JPS6120039A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a titled material which has excellent color formability, obviates the color fading of a cyan dye by the treatment of a fatigued bleaching agent and is improved in a shelf life at the under a high temp. and high humidity by incorporating at least one kind of a specific phenolic cyan coupler in a silver halide emulsion layer. CONSTITUTION:The aliphat. group or arom. group R' necessary for providing diffusion resistance to a ballast group, more specifically a cyan coupler and a cyan dye formed of the cyan coupler in addition to univalent groups R, R1, R2 and Y is added in the formula. A constituting unit for forming a cyan dye image consisting of a red sensitive silver halide emulsion layer contg. a cyan dye forming coupler is carried in the silver halide emulsion photosensitive material and the constituting units for forming a magenta dye image and yellow dye image are likewise carried in the base. The incorporation of the coupler into the red sensitive silver halide emulsion is executed by dissolving the coupler then mixing the soln. with an aq. gelatin soln. contg. a surface active agent and emulsifying the same then adding the emulsion to the red sensitive silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan dye image-forming coupler. The present invention relates to a silver halide color photographic light-sensitive material containing a cyan dye image-forming coupler, which has excellent color development properties and improved storage stability under high temperature and high humidity conditions.

(Prior art) Normally, color images are produced when an aromatic primary amine-based color developing agent reduces oxidized silver halide grains, resulting in oxidation products of the color developing agent and yellow, magenta, and cyan colors. It is formed by oxidative coupling with a dye-forming coupler in a silver halide emulsion.

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

Particularly in the case of 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, it has no absorption in the green region of the spectrum and is sharp. The pigment formed has sufficient fastness against light, heat, moisture, etc. It should have good color development, that is, it should have sufficient color development sensitivity and color density. Further E
It is required that a bleaching bath or a bleach-fixing bath containing D'l'A ferric salt as a main component does not lose color even when fatigued by running.

Although extensive research has been conducted to satisfy the above-mentioned requirements, to the best of the knowledge of the present invention, 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-amylphenoxy) 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. 2-Hebutafluorobutanamide-5-[α-(2°4-di-t-amylphenoxy)hexaneamide 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. Additionally, U.S. Patent No. 3.8
39,044, JP 47-37425, JP 48-36894, JP 50-10135, JP 50-117422, JP 50-130441,
Phenol-type cyan couplers described in Japanese Patent Nos. 50-108841 and 50-120334 are also unsatisfactory in terms of heat resistance and the like. Phenol couplers having a ureido group at the 2-position are disclosed in British Patent No. 1.011,940 and U.S. Pat. No. 3.446,622 and U.S. Pat.
No. 3, No. 3,758,308 and No. 3,880,66
No. 1, etc., the cyan dyes formed by these couplers have a claudatic spectral absorption, and historically the absorption maximum is in the relatively short wave region of the red region, so there is a considerable amount of spectral absorption in the green region of the spectrum. It has absorption and is not good for color reproduction.

Although the phenol 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.

(Problems to be Solved by the Invention) Accordingly, the present invention provides a cyan dye which has excellent coloring properties, does not fade due to fatigue bleaching solution treatment, and has improved storage stability over time under high temperature and high humidity conditions. The object of the present invention is to find a silver halide color photographic material containing an image-forming coupler.

(Means for Solving the Problems) According to the present invention, the above-mentioned problem of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. It has been found that the problem can be solved by a silver halide color photographic light-sensitive side film in which the silver halide emulsion layer contains at least one phenolic cyan coupler represented by the following general formula CI).

General formula CI) R.

In the formula, 几1 represents a ballast group, R represents a monovalent group, R1 and R2 each represent a hydrogen atom or a monovalent organic group, and Y represents a monovalent organic group. , n is 0
Represents an integer from ~4.

The invention will now be described in more detail.

In the general formula (I), R1 represents a ballast group, and more specifically, R1 imparts diffusion resistance to the cyan coupler represented by the general formula CI) and the cyan dye formed from the cyan coupler. Represents an aliphatic group or an aromatic group necessary for imparting, preferably having a carbon atom number of 4
to 30 alkyl groups, aryl groups or heterocyclic groups. For example, straight-chain or branched alkyl groups (e.g., doctyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups and general formula [Ia ] and the like.

(R4)K In the formula, J is an oxygen atom or a sulfur atom, K is an integer from O to 4, t is 0 or 1, and when K is 2 or more, two or more R4s may be the same. May be different, R3
represents a linear or branched alkylene group having 1 to 20 longitudinal atoms; R4 represents a monovalent group; for example, a halogen atom (preferably chloro or bromo); an alkyl group (preferably a linear or branched carbon number); 1 to 20 alkyl groups (e.g. methyl, terj-butyl, tert-pentyl, tcr
t-octyl, dodecyl, pentadecyl, benzyl, phenethyl)), aryl groups (e.g. phenyl), heterocyclic groups (preferably, nitrogen-containing: IA multi-A ring groups), alkoxy groups (preferably straight-chain or branched carbon number 1 to 20
alkyloxy groups (e.g. methoxy, ethoxy, tert-butyloxy, octyloxy, decyloxy, dodecyloxy)), aryloxy groups (e.g. phenoxy), hydroxy, acyloxy groups (preferably alkylcarbonyloxy groups, Arylcarbonyloxy group (e.g. acetoxy, benzoyloxy)), carboxy, alkoxycarbonyl group (preferably a linear or branched alkyloxycarbonyl group having 1 to 20 carbon atoms), aryloxycarbonyl group (preferably phenoxycarbonyl), alkylthio group (preferably tL< is an alkylthio group having 1 to 20 carbon atoms), an acyl group (preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms), an acylamino group (preferably tL< is an alkylthio group having 1 to 20 carbon atoms),
straight chain or branched alkylcarboxamide, benzenecarboxamide), sulfonamide group (straight chain or branched alkylcarboxamide, benzenecarboxamide), sulfonamide group
20 straight-chain or branched alkylsulfonamide group, benzenesulfonamide group), carbamoyl group (straight-chain or branched alkylaminocarbonyl group, phenylaminocarbonyl group, having 1 to 20 carbon atoms), Sulfamoyl groups (preferably linear or branched realkylaminosulfonyl groups having 1 to 20 carbon atoms, phenylaminosulfonyl groups), and the like can be mentioned.

In addition, as the monovalent organic group represented by the general formula [I, R17), for example, an alkyl group (or a straight-chain or branched substituted group having 1 to 40 carbon atoms), or unsubstituted alkyl groups (particularly preferably methyl, Icrt-methyl)), aryl groups (or substituted or unsubstituted phenyl groups), heterocyclic groups (preferably nitrogen-containing heterocycles (particularly preferably pyrrolidine, piperidine)), 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 phenoxy group), acyloxy group (substituted or unsubstituted alkylcarbonyloxy group, arylcarbonyloxy group), mercapto group, alkylthio group (preferably 7L< is substituted or unsubstituted an alkylthio group having 1 to 8 carbon atoms (particularly preferred tL< is a methylthio group), a nitro group, an acyl group (or an alkylthio group having 1 to 8 carbon atoms)
to 80 alkylcarbonyl groups (particularly skilled, acetyl group, pivaloyl group)), amine groups, alkylamino groups (skilled or straight-chain or branched alkylamino groups having 1 to 4 carbon atoms (particularly preferably Methyl-9=amino group, ethylamino group, tcrt-butylamino group), dialkylamino group (preferably dimethylamino group, diethylamino group) can be added.

Next, in the general formula [I], R1 and R2 each represent a hydrogen atom or a monovalent organic group, and examples of the monovalent organic group include a nitro group, a hydroxyl group, a cyano group, and a carboxyl group. , amine group, substituted amino group, sulfo group or substituted or unsubstituted; alkyl group, alkenyl group, aryl group, heterocyclic residue, alkoxy group, aryloxy group, arylthio group, arylazo group, acylamino group, carbamoyl group, Examples include an ester group, an acyl group, an acyloxy group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a morpholino group, a piperazyl group, and an imidanlyl group.

Further, in the general formula [1], Y represents a monovalent organic group, and in this case, the monovalent organic group is preferably an aliphatic hydrocarbon bulk residue, an aromatic hydrocarbon residue, or a polyhydric hydrocarbon residue. Examples include ring residues, alkoxy groups, phenoxy groups, saftoxy groups, alkyl amino residues, polyamino amino residues, mercapto groups, and these groups may have substituents. .

Representative specific examples of the compound represented by the general formula CI"! are described below.

(Exemplary compound) Ha Ha H3 Ct-+3 2Hs C(X)CI2H25 CI I3 C, □H250CHCON[IC2HsC1(z(X)
NHC2H5 CH2Cα)C4H9tnl C1+3 C11z(Y)OC411s(n) CH2CON)ICI2H25 Next, a method for synthesizing the cyan coupler according to the present invention will be described.

Synthesis Example-1 (Synthesis of Exemplified Compound-1) 2-(4-trichloromethyl-2-cyano-phenylureido)-4-chloro-3((2,4-di-tcrt-
amylphenoxy)butylacetamide]-phenol 336I was dissolved in 500% acetic acid, and
．． A sodium nitrite solution prepared by dissolving 6.9 sodium nitrite in 20 and 11 volumes of water was added dropwise, and after stirring for 2 hours, the reaction solution was dissolved in 1
The mixture was poured into ice water in Step 7, and the precipitated crystals were separated by filtration and dried to obtain a quinone compound. Yield 168g (55%).

The above quinone compound 16.8.9 was added to tetrahydrofuran 20
059 and hydrogen reduction using carbon and palladium as a catalyst. After the reduction, the above catalyst was filtered, and M
Acetone 2501, potassium carbonate 36y1, benzyl bromide 4.5.9 were added to the liquid, and the mixture was refluxed for 4 hours under a nitrogen stream.

Subsequently, the reaction solution was concentrated and then subjected to column separation using toluene:acetone=7:3. A monobenzylhydroquinone derivative was thus obtained. Yield 11109 (40%).

The above monobenzylhydroquinone derivative 8.1 and bromoethyl ketone 219 were dissolved in 200 mj of acetone, and 15.9 mj of potassium carbonate was further added and refluxed for 8 hours. The reaction solution was filtered and concentrated, and the intermediate ( This intermediate was dispersed in 200 mL of ethanol and subjected to hydrogen reduction using carbon and palladium as catalysts. After the reaction, filtrate, concentrate, and recrystallize the obtained solid from acetonitrile to obtain the target compound ill 10.8 #
I got it.

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

Photographic elements can be single color or multicolor elements. Multicolored! ! In its raw form, the cyan dye-forming couplers of this invention are generally incorporated into light-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 light-sensitive material of the present invention comprises a cyan dye image-forming structural unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers is present). 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 blue-sensitive halogen having at least one yellow dye-forming coupler; It consists of a yellow dye image-forming structural unit supported on a tabase consisting of a silver oxide emulsion layer. The silver halide photographic material can have additional layers such as a filter layer, an intermediate layer, a protective layer, an undercoat layer, etc.

The coupler of the present invention can be incorporated into a red-sensitive silver halide emulsion using, for example, a high-boiling organic solvent with a boiling point of 175° C. or higher such as tricresyl phosphate or digtylphthalate, or a high-boiling organic solvent such as butyl acetate or butyl propionate. A coupler according to the present invention is dissolved in each of the low boiling point solvents alone or in a mixture thereof as necessary, and then mixed with an aqueous gelatin solution containing a surfactant,
Next, after emulsifying in a high-speed rotating mixer or colloid mill, the emulsion can be 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 in the range of about 0.07 to 07 mol, preferably 0.1 to 0.04 mol, per 1 mol of silver halide. The coupler of the invention is then added.

Examples of the silver halide used in the silver halide emulsion that can be used in the silver halide photographic light-sensitive material of the present invention include silver bromide, silver chloride, silver iodobromide, chlorobromide steel, and ordinary silver halide emulsion. Any of those used in silver halide emulsions may be 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 lower than the bromide end. A process for producing a so-called funversion emulsion, which involves forming an emulsion of silver salt grains that are large in size and consisting of at least a portion of silver salts, and then converting at least a portion of these grains into silver bromide salts or silver iodobromide salts. Alternatively, it can be produced by any production method such as the production method of a Lippmann emulsion consisting of fine grain silver halide having an average grain size of 0.1 μm or less.

Furthermore, the silver halide emulsion according to the present invention has a sulfur sensitizer,
For example, allylthiocarbamide, thiourea, cystine, etc.
Also active or inactive selenium sensitizers, reduction sensitizers such as stannous salts, polyamines, noble metal sensitizers,
For example, gold sensitizers, specifically sensitizers such as kaliuno, oli-ocyanate, potassium chloroaurate, 2-ourosulfobenzthiazolemethylchloride, or water-soluble salts such as ruthenium, rhodium, iridium, etc. , A-type compounds can be chemically sensitized using ammonium chloroparatate, potassium chlorobratate, sodium chloroparadite, etc. alone or in appropriate combinations.

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

For example, R, search I) isclnsure
(Research Disclosure) A photographic additive as described in December 1978 Item 17643.

The silver halide according to the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range necessary for red-sensitive emulsions. As this spectral sensitizing dye, 1fI! Alternatively, two or more types can be used in combination.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
, No. 378, No. 442,710, No. 2,454,6
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 20, No. 2,776,280, and the like.

The color developing solution that can be used in the halogenated photographic material 1 of the present invention is preferably one containing an aromatic primary 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-7-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. salt, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-
3-(N-ethyl-N-dodecylamino)-toluene,
2-Amino-3-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene [111 salt, 4-(N
-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aniline, 2-amino-3-(N-ethyl-N-β-methoxyethyl) Examples include amine toluene.

After development, the conventional steps of bleaching, fixing or bleach-fixing, washing and drying are carried out 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), +11.

001 mole of each fcl was added to a mixture of diptylphthalate in an amount equal to its weight and ethyl acetate in an amount three times its weight, and the mixture was heated 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 respective coupler dispersions.

Next, this coupler dispersion was added to a silver iodobromide emulsion containing 0.1 mol (5 mol % of iodized steel), coated on polyethylene laminate 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 (4) Comparative coupler (■) Comparative coupler 1cI These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing.

Processing Step (30''O) Processing Time [Color Developer Composition] [Bleaching Solution Composition] [Stabilizing Solution Composition] [Stabilizing Solution Composition] The photographic properties of the cyan dye ii!lI image obtained by the above processing were measured. The results are shown in Table 1 below.

(Table 1) (In addition, the relative sensitivity in the table is the sensitivity ratio when the comparative coupler fake) is taken as 100) It is clear from the results in Table 1 above that 11<, the sample using the coupler according to the present invention It can be seen that (Samples A1 to A3) 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 found that the maximum absorption wavelength is in the long wavelength region of the red region, and the L1 short wavelength region exhibits a sharp cut, giving a pigment image that is favorable 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 the color development treatment in Example 1. On the other hand, development was carried out using a bleach-fixing solution with the composition shown below, and the fading properties of the cyan dye artist due to the fatigue bleaching solution were investigated.

(Bleach solution composition) Adjust your strength.

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 #degree portion was determined as follows.

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

Example 3 As in Example 1 above, the light resistance, heat resistance, and moisture resistance of the dye image were examined using the sample obtained in Example 1.

The results obtained are shown in Table 3.

(Table 3) Note that the light resistance in the table is expressed as the residual density after exposing each obtained image to a xenon fade meter for 400 hours as the density before exposure '&100. Also, the moisture resistance is 60”
The residual concentration of the edge stored for 4 weeks under the conditions of 0.0 and 70% relative humidity is expressed with #i degree before the test as 100. Furthermore, heat resistance was expressed as the residual concentration after storage for 4 weeks under conditions of 77° 0, with the concentration before the test being 100. (However, the initial concentration is 1.
0) From Table 3, it can be seen that the samples using the cyan coupler according to the present invention have excellent performance in terms of light resistance, heat resistance, and moisture resistance.

(Effect of the invention) A color photographic material containing a compound represented by the uninvented general formula [I] in the silver halide emulsion layer has high sensitivity and less fading of the cyan dye image due to fatigue bleaching solution treatment. It not only has excellent color development, but also excellent storage stability over time under high temperature and high humidity conditions.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains a phenolic cyan represented by the following general formula [I]. A silver halide color photographic material containing at least one coupler. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R' represents a ballast group, R represents a monovalent group, and R_1 and R_2 are each a hydrogen atom or a monovalent organic group , Y represents a monovalent organic group, and n
represents an integer from 0 to 4. )