JPS6322297B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to a novel blocked magenta dye-forming coupler for silver halide photography, and more specifically, to a blocked photographic coupler that has a high color development speed and a high maximum color density, has improved color development defects over time, and has excellent stability. This invention relates to a magenta dye-forming coupler for use in the United States. Conventionally known magenta dye-forming couplers include the pyrazolotriazole, pyrazolobenzimidazole, indazolone and pyrazolone series. Two-equivalent type magenta dye-forming couplers are known in which a substituent is introduced into the active site of these magenta dye-forming couplers to improve silver utilization efficiency. These conventionally known two-equivalent type magenta dye-forming couplers include, for example, halogen-substituted type (U.S. Pat. No. 3,006,579, etc.), aryloxy-substituted type (U.S. Pat. No. 3,419,391, etc.), and carbonyloxy quantitative type (U.S. Pat. No. 3,311,476). , No. 3422521, JP-A-49
-129535, etc.), nitrogen or sulfur substitution type (JP-A-Sho
No. 49-53435, No. 49-53436, No. 50-53372,
No. 50-122935, etc.), carbon substitution type (U.S. Patent No.
2632702, Japanese Patent Publication No. 51-37646, etc.), substituted methylene substituted type (British Patent No. 963461, Japanese Patent Publication No. 344036, etc.), methylene, alkylidene or arylidene bis type (US Patent No. 2618641, British Patent No.
No. 736859, No. 968461, Special Publication No. 16110,
No. 44-26589, No. 49-37854, JP-A-49-
29638 etc.). Although these two-equivalent type magenta dye-forming couplers have characteristics such as a faster dye formation rate and a higher maximum color density than four-equivalent type ones, they are not necessarily satisfactory. Furthermore, the above-mentioned known two-equivalent type couplers have the disadvantage of being unstable because they are active themselves. Therefore, there have been problems in that fogging is likely to occur during color development, yellow staining is likely to occur in uncolored areas or low density areas, and color development deteriorates over time. In recent years, high sensitivity and high graininess have been desired in color photographic technology. The use of large amounts of silver halide to obtain high sensitivity provides an excess of developing agent oxidation products (i.e., oxidized aromatic primary amino developer) formed therefrom, resulting in large amounts of dye Degrading graininess to produce . In order to improve this, development inhibitor releasing compounds and competitive couplers have been used. However, even when these compounds are used, the effect is not sufficient or the sharpness deteriorates. JP-A-56-133734 describes an excellent magenta dye-forming coupler that eliminates the need for a competing coupler. When using this coupler, 4 or 6 equivalents of silver are required to produce one molecule of magenta dye, so oxidation products of the developing agent produced in excess are less likely to deteriorate graininess. . However, the magenta dye-forming coupler described in the above-mentioned publication is very unstable and has particularly poor storage stability, making it impractical. Furthermore, the magenta dye density obtained from the above couplers is also insufficient. Accordingly, a first object of the present invention is to provide a novel blocked magenta dye-forming coupler for providing a silver halide color photographic light-sensitive material exhibiting high sensitivity and excellent graininess. A second object of the present invention is to provide a novel blocked magenta dye-forming coupler for producing a silver halide color photographic light-sensitive material exhibiting high sensitivity and excellent graininess without using competitive couplers. It is. A third object of the present invention is to provide a blocked magenta dye-forming coupler that has excellent shelf life and color development. The object of the present invention was achieved by using a blocked magenta dye-forming coupler represented by the following general formula (hereinafter referred to as the coupler according to the present invention). General formula () In the above formula, Q represents a group of nonmetallic atoms necessary to form a magenta dye-forming coupler together with a nitrogen atom,

[Formula] represents a blocking group, X represents an oxygen atom or a sulfur atom, R and R' are a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkenyl group, an aryl group, or a heterocycle, and Cp represents a compound capable of causing a coupling reaction with an oxidized form of a developing agent, and is bonded to X at its active site. The Cp moiety forming the blocking group according to the present invention can be selected from, for example, 4-equivalent couplers used in color light-sensitive materials. Examples include magenta couplers such as 5-pyrazolone couplers, yellow couplers such as cyanoacetylcoumarone couplers and acylacetanilide couplers, and siman couplers such as naphthol couplers and phenol couplers. Among the above magenta couplers, those represented by the following general formula [A] are particularly useful. General formula [A] In the formula, R ₁ is an alkyl group selected from primary, secondary, and tertiary groups (e.g., methyl, propyl, n-butyl, t-butyl, hexyl, 2-hydroxylethyl, 2-phenylethyl, etc.). ),
Aryl groups, hetero groups, (e.g. quinolinyl,
pyridyl, benzofuranyl, oxazolyl, etc.)
Amino groups (e.g. methylamino, diethylamino, phenylamino, tolylamino, 4-(3-
Sulfobenzamino) anilino, 2-chloro-5
-acylaminoanilino, 2-chloro-5-alkoxycarbonylanilino, 2-tolylfluoromethylphenylamino, etc.) carbonamide group (e.g. ethylcarbonamide, alkylcarbonamide, arylcarbonamide, benzothiazolylcarbonamide) amido, sulfonamide, heterosulfonamide, etc.), ureido groups (e.g.
R ₂ is an aryl group (e.g., alkylureido, arylureido, heteroureido, etc.).
naphthyl, phenyl, 2,4,6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl,
4-methylphenyl, 4-acylaminophenyl, 4-alkylaminophenyl, 4-trifluoromethylphenyl, 3,5-difuromophenyl, etc.), hetero groups (e.g., benzofuranyl, naphthoxazolyl, quinolinyl, etc.), etc. represents. Among the above yellow couplers, those represented by the following general formula [B] are particularly useful. General formula [B] In the formula, R ₃ is a primary alkyl group having 1 to 18 carbon atoms,
Secondary alkyl group, tertiary alkyl group (e.g. t-
butyl, 1,1-dimethylpropyl, 1,1-dimethyl-1-methoxyphenoxymethyl, etc.),
Aryl groups (e.g. phenyl, alkylphenyl, 3-methylphenyl, 3-octadecylphenyl, alkoxyphenyl, 2-methoxyphenyl, 4-methoxyphenyl, halofenyl, 2-
Halo-5-alkamidophenyl, 2-chloro-5
-[α-(2,4-di-t-amylphenoxy)butyramide] phenyl, 2-methoxy-5-alkamidophenyl, 2-chloro-5-sulfonamidophenyl, etc.) R ₄ is a phenyl group (e.g. 2
-chlorophenyl, 2-halo-5-alkamidophenyl, 2-chloro-5-[α-(2,4-di-t
-amylphenoxy)acetamide]phenyl, 2
-Chloro-5-(4-methylphenylsulfonamido)phenyl, 2-methoxy-5-(2,4-
di-t-amylphenoxy)acetamidophenyl, etc.). Further, the cyan coupler includes, for example, a 2-acylaminophenol type cyan coupler, a 2-aminoacylnaphthol type cyan coupler, and the like. In particular, those represented by the following general formula [C] are useful. General formula [C] In the formula, R ₅ is a substituent used in the cyan coupler,
For example, carbamyl groups (e.g., alkylcarbamyl, phenylcarbamyl, arylcarbamyl,
heterocyclic carbamyl groups such as benzothiazolylcarbamyl), sulfamyl groups (e.g.
Alkylsulfamyl, arylsulfamyl,
phenylsulfamyl, arylsulfamyl,
represents a heterocyclic sulfamyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, etc. Forms the blocking group used in the present invention
The Cp part is the general formula [A], [B] or [C]
Examples include acylacetonitrile couplers, acylacetyl couplers, malonic ester couplers, malonamide couplers, cyanoacetate ester couplers, cyanoacetamide couplers, malonitrile couplers, etc., and JP-A-52 −69624, 50−
Compounds shown in No. 147716, No. 52-36028, US Pat. No. 3,841,800, etc. can also be used. R and R' in the general formula () are not particularly limited as long as they are monovalent groups, but are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. More preferred are those in which both R and R' are hydrogen atoms, and those in which one is a hydrogen atom. The alkyl group and alkenyl group of R and R' may be linear, branched, or cyclic, and the heterocyclic group is, for example, a pyridyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a pyrimidyl group, etc. Indicates 5- and 6-membered rings containing heteroatoms such as oxygen atoms. Here, the above alkyl group, alkenyl group, aryl group and heterocyclic group may have a substituent.

The magenta dye-forming couplers represented by the formula are conventionally known pyrazolotriazole, pyrazolobenzimidazole and indazolone, and are represented by the following general formulas ()() and (), respectively. R ₆ represents a hydrogen atom or a group that is eliminated during color development, and specifically includes a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a sulfonyloxy group, an acyloxy group, a heterocyclic group,
Thiocyano group, alkylthio group, arylthio group, heterocyclic thio group, sulfonamide group, phosphonyloxy group, arylazo group, substituted methyl group,
Represents an a-substituted benzyl group, etc. R ₇ and R ₈ are independent of each other, and each is an alkyl group, aryl group, heterocyclic group, alkoxy group, amino group, acylamino group, anilino group, hydroxy group, aryloxy group, alkylthio group, arylthio group, carbamoyl group, carboxy group, alkoxycarbonyl group, ureido group, imido group, sulfonamide group, sulfamoyl group, and sulfo group, and more specifically, as an alkyl group, for example, a methyl group, isopropyl group, t-butyl group, or dodecyl group. represents a linear or branched alkyl group having 1 to 32 carbon atoms, or a cyclic alkyl group such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, and these groups may further include a halogen atom, a nitro group, a cyano group, etc. , aryl group, alkoxy group, aryloxy group, carboxy group, alkylthio group,
It may be substituted with an arylthio group, carbonyl group, sulfamoyl group, acylamino group, heterocyclic group, etc. It also represents an aryl group such as a phenyl group, an α-naphthyl group, a β-naphthyl group, etc., and these groups can further include a halogen atom, an alkyl group, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, It may be substituted with a carboxyl group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, or the like. Further, a heterocyclic group such as a 5- or 6-membered heterocycle containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom (this heterocycle also includes a fused heterocycle), such as a pyridyl group, a quinolyl group, Examples include furyl group, penzothiazolyl group, oxazolyl group, imidazolyl group, and naphthoxazolyl group. These groups may be further substituted with the same substituents as in the case of the above-mentioned aryl group. Also, an alkoxy group such as a methoxy group or an ethoxy group, an alkylamino group (e.g. n-butylamino group, dimethylamino group, etc.), a cycloamino group (e.g. piperidino group, pyrrolidino group, etc.), or an amino group such as a heterocyclic amino group. represents an acylamino group such as an alkylacylamino group or an arylacylamino group, an anilino group such as a substituted anilino group or a 2,5-disubstituted anilino group, or a phenylureido group or an N,N-disubstituted ureido group. represents a ureido group such as These groups may further be substituted with the same substituents as in the case of the aryl group described above. Among R ₇ and R ₈ listed above, preferred groups include, for example, phenyl group, naphthyl group, 2-chlorophenyl group, 2,6-dichlorophenyl group,
2,4,6-trichlorophenyl group, 3,5-dibromphenyl group, 3-nitrophenyl group, 4-
(2,4-di-t-amylphenoxy)acetamidophenyl group, pentafluorophenyl group, 4
-phenoxyphenyl group, 2,6-dimethyl-4
-methoxyphenyl group, 3-(N,N-dichloro-4-methoxyphenyl group, 2-chloro-4,6
-dimethylphenyl group, pentachlorophenyl group, 2,6-dichloro-4-carboxyphenyl group, 2,5-dimethoxy-3,4-dichlorophenyl group, 4{α-(3-pentadecylphenoxy )
aryl group represented by phenyl group, etc.; heterocyclic group represented by 2-thiazolyl group, 2-benzothiazolyl group, 2-benzooxazolyl group, 2-imidazolyl group, 2-benzimidazolyl group; or methyl Alkyl groups represented by ethyl group, dodecyl group, 1-phenyl-trifluoroethyl group, etc.; α-(3-pentadecylphenoxy)butyramide group, n-tetradecanamide group, α-(2,4 -di-t-amylphenoxy)butyramide group, 3-[α-(2,4-di-
t-amylphenoxy)butylamide] acylamino group represented by benzamide group, 3-acetylamide benzamide group, etc.; phenylamino group;
2-chlorophenylamino group, 2,4-dichlorophenylamino group, 2,4-dichloro-5-hexadecyloxyanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5 −
Octadecenyl succinimide anilino group, 2-
Chlor-5-[α-{3-t-butyl-4-hydroxy)phenoxy}tetradecanamide]anilino group, 2-chloro-3-[2-{1,3-(1-hexadecyl-5-trifluoromethyl) ) benzimidazo}lyl]anilino group, 2-methoxy-5-
Anilino group or phenylureido group represented by (4-hexadecylbenzamide) anilino group, etc.; ureido group represented by 3-{α-(2,4-di-t-amylphenoxy)butyramide} phenylureido group, etc. . n is preferably 1 to 4. Representative couplers according to the present invention are shown below, but are not limited thereto. (Example coupler) The present invention provides a coupler having a high equivalent weight and excellent color development. The meaning of having a high equivalent number was mentioned above, but the necessity of fast coloring speed is also related to graininess. This is because the presence of excess oxidized developing agent causes bleaching of developed silver nuclei. The coupler according to the present invention is an oxidized form of a developing agent.
Cp couples, Cp first desorbs, and then

After [formula] leaves

A magenta dye-forming coupler represented by the following formula couples with an oxidized developing agent to form a magenta dye. The coupler according to the present invention is

The magenta dye-forming coupler represented by the formula

The raw storage stability was improved by blocking with [Formula]. When the compound produced by coupling Cp with the oxidized form of the developing agent is colored, it is desirable that the compound has diffusivity and flows out of the layer after coupling. Diffusible groups added to Cp include carboxy groups, sulfo groups, hydroxy groups, and the like. In Japanese Patent Publication No. 52-90932,

[Formula] (A is a yellow, magenta, cyan coupler residue, R″ is a hydrogen atom,
Represents an alkyl group, etc.

[Formula] is a 5- to 7-membered heterocycle. A two-equivalent coupler represented by the following is described, in which a dye having A as a core is produced by coupling with an oxidized form of a developing agent, and this dye is used for forming color photographic images. In Japanese Patent Publication No. 53-29717,

[Formula] (A is a cyclic colorless coupler residue, R″ represents a hydrogen atom, an alkyl group, etc.,

[Formula] is a heterocyclic compound having a development inhibiting effect. ) DIR couplers are described. This DIR coupler is produced by coupling with the oxidized form of the developing agent.

[Formula] has left, and from now on

[Formula] is formed and the compound has a development inhibiting effect. It shows. General formula of the present invention ()

After coupling Cp with the oxidized form of a developing agent, the coupler represented by the formula (same as above)

[Formula] was desorbed and generated

[Formula] is coupled with one more mole of the oxidized developing agent to form a magenta dye, which is used to form color photographic images. Therefore, the present invention does not utilize a dye having Cp as a mother nucleus as seen in the above-mentioned known documents, but also uses a dye that is produced by desorption.

This method does not utilize the development inhibiting effect of the formula and is essentially different from the above-mentioned known technology. The coupler according to the present invention is a compound represented by the following formula Cp-X-H and

[Processing process (38℃)]

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixation 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] 4-Amino-3-methyl- N-ethyl-N-(β
-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine (1/2 sulfate) 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and use potassium hydroxide to adjust the pH.
Adjust to 10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using ammonia water.
Adjust to 6.0. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162ml Anhydrous sodium sulfite 12.4g Add water to make 1, and adjust to PH6.5 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. The magenta dye image obtained above was measured with green light using a densitometer (PD-7R manufactured by Konishiroku Photo Industry Co., Ltd.). The same-day sensitivity is expressed as a relative sensitivity value when the sensitivity value of sample (5) is set to 100.
Regarding the treatment at 55°C and 10% RH, the relative sensitivity is shown when the same-day sensitivity of each sample is set as 100. or,
Table 1 shows the measured values for fog and D _nax .

[Table] From Table 1, sample (1) using the coupler of the present invention,
It can be seen that samples (2) and (3) clearly have higher sensitivity and D _nax than the samples using comparative couplers A and B, and show good results with less fog. Also 50℃80%
Sample (5) using Comparative Coupler B has poor raw storage stability even after RH treatment and 10% RH treatment at 55°C, resulting in poor color development, but samples using the coupler of the present invention are not susceptible to heat or humidity. It turns out that it is also very stable. On the other hand, samples (1), (3), obtained by same-day development,
The concentrations of (4) and (5) were measured through a green filter, and then the same portion was measured through a blue filter, and color turbidity (DB/DG x 100) was examined. The results are shown in Table 2.

[Table] As is clear from Table 2, all the samples show almost the same color turbidity, and are completely comparable to the sample using comparative coupler A, which does not have a blocking group. It was observed that the compounds formed by the above were leaked out of the system. Example 2 Example coupler (4) was subjected to exactly the same operation as in Example-1 to obtain sample (6). Further, Samples (7) and (8) were prepared in the same manner as above using Example Couplers (11) and (17) in place of Example Coupler (4). On the other hand, samples (9) and (10) were prepared in exactly the same manner as above using comparative couplers (B) and (C) instead of exemplary coupler (4). Furthermore, for comparison, the comparison coupler (C) is 2×10 ^-2
A sample (11) was prepared by using 1×10 ^-3 mol of DIR-(D) and performing the same operation as above. Comparison coupler (C) These samples (6), (7), (8), (9), (10) and (11) were exposed and developed in the same manner as in Example 1, and their photographic performance was examined.
In addition, these developed samples were exposed to green light at a density of 0.7.
RMS (Root-Mean)
Table 3 shows the results measured by the 2-square method.

[Table] From Table 3, which shows the relative sensitivity when sample (10) is set to 100, the sample using the coupler of the present invention clearly has improved graininess compared to the sample using comparative coupler C. It showed the same graininess as the sample (11) in which DIR substance was used in combination with comparative coupler C and the sample in which comparative coupler B was used. On the other hand, the samples (6) to (11) prepared above were left unexposed in a sealed container containing a 1% formaldehyde aqueous solution in a dark room for 3 days without contact with the liquid. These samples and an untreated sample for comparison were exposed and developed in the same manner as in Example 1, the sensitivity and maximum density were measured, and the formalin resistance % (treated sample/untreated sample x 100) was determined. The results are shown in Table 4. In addition, the samples (6) to (11) prepared above were left unexposed.
It was stored for 3 days under conditions of 50°C and 80% RH. These samples and untreated samples for comparison were exposed and developed in the same manner as in Example 1, and the maximum density was measured.
Table 4 shows the results of examining the raw sample storage stability. The storage stability of fresh samples is calculated by multiplying treated sample/untreated sample by 100.

[Processing process (33℃)]

Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 3 minutes [Color developer composition] 4-Amino-3-methyl-N-ethyl-N-(β
-Methanesulfonamidoethyl)-Aniline sulfate 4.0g Benzyl alcohol 10.0ml Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Potassium bromide 0.2g Anhydrous sodium sulfite 2.0g Diethylene glycol 3.0ml Add water to adjust to 1 and adjust pH to 10.0 adjust. [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 10.0g Sodium metabisulfite 3.0g Add water to 1 and adjust the pH to 6.6. Samples (12), (13), (14) obtained in this way
was irradiated with a xenon fade meter for 4 days, and the light resistance of the color image and the yellow stain in the uncolored area were investigated. Table 5 shows the results. Furthermore, lightfast dye residual rate%
was calculated at an initial concentration of 1.0.

[Table] It is understood from Table 5 that the sample using the coupler of the present invention has excellent light resistance and less yellow stain than sample (14) using comparative coupler B.

Claims (1)

[Scope of Claims] 1. A blocked magenta dye-forming coupler represented by the following general formula (). General formula () (In the above formula, Q represents a group of nonmetallic atoms necessary to form a magenta dye-forming coupler together with a nitrogen atom, [Formula] represents a blocking group, X represents an oxygen atom or a sulfur atom, R and R ′ is a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkenyl group, an aryl group, or a heterocyclic group, and Cp represents a compound capable of causing a coupling reaction with the oxidized form of a developing agent, and X at its active site.
is combined with )