US3591384A - Silver halide emulsion containing naphthamide photographic couplers - Google Patents

Abstract

THIS INVENTION RELATES TO COMPOUNDS USEFUL AS PHOTOGRAPHIC COUPLERS HAVING THE GENERAL FORMULA:

1-HO,2-((2-X,5-(R-Y-)PHENYL)-NH-CO-),4-Z-NAPHTHALENE

WHEREIN X IS ALKYL, Y IS EITHER CARBONYL OR SULFONYL, R IS ALKYL HAVING FROM 5 TO 20 CARBON ATOMS AND Z IS HYDROGEN OR HALOGEN. THE INVENTION ALSO RELATES TO THE USE OF THE ABOVEMENTIONED COMPOUNDS IN PHOTOGRAPHIC EMULSIONS.

Description

July 6, 1971 uzz ETAL 3,591,384

SILVER HALIDE EMULSION CONTAINING NAPHTHAMIDE PHOTOGRAPHIC COUPLERS Filed Jan. 31, 1968 FIG.

5 0 a \CREWQ 63 mskvqmk 5 m wwm N m EUG V0 MW? 7 m 7M, E E0 mm M A m W m M 0 m United States Patent Int. Cl.- G03c 1/40 US. Cl. 96-100 6 Claims "ABSTRACT OF THE DISCLOSURE This invention relates to compounds useful as photoand moisture and having good spectral characteristics, particularly low secondary absorptions.

It is an object of this invention to provide a new class of outstanding cyan couplers and photographic emulsions 5 incorporating such couplers.

The cyan couplers of this invention have the formula:

i Y.R wherein X is alkyl, preferably a lower alkyl (C -C Y f P couplers h e the general e m is either carbonyl or sulfonyl, R is C -C alkyl, and Z is r X hydrogen or halogen, preferably chlorine or bromine. g i r 1 These couplers are easily obtained in a'very high purity by methods described later. 20 Illustrative couplers are as follows:

(|)H (EH3 i 3L3 CONH wherein X is alkyl, Y is either carbonyl or sulfonyl, R r is alkyl having from 5 to 20 carbon atoms and Z is hydrogen or halogen. The invention also relates to the use of (1) the abovementioned compounds in photographic emul- OH sions. l

V -CONH This invention relates to a class of couplers capable of forming stable cyan or blue-green dyes by color development in color photographic materials.

In the production of colored images by the color devel- 01 00011 23 opment of silver halide emulsion layers in a multi-layer 0H CH3 film construction the image formed after light exposure of the reducible silver salts is developed in the presence -C0NH of a coupler, i.e. a compound which reacts with the oxidation products of the color developer to form a dye. Cyan images are generally obtained by the formation of an 40 indophenol dye from a l-hydroxy-Z-naphthamide coupler. S OZONE (3) One important requirement of color couplers used in 0H color photography is the ability to resist bleeding or I I migration through and outside of the photographic emul- OONH sion layers in which they are contained. An effective means for solving the migration problem is provided by the dispersed coupler method, in which the coupler is dissolved in high boiling organic solvents, such as tricresyl 01 3010181138 phosphate or dibutyl phthalate, and the resulting solution Table I shows some analytical data of these illustrais intimately dispersed throughout the silver halide emultive couplers, the analyses being made after only one cryssi on To obtain the best results in terms of the dispersion tallization of the raw reaction product. Included are their and photographic efficiency the solution of coupler in the desirable melting points. Their high degree of solubility organic solvent should be highly concentrated. Couplers in organic solvents normally used for dispersing couplers which are highly soluble in or miscible with the organic in a gelatin emulsion permits the use of a solvent/coupler solvent are therefore commonly selected for use in disratio far lower than 1.0 without any noticeable decrease persed coupler systems. In general, couplers having a relain yield of dye formed by normal color development protively low melting point are quite soluble in such organic cedures. For example, coupler (l) can be incorporated solvents. However, it is also desirable to select couplers into a photographic emulsion with 1 part dibutyl phthalate which produce dyes having good stability to light, heat containing 4 parts of coupler.

TABLE I OH, Melting C, percent H, percent N, percent 01, percent percent Crystal- Coupler point content lization No. F.) Found Cale. Found Cale. Found Gale. Found Cale. found solvent 1 15. 5-2192 78.46 78.39 8.28 8.11 3.00 3. 04 99. 27 Ethanol.

(102-104 0.) 2 149. 0-150 8 72.55 72.9 7. 25 7.3 7,16 7.17 98.81 Heptane 99.41 Acetic acid. 240.8-2425 5.86 5. 98.44 Do.

-'In addition to the above-mentioned characteristics the claimed couplers react with N,N-dialkyl-p-phenylenediamine during color development to provide dyes which are particularly stable to light, heat and moisture. For example, if one of thesecouplers is dissolved in dibutyl phthalate, dispersed in a photographic emulsion, coated onto a transparent support, exposed and developed with diethyl p phenylenediamine, the resultant color shows no noticeable change in either color density or hue after exposure to a xenon lamp for 10 hours. Coated samples prepared insimilar manner were exposed through a scale of decreasing densities, i.e. grey scale, and developed in color developer with. excellent sensitometric results, even after storage for 2 hours at 'a temperature of 194.0 F.

(90 C.) and a relative humidity of 75%. In FIG. 1

curve A is the sensitometric curve '(read in red light) for coupler (1) and curve B is the sensitometric curve for coupler (1) after 24 hours storage under the abovementioned conditions. These curves show the excellent stability of dyes prepared from the couplers of this invention. The spectral absorption of the cyan dyes obtained from these couplers and N,N-dialkyl-p-phenylenediamine developers make then particularly suitable for preparing color negative materials. Furthermore, they have a low absorption in the green portion of the spectrum, which is very desirable. In FIG. 2 an illustrative comparison of the spectral absorption of N,N-diethyl-p-phenylenediamine developed couplers in dibutyl phthalate, absorption curve A being that of abov'ementioned coupler (3) and absorption curve B being that of a coupler of the formula:

The coupler of curve B is a known coupler having some strutural similarity to the couplers of this invention. From a comparison of curves A and B it is apparent that curve A represents lower absorption in the 500 and 600 millimicron region than curve B.

The couplers of the present invention can be prepared by reacting the suitable amines with 1-hydroxy-2-naphthoic acid or 1-hydroxy-4-halo-2-naphthoic acid derivatives, such as their phenyl esters. In particular, the preparations of some couplers of said class were carried out in the following; way:

(a) PREPARATION OF 4-METHYLLAURO- PHENONE 1 a Into a 500 ml. flask containing a suspension of 59" g. of AlCl in 168 ml. of dry toluene, 69.2 g. of lauroyl chloride were rather quickly introduced. The temperature rose to 14O.0 F. (60 C.). The mixture was kept under stirring at a temperature of 176.0 F. (80 C.) for 22 hours, then was poured with vigorous stirring into 1000 ml. of water and 66.5 ml. of concentrated hydrochloric acid. After about one hour the organic layer was removed and washed, first with a 1% Na CO solution and then with water. The toluene solution was then dried with calcium chloride, and the solvent was removed under vacuum. The residue, consisting of a readily solidifying oil, was crystallized from ethanol. Yield: 58.8 g. (67% M- PF. l15,-.5,"v .F., (4.5f46.5 ,.C.).

Analysis-Calculated for C H O (percent): C, 83.57;

H, 10.94. Found (percent): C, 83.27; H, 10.94.

(b). PREPARATION OF 3-NITRO-4-METHYL- LAUROPI-IENONE In a beaker provided with stirrer and thermometer, was placed 190 m1. of HNO (d=1.52) and then 69.9 g. of 4-methyllaurophenone was added in increments. The operation was carried out as rapidly as possible while maintaining the reaction temperature below 44.6" F.

(7 C.). After completion, of the ketone addition the the mixture was added dropwise into one liter of ice water. The precipitated product was filtered off and thoroughly washed with water, then allowed to dry in the air. By crystallization from methanol 86.4 g. of the nitro derivative with M.P.: l22.0-123.8 F. (5051 C.) was obtained.

(c) PREPARATION OF 3-AMINO-4-METI-IYIIQ LAUROPHENONE 56.4 g. of 3-nitro-4-methyllaurophenone was dissolved in a boiling mixture of 530 ml. of 90% acetic acid and 260 ml. of ethanol. Then 106 g. of iron powder was slowly added. After completion of the addition boiling was continued for about 30 minutes, after which the ferrous slime .was hot filtered and the filtrate was poured with stirring into 17.5 ml. of water. The amine which separated was filtered oil and thoroughly washed with water. Yield of raw product: 48.6 g. By crystallizing the raw product from 485 ml. of ethanoland decolorizing with charcoal, 41.5 g. (81.2%) of product having a M.P. of 167.0-l70.6 F. (77 C.) was obtained.

Analysis.Calculated for C I-1 1810 (percent): N, 4.84. Found (percent): N, 4.65; --NH content, 100.00.

((1) PREPARATION OF l-HYDROXY-2-(2'-METHYL- 5-LAUROYL) NAPHTHANILIDE (COUPLER- 1) In a Claisen flask arranged for distillation under vacuum a mixture of 63.6 g. of 3-amino-4-methyllaurophenone and 63.6 g. of phenyl 1-hydroxy-2-naphthorate was melted. At this point vacuum was applied in order to remove the phenol which was liberated as the reaction continued. After about half an hour the amount of distilled phenol was 22 g. (theory: 22.6 g.). The residue was crystallized from ethanol. Yield of coupler: 91.5 g.

(e) PREPARATION OF l-HYDROXY-4-CHLORO-2- 2 METHYL 5 LAUROYL)NAPHTHANILIDE (COUPLER 2) By working in the same way as described for the coupler 1 and employing an equivalent amount of phenyl 1-hydroxy-4-chloro-Z-naphthoate instead of phenyl l-hydroxy-2-naphthoate 86 g. of coupler was obtained after crystallization from heptane.

(f) PREPARATION OF p-TOLYL CETYL S'ULFONE (g) PREPARATION OF 3-NITRO-4-METHYL- PHENYL CETYL SULFON'E It was obtained in a way similar to the 3-nitro-4-methyllaurophenone by using 112 ml. of fuming HNO for -56.8 g. of-p-tolyl-cetyl-"sulfone. Yield? 55.2 g. (from ethanol) M.P.: 161.6163.4 F. (7273 C.).

(h) PREPARATION OF 3-AMINO-4-METHYL- PHENYL ACETYL SULFONE (i) PREPARATION OF l-HYDROXY-2-(2'-METHYL- 5-CETYLSULFONYL) NAPHTHANILIDE (COU- PLER 3) By following the same procedure as with coupler (1), 47.3 g. of 3-amino-4-methylphenyl cetyl sulfone was reacted with 34.7 g. of phenyl l-hydroxy-Z-naphthoate. 59.2 g. of coupler (3) was obtained.

(l) PREPARATION OF l-HYDROXY-4CHLORO-2- (2'-METHYL-5 -CETYLSULFONYL) -NAPHTHANI LIDE (COUPLER 4) The product was obtained by procedures similar to those used in the preceding examples from 39.5 g. of 3-amino-4- methylphenyl cetyl sulfone and 32.8 g. of phenyl l-hydroxy-4-chloro-2-naphthoate. Yield was 43 grams.

(k) PREPARATION OF 1-HYDROXY-2-(2'-METH- YL-S -DECYLSULFONYL) NAPHTHANILIDE Obtained by a synthesis similar to that of the coupler (3), using decyl bromide instead of cetyl bromide.

The properties of the intermediates are the following:

The coupled was obtained by the reaction of the raw amine with phenyl l-hydroxy-Z-naphthoate and, after crystallization from ethanol, the M.P. was 273.2-277.5 F. (l34-l36.5 C.).

A nalysisSOH/c011tent=96.87%

Example 1 2 grams of coupler (1) was dissolved in a mixture consisting of 0.5 ml. of dibutyl phthalate and 12 ml. of ethyl acetate by heating on a boiling water bath. The resulting clear solution was poured into 40 ml. of 4% gelatin containing 4 ml. of sodium tetradecyl sulfate solution. At a temperature of about 104.0 F. (40 C.) the mixture was dispersed in a homogcnizer. The dispersion thus obtained was added to 200 g. of silver halide photographic emulsion sensitized to red light. The thus modified emulsion was spread on a transparent support, dried and exposed through an original. By chromogenic development in a N,N-diethyl-p-phenylenediamine developer, a negative blue-green colored image was obtained. The stable blue-green dye forming the image had an absorption peak at 688 m Example 2 A dispersion of the following formulation:

Coupler (3)2 grams Dibutyl phthalate-4 ml.

Ethyl acetate12 m1.

4% gelatin40 m1.

10% sodium tetradecyl sulfate solution-4 ml.

was added to 200 grams of a negative-type silver halide emulsion, sensitized to red light. The thus modified emulsion was spread onto a transparent support and dried. The photosensitive material thus obtained was exposed through an original and developed in a color developer of the following formulation:

Grams Hydroxylamine hydrochloride 1 Diethyl-p-phenylenediamine sulfate 2.8 Sodium tripolyphosphate 2 Anhydrous sodium carbonate 65 Anhydrous sodium sulfite 25 Potassium bromide 1.2

Water to make 1000 ml. (pH 10.88.11 with NaOH).

After the usual steps of bleaching, fixing and washing, a blue-green colored negative image of the original was obtained. The absorption curve of the blue-green dye forming the image is the same as curve A in FIG. 2. The absoprtion peak of the dye lies at 697702 III-,u.

Various other embodiments of the present invention will be apparent to those skilled in the art without departing from the scope thereof.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A silver halide photographic emulsion containing dispersed therein at least one compound of the general formula:

wherein X is lower alkyl, Y is carbonyl or sulfonyl, R is an alkyl group having from 5 to 20 carbon atoms, and Z is hydrogen or halogen.

2. A photographic element having at least one layer comprising the emulsion of claimv 1.

3. The emulsion of claim 1 wherein said compound has the formula 4. The emulsion of claim 1 wherein said compound has the formula OH CH3 CONH C1 OCnHza 5. The emulsion of claim 1 wherein said compound has the formula (IJH $113 Q C O U l SOzCroHas 6. The emulsion of claim 1 wherein said compound has the formula References Cited UNITED STATES PATENTS 3,459,552 8/1969 Yoshida et a1. 96-100 J. TRAVIS BROWN, Primary Examiner US. Cl. X.R. 260-559 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3.591.38" Dated Jul; 6 1971 lnventofls) Alberto Guzzi and Remo Magagnoli It is certified that error appears in the above-identified patent and that. said Letters Patent are hereby corrected as shown below:

Column 3, line 1 "2 hours" should read 24 hours Column 4, line 33, "l-hydroaw-iQ-naphthorate" should read l-hydroxy2-naphthoate Column 1%, line +0, "2-methyl" (etc.) should read (2'-methyl (etc.);

Column line 70, "acetyl" should read cetyl Column 5, line 31, "coupled", should read coupler Column 6, line 15, OH

/I CONH Signed and sealed this 2 6th day of Sept ember l9 7 2 SEAL) Arrest;

'l EDWARD M VTTETCHER'L JR ROBERT GOTTSCHALK A? t est i n 0F f' i uer Comml' ssioner of Patent 5

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