Multilayer silver halide material containing a white coupler
United States Patent 1191 Murin et al. 1 Apr. 8, 1975 [54] MULTILAYER SILVER HALIDE MATERIAL 3,155,510 11/1964 Nogradi et a1. 96/100 CONTAINING A WHITE COUPLER 3,580,722 5/1971 Sakamoto et al. 96/100 [76] Inventors: Borys Murin, Agfa-Gevaert AG, FOREIGN PATENTS OR APPLICATIONS Werk Perutz, Kistlerhofstrasse 75, 8 914,145 12/1962 United Kingdom 96/100 Munich 25; Walter Puschel, Agfa-Gevaert AG, D-509O Primary E.\&#39;aminerJ. Travis Brown Leverkusen-Bayerwerk; Hans Attorney, Agent, or F irmConnolly and Hutz Glockner, Agfa-Gevaert AG, Werk Perutz, Kistlerhofstrasse 75, 8 [57] ABSTRACT Mumch of Germany Color photographic&#39;material containing as a white [22] Filed: Mar. 11, 1974 coupler of a pyrazolone derivative of the formula [211 App]. No.: 449,596 HN Related US. Application Data I [63] Continuation of Ser. No. 247,291, April 25, 1972, 01c abandoned, which is a continuation-in-part of Set. No. 13,805, Feb. 24, 1970, abandoned. 2  
 [30] Foreign Application Priority Data wherein Feb. 24, 1969 Germany 1909067 1 is alkyl, substituted or unsubstituted;  
  R is a radical with at least 8 carbon atoms, a phenyl 521 U.S. c1 96/74; 96/100 group Substituted with Suite or an 1 group; 1511 1m. 01. 003C 1/40 1 is hydrogen or alkyt, halogen. p. [58] Field of Search 96/100, 74 alkylsulfonyl,  
  and wherein R and/or R may carry a straight or [5 References Ci d branched aliphatic hydrocarbon radical which pre- UNITED STATES PATENTS vents diffusion. R represents a phenyl or a 2- 2,998,314 8/1961 Puschel 96/100 phenoxyethy] group 3,028,238 4/1962 Puschel et a1 96/100 2 Claims, No Drawings BACKGROUND OF THE INVENTION The invention relates to novel compounds for the improvement of the color quality of multi-layer dye images which are obtained by chromogenic development of imbedded color couplers in color photographic multi-layer materials.  
  The improvement of the color reproduction of color materials by using the so-called white coupler is known (see W. Pueschel, Mitteilungen aus den Forschungslaboratories [Reports from Research Laboratories] of Agfa-Gevaert AG., Leverkusen-Munich, 1964, Vol. IV, pp. 35 2367). The effect of these white couplers is based on the fact that they react with the oxidation products of developer substances to result in colorless compounds. They are used where undesired oxidation products of developer substances should be eliminated in order to avoid a deterioration of the color quality of the image. Generally, a high developing activity is required of such white couplers.  
  In the German published application No. 1,155,675 and in the British Pat. No. 914,145, there are suggested for the stated purpose inter alia pyrazolone developers carrying in the coupling position an unsubstituted or a substituted alkyl group. The pyrazolone white couplers disclosed in these patents, however, are relatively weak in their developing activity, so that they insufficiently fulfill their purpose of reacting with undesired oxidation products of developer substances. Quickly reacting compounds are therefore of great interest for the preparation of color photographic materials.  
  It is an object of this invention to provide a color photographic material in which there is reduced secondary color density in the developed material.  
  It is another object of this invention to provide multilayer dye containing photographic material having improved characteristics.  
  A still further object is to minimize color fog and improve the gradation of photographic material by adding pyrazolone white couplers.  
 SUMMARY OF THE INVENTION According to the invention, it has been established that the pyrazolone derivatives which are particularly active and consequently are very well suited for the im- 15 provement of the color quality of multi-layer dye images, having the following general formula:  
 wherein R is a methyl, ethyl or cyanoethyl group; R is a radical with at least 8 carbon atoms, a phenyl group substituted with sulfo or an 011,, group; R is hydrogen, alkyl, halogen, a sulfo group, alkylsulfonyl; R represents a phenyl or a 2-phenoxyethyl group; wherein R and/or R may carry a diffusion-preventing straight or 30 branched aliphatic hydrocarbon radical.  
 DETAILED DESCRIPTION OF THE INVENTION White couplers of the invention are the following compounds, for example:  
  3 4 III, H  
  D -O-CO-NH-C C-CH CH -CN n 2 2 M H c 3 3 \N/ Compounds Il-V are derivatives of carbamic acid.  
 3L H They are particularly suitable for the purpose of the invention. The white couplers of this invention illustrated cl by Compounds l-Vll have in the group in the 3- t 3 position of the pyrazole ring the particular group of N 0% radicals which provide the improved developing activ- C H 0 ity.  
  29 In the instance where it concerns diffusion-proof compounds, the application of the novel white developers may take place either by imbedding into one or several separating layers between the developercontaining emulsion layers or they may be directly Cl added to the developer-containing emulslon layers. In the first instance, the developing oxidation products 01 0-03 --CH -0 O-NH-CHH-CH n GUI-H29 fo diffusing from an emulsion layer to an adjacent layer (11, are apprehended in the separating layer, whereby a color falsification is avoided. In the second instance,  
 the gradation of a layer may be controlled, which is im- 2 5 portant for the correct gradation of color shades. In the latter type of application, the advantages of the use of high silver halide amounts may also be utilized.  
 The novel diffusion-proof white couplers may be introduced into the gelatin separating layer or into the 18 37 emulsion layer in accordance with known processes.  
 U Preferably, dispersions are prepared in a known manner from the water-insoluble compounds. This may take place, for example, by dissolving in a low-boiling solvent, e.g. ethyl acetate, and subsequent dispersion in gelatin solution with the aid of a wetting agent. In order H to avoid crystallization of the compounds, a so-called I oil former may be employed in addition. NH C C.CH Compounds with sulfo-groups or with carboxyl grou- 3 ps in the form of aqueous-alcoholic solutions of an al- 3 N C kali salt may be added to the gelatin solution or to the \o 5 emulsion. Non-diffusion proof novel white couplers may also be added to the photographic baths, specifically to the color developer. Used in this manner, color fog can be avoided and the gradation of the material can be controlled.  
  The diffusing compounds are added to a processing bath in the form of an aqueous, alcoholic or aqueousalcoholic solution, if necessary with the aid of alkali.  
  A comparison of the properties of the novel white coupler having the above-mentioned vital group in 3- position with previously known white couplers without an acylamino group in the 3-position of the pyrazole ring, when conducted by dispersing the novel white coupler and the previously known white coupler in identical but separate parts of a gelatin solution containing a blue-green coupler, showed that, on exposure, in the subsequent developed color negative the color density of the blue-green coupler in the part containing the novel white coupler had substantially less density than in the other part. This lesser density is attributable to the higher reactivity of the white coupler of this invention.  
  The preparation of the novel white couplers may occur according to principally known processes.  
 EXAMPLE I A color photographic negative material is synthesized as follows:  
 1. On the carrier a spectral red-sensitized layer which contains a color coupler for blue-green is placed.  
 2. On that red-sensitized layer is placed a separating layer which contains the white coupler of formula ll. The separating layer is ca. 1 p. thick; the ratio of white coupler to gelatin is 1:2.  
 3. On that separating layer is placed a green-sensitive layer with a color coupler for purple.  
 4. A yellow filter layer of colloidal silver.  
 5. A spectral non-sensitized, hence blue-sensitive,  
 layer with a color coupler for yellow.  
  As a comparison to this material A, a corresponding material B is synthesized, wherein the separating layer 2 contains no white coupler but only consists of an equally thick gelatin layer.  
  From assays of both materials are prepared color extract wedges behind the filters blue, green and red. The wedges are then subjected to a normal color negative developing process; color developing substance is N- ethyl-N-(-methanesulfonamidoethyl)-3-methyl-4- aminoanilinosulfate.  
  In comparing the wedges, the following is determined: The purple wedge with white coupler A shows a pure purple, the purple wedge without white coupler B, however, is more bluish tinged. The measurement in the densitometer indicates that the secondary color density behind the red filter in B is about 20% higher than in A. Thus the white coupler of this invention with the described group in the 3-position of the pyrazole ring improves the picture quality in color reproduction of color materials.  
 The same holds true for both blue-green wedges; Thesecondary color density behind the green filter without the white coupler is about higher than with the white coupler.  
  The white coupler employed in this example was prepared as follows:  
 STEP 1 -Methyl-8 imino-8-ethoxy-propionic acid ethyl ester (&#34;methyl-maloniminoether) To 230 g -cyanopropionic acid ethyl ester in 100 ml absolute alcohol were added 68 g HCl gas while cooling with ice water. Temperature l5-20C. The reaction mixture was cooled several days. Then the crystal mass finely ground with benzine/benzole (1:1) and the crystals separated and washed with benzine/benzole mixture. Dried by means of KOH. Yield 230 g, F. C.  
 STEP 2 p-Methylsulfonylhydrazine 276 g p-aminophenyl-methylsulfone in 3 1. water and 520 ml concentrated hydrochloric acid are diazotized with 1 12 g sodium nitrite in ml water. The diazonium salt solution is poured while stirring into 1680 g Na SO .7l-l O in 1680 ml water; pH is kept at 7-7.5; heated for one hour to 80C and then 960 ml concentrated hydrochloric acid are added. Then this was vaporized until dry. The residue was boiled with 1.6 1. water and 0.8 l. concentrated hydrochloric acid for one hour. After cooling drawn off and the precipitate dissolved in 1.5 1. water and then suspended with ammonia to pH 7. After cooling, the precipitated hydrazine is drawn off and dried. Yield g, F. 134C.  
 l-( 4 -Methylsulfo-phenyl)-3-amino-4-rnethylpyrazolone-(5) STEP 4 2-Tetradecyl-4-chloro-5-methylphenol 1,000 g 4chloro-m-cresol (Raschit) are melted in an oil bath at 70C and 14 g bortrifluoride are introduced in 10 minutes. In two hours to this are added by drops 393 g 1-tetradecene at 70C, restirred for one hour, then poured into a mixture of 2 1. water and 0.9 l. soda lye of 30% and well stirred for 5 minutes. After the layers have separated, the aqueous layer is rejected. The oil layer is then washed twice with soda lye, then treated with thinned hydrochloric acid and the oil layer is taken up in 600 ml. methylene chloride. After drying, methylene chloride is evaporated and the residue distilled in vacuo. Yield 520 g, Kp 0.05 mm l65l70C.  
 STEP 5 2-(2-Tetradecyl-4-chloro-5&#39;-methylphenoxy)- ethanol-(l) 34.5 g sodium are dissolved in 260 ml methanol. In the solution are dissolved now 408 g phenol from step 4 while stirring and subsequently 73.5 g 2- chloroethanol are added. After 3 hours again 73.5 g 2- &#39;highly viscous oil is then further processed without purification.  
  The layer is poured into three variants:  
 STEP 6 manner. The processing of the wedges occurs in a color reversal process. The developing substance is Z-methyl- 4-diethylamino-aniline sulfate. The wedges are measured behind red, green and blue filters.  
  1M0 950 ml toluol y) are introduced in 40 minutes The results obtained from behind the red filter char- While Stirring 150 g phosgene- Thereto are added y acterize the properties of the blue-green layer. The fol- 2-(2&#39;-Tetradecyl-4&#39;-chloro-5 -methylphenoxy)-ethylchloroformate-( l drops within 3 hours a mixture of 400 g Phenoxyethal wi values are measured, E being the expresnol from step 5, 126 g dim thylanilin, 0 t01ll0lsion for the usable sensitivity and in particular log It of After standing overnight there are added to the reac-- (D col f /2) tion solution 600 ml cold water and air is blown 10 through until the excess phosgene is removed. The water is separated from the toluol solution, and the tolu, E  
 uol solution is additionally thinned with HCl and washed with water. After distilling off the toluol there remain ca. 440 g oily residue with a content of 92-95% 5 2.78 2. l 4 Comparison 2.18 1.87 0.8 DlN 1.60 1.30 1.2 DIN of chloroformic acid ester.  
  STEP 7 The white coupler lIl mentioned in this Example is White coupler of the formula prepared as follows:  
 267 g Pyrazolone of Step 3 are dissolved in 1.5 l. pyri- STEP 1 dine and mixed with 66 g aluminum chloride. The reaction is exothermic. After cooling to 45C 490 g chloro- Color coupler of the formula formic acid ester of Step 6 (100%) are added and after 3 hours poured on thinned hydrochloric acid, the hydrochloric acid then being separated, washed with 0 0-51 5 thinned hydrochloric acid and the oily cake taken up with acetone, treated with animal charcoal and the fil- N 9* trate mixed with benzine (ca. 4 1.). The acetone is re- 15 31 0 moved by washing with water, the developer being N crystallized out, after standing drawn off and washed with benzine. Yield 200-230 g, F. 110C.  
 EXAMPLE II A highly sensitive color reversal film (film developed C1 by reversal) is synthesized as follows:  
  1. On the base a spectral red-sensitized emulsion layer rich in silver. The emulsion contains SOg/kg of the. blue-green coupler a-naphthacidic octadecylamide.  
 was prepared by acylation of 1-(3&#39;-chlorophenyl)-3- aminopyrazolone-(S) with chloroformic acid(m-pentadecylphenyl-ester). Such couplers and the process for their preparation are disclosed in the German pubwithout white coupler lished application No. 1,176,479.  
 B. in addition to the 50 g color coupler 50 g white coupler of Formula 111,  
 C. in addition to the 50 g color coupler 45 g white STEP 2 coupler of Formula 111- White coupler of the Formula 111 2. A gelatin separating layer.  
  3. A green-sensitive layer with a color coupler for 21.6 g of the purple coupler of Step 1, 300 m1 methapurple. nol, 26.5 g acrylonitrile, 1 ml sodium methylate solu- 4. A fadeable yellow filter layer. tion (35% in methanol) and 0.2 g hydroquinone di- 5. A spectral unsensitized layer with a color coupler methyl ether are heated for 5 hours in an autoclave to for yellow. C. The reaction mixture is concentrated under re- From the three experimental pourings A, B, and C, duced pressure and the residue is recrystallized from color separation wedges are prepared in the customary acetic ester petroleum ether. Yield 1 1.3 g, F. 6368C.  
 What is claimed is:  
  1. A multilayer silver halide color photographic material containing a white coupler of the following general formula wherein R represents a methyl, ethyl or cyanoethyl group;  
 R represents (1) phenyl substituted with chlorine and/or an alkyl hydrocarbon radical with at least 8 carbon atoms or (2) Z-phenoxyethyl substituted with one or more substituents selected from the group consisting of alkyl and chlorine;  
 R represents one or several members of the group consisting or hydrogen, halogen, sulfo, thioalkyl and alkylsulfonyl.  
  2. A silver halide photographic material having multilayer color couplers which comprises the following layers:  
 a red-sensitive silver halide emulsion layer containing a color coupler for blue-green a green-sensitive silver halide emulsion layer containing a color coupler for purple a blue sensitive silver halide emulsion layer containing a color coupler for yellow and contained in the 5 photographic material a white coupler of the following formula:  
 wherein R represents a methyl, ethyl or cyanoethyl group; R represents (1) phenyl substituted with chlorine and/or an alkyl hydrocarbon radical with at least 8 carbon atoms or (2) Z-phenoxyethyl substituted with one or more substituents selected-from the group consisting of alkyl and chlorine; R represents one or several members of the group consisting of hydrogen, halogen, sulfo, thioalkyl and alkylsulfonyl. =1