JP2769022B2 - Color photographic recording materials containing pyrazoloazole color couplers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises at least one silver halide emulsion layer and a pyrazoloazole-based color coupler and provides a high color density formed due to the presence of special groups in the ballast residue. And a color photographic recording material capable of forming a magenta color image.

In summary, the use of a color photographic recording material containing a pyrazoloazo coupler of the general formula I as a magenta coupler results in a color photographic image with excellent photosensitive properties, especially a high magenta color density. The recording material is not very sensitive to variations in processing conditions, and in particular shows less tendency to turn yellow after it has been treated in a formaldehyde-free finishing bath.

In the formula PAZ-L ¹ -YL ² -SO ₂ -R I, PAZ represents a pyrazoloazole-based color coupler group capable of performing a color coupling reaction, and L ¹ and L ² represent the same or different. T) represents an alkylene, aralkylene, or arylene group, Y represents O, S, or SO, and R represents alkyl or amino.

Color development, that is, a developer formed corresponding to a silver image by developing an imagewise exposed silver halide emulsion layer with a suitable color developer, a so-called color developer, in the presence of a suitable color coupler It is known that the oxidation products of the above react with the color coupler to form a dye image, forming a color photographic image. The color developer used is generally an aromatic compound containing a primary amino group,
Particularly, it is a p-phenylenediamine compound.

Pyrazolone-based couplers are commonly used to produce magenta dye images. In many cases, dye images formed from these pyrazolone-based couplers do not have ideal light absorption characteristics. The density of the yellow area is very troublesome, and if you want to get a vivid photographic image,
Requires the use of mask couplers or other masking techniques. Another disadvantage of conventional pyrazolone couplers is that they often have poor resistance to formaldehyde attack and the effects of light, heat and humidity during storage.

Another disadvantage is that the pyrazolone couplers remaining in the processed photographic material have a marked tendency to turn yellow during storage, especially when using a formaldehyde-free finishing bath.

Pyrazoloazole-based magenta couplers were found to be superior in many respects. They generally produce a pure color magenta dye image, but it is difficult to obtain sufficient color density by ordinary processing methods. Magenta couplers of the pyrazoloazole type are described, for example, in German Patent Publication 1810462, German Patent Publication 3516996, European Patent Publication 0143570, and European Patent Publication 0176804.

It is an object of the present invention to provide a coupler photographic recording material comprising at least one silver halide emulsion layer and at least one magenta coupler from which a magenta dye having a desired color purity and a high color density can be produced by color development. It is an object of the present invention.

In the present invention, at least one kind of silver halide emulsion layer and at least one kind of the following general formula I PAZ-L ¹ -YL ² -SO ₂ -R I wherein PAZ undergoes a color coupling reaction. Represents a pyrazoloazole-based color coupler group, wherein L ¹ and L ² are the same or different alkylene,
A aralkylene or arylene group; Y represents O, S, or SO; and R represents alkyl or amino; and a pyrazoloazole non-diffusible color coupler represented by

L ¹ is preferably attached to a position which does not cause a coupling reaction of the coupler residue represented by PAZ.

The alkylene residues represented by L ¹ and L ² contain up to 10 carbon atoms. : Preferably containing 2 to 6 carbon atoms and being linear or branched. The aralkylene residue represented by L ¹ and L ² is, for example, Corresponding to

The arylene residue contained in L ² and L ² is preferably a phenylene group, which may be substituted by, for example, C1, alkyl, alkoxy, or acylamino.

The alkyl residue represented by R is straight or branched and contains, for example, up to 20 carbon atoms. The amino group represented by R is mono- or disubstituted by a heterocyclic group such as an alkyl, aralkyl, aryl, or 1,1-dioxothiolane group, or a cyclic amino group such as a pyrrolidino, piperidino or morpholino group. It may be a group.

The alkyl and aryl groups present as substituents in the alkyl group represented by R and the amino group represented by R in Formula I may be further substituted by a nonionic hydrophilic group such as, for example, a hydroxyl group. And may further include substituents such as alkylsulfonyl or arylsulfonyl. The following substituents are examples: The coupler residue PAZ is pyrazolo [3,2-c] -1,2,4
-Triazole group, pyrazolo [2,3-b] -1,2,4-triazole group, pyrazolo [2,3-c] -1,2,3-triazole group, imidazolo [1,2-b] -pyrazole Group, imidazolo [3,4-b] -pyrazole group, pyrazolo [2,3-b]
It may be a pyrazole group or a pyrazolobenzimidazole group. The corresponding structures of these residues are shown by the following formulas I-1 to I-7: In the general formulas I-1 to I-7, the substituents represented by Z ¹ , Z ² and Z ³ are hydrogen, alkyl, aralkyl, aryl, alkoxy, alloxyalkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl , Carbamoyl, or sulfamoyl, these residues may be further substituted, and two adjacent residues Z ² and Z ³ form a fused ring, optionally a substituted benzene ring In some cases.

Formula I-7 is a special case of the substituents Z ² and Z ³ of formula I-4 to form a benzene ring fused. In this formula, Y ¹ , Y ² and Y ³ represent H, Cl, alkyl, alkoxy, alkylthio, alkylsulfonyl, CF ₃ , acylamino or sulfo.

At least ^{one of} the residues Z ¹ , Z ² and Z ³ , or (formula I
−7) at least ^{one of} residues Z ¹ , Y ¹ , Y ² and Y ³
Is a residue represented by the following formula: -L ¹ -YL ² -SO ₂ -R wherein the symbols have the previously defined meanings.

In the formulas I-1 to I-7, X represents hydrogen or a residue which can be eliminated during a color coupling reaction, for example, a halogen atom or a group condensed to a coupling position via oxygen, sulfur or nitrogen. Preferably the group at the position is a cyclic residue.

When the leaving group is a cyclic residue, the condensation at the position where the coupler molecule is bonded may be direct bonding, or when the bonding is via an atom that becomes a part of the ring, for example, a nitrogen atom. Alternatively, they may be indirectly bonded via an intermediate bonding atomic group. Many such detachable atomic groups are known, such as the divalent magenta coupler's fragile atomic group.

Examples of eliminable residues attached via oxygen include the following formula: -OR ^{1 wherein} R ¹ is derived, for example, from an alkyl, aryl or heterocyclic group, or an organic carboxylic acid or sulfonic acid. Represents a cyclic or non-cyclic organic residue such as an acyl group to be formed. Especially preferred removable residues R ¹ of this type, sometimes represents a phenyl group having a substituent.

Examples of releasable residues linked via nitrogen are the following German Patent Publication Nos. 2536191, 2703589, 2713522.
And No. 3339201.

These residues are often 5-membered heterocyclic rings that are attached to the position at which the coupling reaction of the magenta coupler occurs by a ring nitrogen atom. These heterocycles often contain an active group such as a carbonyl, sulfonyl, or double bond at a position adjacent to the nitrogen atom that bonds to the coupler molecule.

When the eliminable residue is bonded via a sulfur atom to the position where the coupling reaction of the coupler occurs, a residue of a diffusible carbocyclic or heterocyclic mercapto compound which can inhibit the development of silver halide. It is. Residues of such inhibitors are often described as releasable groups attached to the coupling site of a coupler such as a magenta coupler, for example, in US Pat. No. 3,227,554.

The following compounds are examples of pyrazoloazole-based couplers according to the invention: Carboxylic acids and their carboxylic acid derivatives such as iminoethers and orthoesters are often used as intermediates for the synthesis of the pyrazoloazole couplers according to the invention.

The synthesis of these compounds is carried out, for example, as follows: The coupler according to the invention can be synthesized by different routes: The couplers according to the invention have not only the excellent spectral properties of the dye images produced therefrom and the excellent stability of the emulsion, but also when developed according to the usual color developing methods.
Since the dye is produced in a high yield, it is particularly excellent in that a high color density can be obtained. In addition, their coupling activity is less affected by fluctuations in the pH of the developer, especially the occasional inevitable drop in pH. This characteristic is particularly advantageous for the photosensitive characteristics of the color photographic recording material.

In producing a photosensitive color photographic recording material, the coupler having a high diffusion rate according to the present invention can be added to a coating solution for a silver halide emulsion layer or another colloid layer according to a known method. For example, an oil-soluble or hydrophobic coupler is advantageously added to the hydrophilic colloid liquid as a suitable coupler solvent (oil former) solution, optionally in the presence of a wetting or dispersing agent. Of course, the hydrophilic coating solution contains other usual additives in addition to the binder. The coupler solution does not need to be directly dispersed in the coating solution of the silver halide emulsion layer or other water-permeable layer, but is initially dispersed in an aqueous solution of a non-photosensitive hydrophilic colloid. It is also advantageous to remove the used low-boiling organic solvent, if necessary, and then to add it to the coating solution for the photosensitive silver halide emulsion layer or other water-permeable layer immediately before coating.

The photosensitive silver halide emulsion used may be silver chloride, silver bromide, or a mixture thereof, dispersed in one of the commonly used hydrophilic binders, and in some cases, small amounts of up to 10 mol% silver iodide. An emulsion comprising: The binder used in the photographic layer is preferably gelatin, but part or all of it can be replaced by other natural or synthetic binders.

The emulsion can be chemically or spectrally sensitized according to a conventional method, and the emulsion layer can be formed, similarly to other non-photosensitive layers, according to a known method using a known curing agent, especially a carboxyl group such as carbamoylpyridinium salt. (See, for example, German Patent Publication Nos. 2225230, 2317677 and 2439).
No. 551).

Color photographic recording materials usually have three spectral wavelength ranges,
It contains at least one silver halide emulsion layer corresponding to each of red, green and blue, and each of these photosensitive layers has a suitable sensitizing dye for recording light in each spectral wavelength range. Sensitized by a known method. However, a silver halide emulsion layer that feels blue light does not necessarily need to contain a spectral sensitizing dye because the intrinsic sensitivity of the silver halide is often sufficient to record blue light.

Each of the aforementioned photosensitive layers may consist of a single layer, for example, in a double-layer arrangement (DE 1121470).
In some cases, two or more silver halide emulsion partial layers are included by a known method referred to as (1).
The silver halide emulsion layer that senses red light is usually located closer to the support than the silver halide emulsion layer that senses green light, and the latter is located closer to the support than the layer that subsequently senses blue light. , And other arrangements are possible,
A non-photosensitive yellow filter layer is usually disposed between the layer that senses green light and the layer that senses blue light. The layers with different spectral sensitivities are separated by a non-photosensitive intermediate layer which usually contains substances to prevent unwanted diffusion of the oxidation products of the developer. When several silver halide emulsion layers have the same spectral sensitivity, they may be directly adjacent to each other or may be separated by a photosensitive layer having another spectral sensitivity ( German Patent Publication Nos. 1958709, 2530645 and 2629222
issue).

Color photographic recording materials for forming multi-color images by color development usually include different silver halide emulsion layers with different spectral sensitivities and spatial positions and to produce images of different color separations, cyan, aagenta and yellow. A non-diffusible color coupler is included so that the spectral characteristics correspond.

“Spatial position correspondence” means that the color coupler spatially corresponds to the silver halide emulsion layer so that the silver image produced by development interacts with the dye image produced by the color coupler to obtain a consistent image. Means that it exists. This can generally be achieved by including the color coupler in the corresponding silver halide emulsion layer itself, or in a non-photosensitive adjacent binder layer.

The "correspondence of spectral characteristics" means that the spectral sensitivity of each photosensitive silver halide emulsion layer and the color of the separated color image generated from the color coupler corresponding to the spectral characteristics have a complementary color relationship with each other, that is, the respective spectral sensitivities (red , Green, and blue) from the photosensitive layer having a corresponding color (generally cyan, magenta, and yellow).

One or more color couplers may each correspond to a spectrally sensitized silver halide emulsion layer. When several silver halide emulsion layers have the same spectral sensitivity, these colors can be used as long as the color coupler develops a color corresponding to a color complementary to the color of the main photosensitive wavelength range of the silver halide emulsion layer by color development. The emulsion layers of the present invention may contain the same color coupler or separate color couplers.

Thus, in a preferred embodiment, the silver halide emulsion layer sensitive to red light comprises at least one or more non-diffusible color couplers, generally of the phenol or alpha-naphthol type, corresponding to the cyan separation image. The silver halide emulsion layer sensitive to green light comprises at least one or more non-diffusible color couplers corresponding to the magenta separation image, the color coupler of formula I in the present invention, and a halogen sensitive to blue light. The silver emulsion layer contains at least one or more non-diffusible color couplers, generally having an acyclic ketomethylene group, to produce a yellow dispersion image. Many color couplers of this type are known and have been described in numerous patent publications and other documents; see, for example, W. Pelz, "Agfa, Republsen / Munich Institute Report," Vol. 8, page 111 (1961). ) Papers "Color Couplers" and "The Chemistry of Synthetic Dye"
s) "(Academic Press, 1971), vol. 4, pages 341 to 387, see the dissertation" Color Coupler "by K. VENKATARAMAN.

Color couplers include four-equivalent couplers and two-equivalent couplers. The latter is derived from a 4-equivalent coupler, which has a substituent at the coupling position that is eliminated during the coupling reaction, as is known. Two-equivalent couplers include essentially colorless couplers and couplers (masking couplers) which have an inherently strong color but which disappear by the color coupling reaction and change to the color of the image dye. Known white couplers produce a substantially colorless product upon reaction with the oxidation product of a color developer, but are basically classified as two equivalent couplers. The two-equivalent coupler has a removable group released during the reaction of the color developer with the oxidation product, either directly or after one or more further groups have been released from the initially released group. For example, some couplers have a group having a specific photographic activity, for example, as a development inhibitor or accelerator, in a coupling reaction position (for example, German Patent Publication Nos. 2703145, 2855697, 31st publication).
No. 05026 and 3319428). DIR coupler, D
AR and FAR couplers are examples of such bivalent couplers.

Examples of suitable DIR couplers are, for example, GB 953454, DE 1800420, 201
No. 5867, No. 2414006, No. 2842063, No. 3427235
And EP-A-0287833.

Suitable DAR and FAR couplers are described, for example, in British Patent Publication No. 1591641, German Patent Publication No. 3209110, European Patent Publication Nos. 0089834, 0117511 and 0118.
No. 087.

For DIR, DAR and FAR couplers, the activity of the groups released during the coupling reaction is mainly important, and the color properties generated from this coupler are less important, as described, for example, in DE-A-1547640. There are also DIR, DAR and FAR couplers that result in a substantially colorless product upon the coupling reaction.

The leaving group may be, for example, as described in U.S. Pat.No. 4,420,556, in which the coupling product obtained by reaction with the oxidation product of the color developer is diffusible, or at least weak or limited. Since it is a dye having mobility, it may be a ballast group.

High molecular weight color couplers are described, for example, in German Patent Nos. 1297417, 2407569 and 314812.
No. 5, No. 3217200, No. 3320079, No. 3324932,
No. 3333743, No. 3340376, European Patent Publication No.
No. 27284 and U.S. Pat. No. 4,802,111. A high molecular weight color coupler is generally synthesized by addition polymerization of a monomeric color coupler having an ethylenically unsaturated group, but can also be synthesized by polyaddition or polycondensation.

The color photographic recording material according to the invention comprises at least one coupler of the structure corresponding to formula I. The advantages provided by this are shown, for example, in the embodiments described below. Although the exact mechanism has not been revealed in detail, the advantages of the coupler according to the invention are:
It is believed to be based on the structure of the coupler corresponding to Formula I, especially the special structure represented by the following formula: -L ¹ -YL ² -SO ₂ -R.

The characteristic groups of the couplers represented by Formula I have no significant effect on the spectral properties of the resulting dye image, but have a beneficial effect on the maximum color density obtained and the stability of the color developer to fluctuations in pH. There is.

The color photographic recording material according to the present invention may contain, in addition to the above-mentioned components, other additives such as an antioxidant, a dye stabilizer and an agent for improving mechanical and electrostatic properties. To remove or reduce the undesirable effects of ultraviolet light on the color images formed by the color photographic recording materials according to the present invention, for example, in one or more layers, preferably one of the upper layers in the recording material Advantageously, an ultraviolet absorber is used. Suitable UV absorbers are described, for example, in U.S. Pat.
No., German Patent No. 2036719 and European Patent Publication 0
No. 057160.

To form a color photographic image, the color photographic recording material of the present invention having at least one or more silver halide emulsion layers and at least one or more layers containing a coupler of Formula I corresponding to a color developer Is developed. The color developer used is one capable of reacting with a color coupler to form an azomethine dye when it becomes an oxidation product. P- having at least one primary amino group
Phenylenediamine-based aromatic compounds such as N, N-
Diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3-ethyl-
p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3
N, N-dialkyl-p-phenylenediamine, such as -methyl-p-phenylenediamine, is a color developer suitable for this purpose.

Other preferred color developers are, for example, J. Ame
r. Chem. Soc. 73 , 3100 (1951) and G. Heist (Hais
t) “Modern Photographic Pro
cessing) "(John Wiley and Sons, New York, 1979)
545 pages and below.

The photographic recording material is usually bleached and fixed after color development. Bleaching and fixing may be performed separately or simultaneously. Usual bleaching agents include, for example, ferricyanides and bichromates such as Fe
³⁺ salts, Fe ³⁺ complexes, water-soluble cobalt complexes, and the like are used. For example, iron (III) complexes of aminopolycarboxylic acids and corresponding iron (III) complexes of sulfonic acid, such as ethylenediaminotetracomplex acid, N-hydroxylethyl-ethylenediamino-tricomplex acid, and alkyliminodicarboxylic acid, Particularly preferred persulfates are preferred as bleaching agents.

Example 1 8 mMol of any of the following magenta couplers is dissolved in ethyl acetate (EA) at about 50 ° C. at a weight ratio of 1: 3, and dibutyl phthalate (DBP) and manoxol (sulfosuccinic acid-di-n-octyl ester) Is added so that the final ratio becomes coupler: DBP: EA: manoxol = 1: 1: 3: 0.1.

The reaction mixture is then emulsified in a 7.5% gelatin solution. The emulsion is stirred at 1000 rpm for 6 minutes, during which the temperature rises to about 50 ° C., after which the EA is removed by distillation under reduced pressure of a water pump (200-300 mbar).

The obtained emulsion was mixed with a silver iodobromide (0.7 mol% of silver iodide) emulsion at a molar ratio of AgNO _{3 of} 5.2 mol per 1 mol of the coupler, coated on a support layer of cellulose acetate, and further cured. A protective layer of a 3% gelatin solution containing carbamoylpyridinium petaine as an agent is applied (CAS Reg. No. 654411-60-1). After the sample has dried, cut it into a band, and after exposing the band, slowly immerse it in a color developing bath having the following composition at a constant speed within 200 seconds at a constant speed, take it out of the bath, and then perform the post-processing described below. I do. Bath time (min) Bleaching bath 6.5 Washing bath 3.0 Fixing bath 6.5 Washing bath 6.0 The following baths were used: Color developing bath In 800 ml of water 17 g of sodium hydroxyethanediphosphate 17 g of ethylenediaminetetraacetic acid (EDTA) 12 g of 1- (N-ethyl) -N-Hydroxyethyl) -3-methyl-p-phenylenediamine 47 g Hydroxyammonium sulfate 25 g Sodium sulfite 39 g Sodium hydrogen carbonate 15.5 g Potassium carbonate 335 g Dissolve 13.5 g of bromide color and add 10 to water; pH 10. 0.

Bleaching bath Dissolve 800 g of water in 800 ml of ammonium bromide 1390 g EDTA NH ₄ -Fe salt 865 g EDTA 163 g ammonia 100 g, add water to make 10 and pH 6.0 with about 15 ml of glacial acetic acid
Adjust to ± 0.1.

Settling bath Dissolve 800 g of ammonium thiosulfate in 800 ml of water, 100 g of sodium sulfite, 20 g of sodium hexametaphosphate, and add water to 10; pH 7.5.

A second sample of the coated and dried strip was treated similarly, but the color developing bath was adjusted to pH 9.0.

After bleaching and fixing, these samples were measured with a densitometer,
It was found that the color density had an effective development time dependency as shown in FIGS.

Here, the following magenta coupler was used: FIG. 1: coupler M-4 FIG. 2: coupler M-12 FIG. 3: Comparative coupler CM-1 corresponding to the following equation: The coupler according to the present invention not only causes a more rapid coupling reaction at pH 10 but also changes in pH, especially
Not very sensitive to pH drop. Even at pH, sufficient color density is obtained after only 150 seconds of development.

Example 2 Couplers according to the invention, M-8, M-10, M-12 and M-41, and comparative couplers, CM-2, CM
-3 and CM-4 layers were prepared as in Example 1, exposed through a step wedge, and processed as in Example 1 (development time 200 seconds).

Other pH of color developing bath is 9.6, 9.8, 10.2 and 10.4
The development was carried out while adjusting and changing the values. Table 1 shows the obtained magenta color densities.

The following comparative symmetric coupler was used: Example 3 The layers of the couplers M9 and M-17 according to the invention and the control coupler CM-5 were prepared as in Example 1 and post-exposed through a step wedge as in Example 2.

In addition, a series of treatments was performed using a formaldehyde-free finishing bath.

The resulting samples were stored for 0, 7, 14, and 28 days in a cabinet air conditioned at 80 ° C. and 50% relative humidity.

 Thereafter, the density in the yellow region was measured.

The following control coupler was used: Example 4 A color photographic recording material for negative color development was produced by coating the following layers on a transparent cellulose triacetate support layer. In all cases, it is represented by the amount of per 1m ^2. The amount of silver halide applied is expressed by the corresponding amount of AgNO ₃ . All silver halide emulsions, the AgNO ₃ 100 g per 0.5 g 4-hydroxy-6-
It is stabilized by methyl-1,3,3a, 7-tetraazaindene.

First layer (antihalation layer) Black silver colloid sol containing the following components: 0.18 g of Ag, UV-1 0.30 g of UV absorber, 1.5 g of gelatin.

Second layer (intermediate layer) AgNO ₃ 0.15 g of silver iodobromide (silver iodide 0.8 mol%) emulsion containing the following additives: 0.15 g of 2,5-dioctylhydroquinone, 0.11 g of coupler RM-1 and 0.3g of gelatin.

Third layer (first red light sensitive layer) AgNO ₃ sensitized to 0.7 g AgNO ₃ silver iodobromide (0.5 mol% silver iodide) emulsion containing the following additives: Coupler C- 1 0.1 g, coupler C-2 0.3 g, coupler DIR-1 0.01 g, and gelatin 1.2 g.

Fourth layer (second red light sensitive layer) 1.2 g of AgNO ₃ sensitized to red light and containing the following additives, silver iodobromide (silver iodide 10 mol%) emulsion: Coupler C- 1 0.1 g, coupler C-2 0.05 g, coupler C-3 0.05 g, and gelatin 0.9 g.

Fifth Layer (Third Red Light Sensitive Layer) 2.0 g of AgNO ₃ sensitized to silver iodobromide (10 mol% silver iodide) emulsion sensitized to red light, containing the following additives: Coupler C- 2 0.05 g, coupler C-3 0.15 g, coupler DIR-2 0.003 g, and gelatin 0.8 g.

6th layer (intermediate layer) Gelatin 0.5g 7th layer (first green light sensitive layer) 0.5g of AgNO ₃ sensitized to green light containing the following additives: silver iodobromide (silver iodide) (5 mol%) Emulsion: 0.3 g of coupler CM-6, 0.4 g of coupler YM-1, 0.5 g of coupler YM-2, 0.5 g of coupler DIR-3, and 1.2 g of gelatin.

Eighth Layer (Second Green Light Sensitive Layer) 1.0 g of AgNO ₃ sensitized to green light and containing the following additives, silver iodobromide (silver iodide 6 mol%) emulsion: Coupler CM- 6 0.25 g, coupler YM-1 0.01 g, coupler YM-2 0.01 g, coupler DIR-3 0.01 g, and gelatin 1.7 g.

Ninth layer (third layer sensitive to green light) 1.5 g of AgNO ₃ sensitized to green light and containing the following additives: silver iodobromide (10 mol% silver iodide) emulsion: Coupler YM- 1. 0.015 g, coupler CM-7 0.07 g, coupler FAR-1 0.002 g, and gelatin 1.0 g.

10th layer (yellow filter layer) Yellow silver colloid sol containing the following components: 0.05 g of Ag, 0.03 g of 3,5-di-t-octylhydroquinone, and 0.6 g of gelatin.

Eleventh layer (first blue light sensitive layer) AgNO ₃ 0.3 g silver iodobromide (5 mol% silver iodide) emulsion containing the following additives: coupler Y-1 0.7 g, coupler DIR-4 0.03 g, and 1.4 g gelatin.

12th layer (second blue light sensitive layer) AgNO ₃ 0.3 g silver iodobromide (5 mol% silver iodide) emulsion containing the following additives: coupler Y-1 0.25 g, and gelatin 0.6 g .

Thirteenth layer (microlate layer) AgNO ₃ 0.4 g silver iodobromide (silver iodide 2 mol%) emulsion containing 0.1 g gelatin.

Fourteenth layer (third blue light sensitive layer) AgNO ₃ 0.8 g silver iodobromide (10 mol% silver iodide) emulsion containing the following additives: coupler Y-1 0.2 g, and gelatin 0.5 g .

Fifteenth layer (first protective layer) UV absorber UV-1 0.14 g, UV absorber UV-2 0.20 g, and gelatin 0.4 g.

Sixteenth layer (second protective layer) Hardener, CAS Reg. No. 65411-60-1 0.95 g, and gelatin 0.23 g.

The recording material thus manufactured is referred to as a recording material A (not according to the present invention). The recording material B according to the present invention is manufactured in the same manner, but differs from the recording material A only in that a coupler M-8 is used in place of the couplers CM-6 and CM-7 of the seventh, eighth and ninth layers.

Exposure and processing were performed in the same manner as in Example 1 to obtain the following Table 3.
Photosensitivity data was obtained as shown below: 10 ppm of recording materials A and B at 70% relative humidity before exposure
m, for 0, 3, 7, 14 and 21 days, respectively, exposure and processing to obtain Dmax values as shown in Table 4 below: The following compounds were used: The main features and aspects of the present invention are as follows.

1. at least one silver halide emulsion layer and at least one general formula I PAZ-L ¹ -YL ² -SO ₂ -R I wherein PAZ is a pyrazolo capable of undergoing a color coupling reaction Represents an azole color coupler group, wherein L ¹ and L ² are the same or different alkylene,
A color photographic recording material comprising: a aralkylene or an arylene group; Y represents O, S, or SO; and R represents an alkyl or an amino.

2. When the PAZ of the formula I is a pyrazolo [3,2-c] -1,2,4-triazole group, a pyrazolo [2,3-d] -1,2,4-triazole group, a pyrazolo [2,3- c] -1,2,3-triazole group, imidazolo [1,2-b] -pyrazole group, imidazolo [3,4
The recording material according to claim 1, wherein the recording material represents a -b] -pyrazole group, a pyrazolo [2,3-b] pyrazole group, or a pyrazorobenzimidazole group.

3. The following formulas I-1 to I-7 In the formula, X represents H or a residue which can be eliminated during a color coupling reaction, and Z ¹ , Z ² and Z ³ represent H, alkyl, aralkyl, aryl, alkoxy, alloxy, alkylthio, arylthio, amino, anilino, Represents acylamino, cyano, alkoxycarbonyl, carbamoyl or sulfamoyl; Y ¹ , Y ² and Y ³ represent H, Cl, alkyl, alkoxy, alkylthio, alkylsulfonyl, CF ₃ , acylamino or sulfo; At least one of the substituents represented by Z ¹ , Z ² and Z ^{3 in} Formula I-6 and less than one of the substituents represented by Z ¹ , Y ¹ , Y ² and Y ³ in Formula I-7 least one alkylene here following formula _{^{-L 1 -Y-L 2 -SO 2}} -R, L 1 and L ² are comprising (identical or differ) 10 or fewer carbon atoms, Formula Represents an aralkylene group or a phenylene group corresponding to, Y represents O, S or SO, and R represents an alkyl group or an amino group containing not more than 20 carbon atoms. Recording material according to claim 1, characterized in that it comprises a color coupler represented by one of the following.

4. In the formula I, the alkyl or aryl group represented by R or the alkyl or aryl group present in the substituted amino group represented by R is substituted by a nonionic hydrophilic group. 2. The recording material according to item 1.

[Brief description of the drawings]

FIG. 1 shows a coupler M-4, and FIG. 2 shows a coupler M-12.
FIG. 3 shows the relationship between the color density and the effective development time when the coupler CM-1 is used.

Continuation of the front page (72) Inventor Harii Elias Day 5090 Leif Elksen Huon-Diehlgardt-Schülase 48 Germany (56) References JP-A-63-30847 (JP, A) JP-A-63-231341 ( JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 7/38 G03C 7/32

Claims (1)

(57) [Claims] (1) at least one silver halide emulsion layer and at least one of the following general formulas I PAZ-L ¹ -YL ² -SO ₂ -R I wherein PAZ undergoes a color coupling reaction; L ¹ and L ² (same or different) each represent an alkylene, aralkylene, or arylene group, Y represents O, S, or SO, and R represents an alkyl group. Or a color photographic recording material comprising a non-diffusible pyrazoloazole color coupler represented by