toluene, 2-amino-5-(N-ethyl-N-β-methanesulfonamide ethyl)aminotoluene sulfate, 4-(N-ethylN-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N
-β-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-N-β-methoxyethyl)amine toluene, and the like.

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

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

Take 0.01 mol each of (B) and (C),
The Keiyo was added to a mixture of diptylphthalate (1°) and ethyl acetate (3 overtones) and heated to 60°C to completely dissolve. This solution was added to an aqueous solution of Flukanol B (alkylnaphthalene sulfone, manufactured by DuPont) and gelatin, and emulsified using a colloid mill to prepare each coupler dispersion.

Next, this dispersion was added to a silver iodobromide emulsion containing 0.1 mol of silver (5 mol% silver iodide), coated on a cellulose aptate film base, and dried to form a stable coating film. Six types of silver halide color photographic materials (sample numbers 1 to 6) having the following properties were obtained.

Comparative coupler (Al Comparative coupler (B) H c41 (e) These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing.

Processing Step (30'C) Processing Time [Color Developer Composition] [Bleaching Solution Composition] [Fixer Composition] The photographic properties 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 sample using the coupler according to the present invention (sample N[11 It can be seen that samples 3) to 3) are 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 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, development was carried out using a whitening fixer having the composition shown below, and the fading resistance 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 by K as follows.

(Table 2) From the results in Table 2 above, it was understood that the samples using the couplers according to the present invention (samples m7 to 9) showed less fading of the cyan dye when treated with fatigue bleaching solution.

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 results obtained are shown in Table 3.

(Table 3) The light resistance in the table is expressed as the residual density after exposing each image obtained for 400 hours using a xenon fade meter, with the density before exposure being 100 as 100. In addition, the humidity resistance is 60℃,
The residual concentration after storage for 4 weeks under conditions of relative humidity [70%] was expressed with the concentration before the test as 100. Saratra 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 the cyanide coating according to the present invention have excellent performance in terms of light resistance, heat resistance, and moisture resistance. ).

Take 0.03 mol of each of the couplers of the present invention as shown in Table 84 and the following comparative couplers (DJ, (El, (Fl), was added to the mixed solution and completely dissolved by heating to 60 ° C. This solution was added to an aqueous solution of Flukanol B (Flukylnaphthalene sulfonate, manufactured by DuPont) and gelatin, and emulsified using a colloid mill.
Each coupler dispersion was prepared. Next, this coupler dispersion was added to a silver chlorobromide emulsion containing 0.1 mol of silver (30 mol% silver bromide), applied to polyethylene laminate paper, and dried to form a stable coating layer. Silver halogenide color photographic materials of type 6a (sample numbers 19 to 24) were obtained.

Comparative coupler (DJ) Comparative coupler (EI C□HtBC1 Comparative coupler (F) H E These samples were subjected to extraction process using wedge exposure according to the usual method. However, the color development process was performed using a ventilator. /L
Two types of compositions were tested: one with /Fulcol added (color development [■]) and one without (color development [2]).

〔process〕

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

[Color developer composition l]

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

The results are shown in Table 4 below. In ash, the relative sensitivity value was expressed with the maximum sensitivity value when processed with color developer [1] being 100.

1) As is clear from Table 4 above, the samples obtained by the Kabra according to the present invention are excellent, with good sensitivity and maximum concentration obtained regardless of the presence or absence of benzyl alcohol. . As a result of measuring the excellent color development spectrum, it was found that the dye using the coupler of the present invention has a relatively long partial pressure absorption maximum in the red region, and exhibits excellent color purity with little absorption on the short wavelength side. did it.

Agent: Yoshimi Kuwa and Hara

Claims (1)

[Claims] A phenylfreid group having -80,R at the 2-position of the phenol ring (R is a cation), a group that can be removed during a coupling reaction with hydrogen or an oxidation product of a color developing agent at the 4-position, and an acylamino group at the 5-position. 1. A silver halide photographic light-sensitive material having on a support at least one silver halide emulsion layer containing a phenolic cyan coupler.