US3658545A - Light-sensitive silver halide color photographic material containing cyan couplers - Google Patents

Abstract

New colored cyan couplers useful in color photography can be obtained by substitution of a cyan coupler of the 1-hydroxy-2naphtamide type at its 4-position with a particular new arylazo group. These colored cyan couplers provide light-sensitive silver halide color-photographic material, which exhibits high photographic speed and which is free from color tone deviation over a wide pH range.

Description

United States Patent Iwama et al.

[ 51 Apr. 25, 1972 LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING CYAN COUPLERS Inventors: Masakuni lwama; Mitsuto Fujiwara; Tamotsu Kojima; Hiroyuki Imamura; Toshihiko Yamamoto, all of Tokyo, Japan Assignee: Konishiroku Photo Industry Co., Ltd.,

Chuo-ku, Tokyo, Japan Filed: Dec. 19, 1969 Appl. No.: 886,779

Foreign Application Priority Data Dec. 20, 1968 Japan ..43/93070 US. Cl ..96/l00, 96/9 Int. Cl ..G03c l/40 Field of Search ..96/9, 56.1, 100

[56] References Cited UNITED STATES PATENTS 2,521,908 9/1950 Glass et al ..96/5 6.1 2,808,329 lO/l957 Whitmore ..96/9 3,034,892 5/1962 Gledhill et al. ..96/100 Primary ExaminerJ. Travis Brown Attorney-Waters, Roditi, Schwartz & Nissen [5 7] ABSTRACT 2 Claims, No Drawings LIGHT-SENSITIVE SILVERHALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAININGCYAN COUPLERS The present invention relates to a light-sensitive silver halide color photographic material containing cyan coupler which has appreciable solubility in a water-immiscible high boiling solvent (hereinafter known as coupler solvent), said cyan coupler falling within the class of so-called colored couplers which provide auto-masking mechanism for the lightsensitive silver halide color photographic material so as to compensate for the deficient color reproductivity' of said material. Almost all the cyan couplers used as color former in color photography are compounds of l-naphthol-Z-carboxylic acid or aminophenol type. Where these coupler compounds are intended for use in photographic emulsions, a long chain alkyl group or a dialkylphenoxy group should preferably be introduced as a diffusion-preventing group into their molecule so that diffusion of the couplers from photographic layers can be prevented.

Among the cyan couplers, those which-have an arylazo group at their 4-position have been known as colored couplers provided with auto-masking mechanism so as to compensate for deficiencies in color reproduction of color photographic materials concerned. See US. Pat. Nos. 2,449,966 and 2,455,169. Particularly, a coupler of the l-hydroxy-4-ary1azo- Z-naphthoamide or naphthoanilide type, having the formula wherein X is hydrogen or alkyl, Y is a mononuclear aryl or aralkyl radical and R is a mononuclear aryl radical (cf. U.S. Pat. No. 2,521,908), or X is hydrogen, Y is a mononuclear aryl radical substituted in a position ortho to the amido group with either halogen, alkoxy or mononuclear 'aryloxy radical and R is a mononuclear aryl radical (US. Pat. No. 2,706,684), and a coupler having the formula wherein .r is an integer in the range of 0-4, y is 0 or 1 R is a member selected from the group consisting of phenyl radical, alkyl radical having from six to carbon atoms, alkyl-substituted phenyl radical and alkyl-substituted phenoxy-phenyl radical, and R is an alkyl group of one to four carbon atoms in either straight or branched chains (cf. U.S.. Pat. No. 3,034,892), are well knownas good couplers.

However, colored cyan couplers of the 4-ary1azo-substituted l-hydroxy-2-naphthoamide type generally are not so good in solubility in coupler solvents, and this has been appreciated as a great disadvantage in the production of lightsensitive color photographic materials. Further, almost all of these couplers have an aryl group at the 2-position of their naphthol nucleus. The introduction of an aryl groupat the 2- position of the naphthol nucleus causes a decrease in solubility of said couplers in coupler solvents, wherebythe couplers become difficult to be prepared in dispersion and tend to cause undesired crystallization in photographic-emulsions. Accordingly, many attempts have been made to improvetheir solubility, but they are not successful.

In view ofthe state of the prior-art, we have made extensive studies and'have found that a novel compound of the general formula (wherein .r is an integer in the range of 0-4 is 0 or 1, R is phenyl radical, alkyl or alkenyl radical having four to 15 carbon atoms in either straight or branched chain, alkyl-substituted phenyl radical, alkyl-substituted phenoxyphenyl radical, alkylsuccinimido or alkoxycarbonylalkyl radical, and R is substituted or non-substituted aryl or aralkyl radical) is excellent as colored cyan coupler.

The above compounds have good solubility in coupler solvents and have good dispersibility in photographic emulsions. Further, the photographic emulsions containing the above coupler compounds have high relative speed and are excellent in color shade of the resulting color image andin photographic properties, eg fog, etc. Density and spectral characteristics of the colored cyan coupler which may remain unreacted are not changed through the overall process of color development, while said coupler can provide an image having sufficient color density. Thus, a light-sensitive color photographic material having said coupler incorporated therein has good color reproductivity and is quite satisfactory in photographic properties.

Typical concrete examples of the above-mentioned couplers employed in the present invention are shown below, but couplers usable in the invention are notlimited only to these.

(1) l'hytgfplxy i-(tl-carboplienoxyphenylazo)-N-(10decyl-2'naphthtnnidv CONHC12H25 (2) 1-hydroxy-4-(2-carbophenoxyphenylazo)-N-[6-(2,4-di-tert-amylphenoxy)-l)uty1]-2-naphthumide ?II t C5II11 CONII(CH2)4O tC IIn (11) 1 hydroxy 4 (2 carbobenzyloxyphenylazo) N [6 (2, 4 di tort amylphonoxy)butyl]-2-naphthamide tCsHn i/ l N H N I Concrete procedures for synthesizing several couplers eml'oyed in the presentinvention are illustrated below with reference to synthesis examples.

SYNTHESIS EXAMPLE 1 Synthesis Example 1 was repeated, except that l-hydroxy- N [8-(2,4-di-tert-amylphenoxy) butyl]-2-naphthamide was used in. place of the 1-hydroxy-N-dodecyl-2 naphthamide, whereby the above-mentioned compound was obtained, yield about 80 percent, m.p. 149 150 C.

SYNTHESIS EXAMPLE 3 Synthesis of 1-hydroxy 4 2-carbo-( 2-methylphenoxy phenylazol-2-N-['y-(n-dodecylsuccinimide) propyH-naiah'thamide [the coupler of exemp1ific'ation(7)]: I

Using o-cres'ol in place of the phenol employed in Synthesis Example 1, the same treatment as in Synthesis Example 1 was effected to obtain (2-methylpheny1) 2-aminobenzoate ester as intermediate. Thereafter, the same procedures as in Synthesis Example 1 were repeated, using' t'he above-mentioned ester in place of the phenyl 2-aminobenzoa'te ester and using 1- hydroxy-N-['y-(n-dodecylsuccinimide) propyll-Z-naphthamide in place of the 1-hydroxy-N-dodecyl2-naphthamide, whereby the above-mentioned compound was obtained, yield 85 percent, m.p. 116- 117 C.

According to these synthesis examples, the couplers represented by the aforesaid structural formulas can be synthesized. Physical properties of the exemplified couplers synthesized in the above mariner are set forth in the table 353 .2 g. of benzenesulfonyl chloride. Subsequently, 94.1 g. of below.

Elementary analysis Melting Absorption Calculated Found point; Yield maximum Structural formula 0.) (percent) (ma) C H N Cl C II N Cl phenol was added with cooling, and the mixture was stirred'for 1 hour. This reaction liquid was introduced intoice water,-and a white precipitatedeposited was filtered, water-washed, dried and then recrystallized from n-hexane toobtain a phenyl onitrobenzoate ester. 121.6 g. of the thus obtainedesterwas dissolved in 1.2 l of '80 percent acetic acid, and the solution ,was charged with 89.6 g. of iron powderand then stirred for 1 hour. This reaction liquid was subjected to "filtration to recover a precipitate, whichwas then washed with 20 0 ml. of hot 80 percent acetic acid.'To the filtrate was addedZ-A lof water, and a deposited crystal was recovered by filtration,

water-washed and then dried to obtain a phenyl 2- aminobenzoate ester. 23.4 g. of 'this ester was dissolved in 300 ml. of 10 percent hydrochloric acid, and the solution was stirred with cooling. During the stirring, a solution of7.94 g. of sodium nitrite in 20ml. of water was dropped intosaid solution, and the mixed solution-was reacted for minutesfl' his solution was dropped into a solution comprising 35.5 g. of 1- hydroxy-N-dodecyl 2-naphthamide and 1.5 l of pyridine, andwas then stirred with cooling for 2 hours to form a 1 red. precipitate. This reaction liquidwas charged into-a solution comprising 2 l of concentrated hydrochloric-acid and 2 kg. of ice, and the deposited red precipitatewas recovered by filtration, water-washed, driedand then recrystallized from propyl alcohol, whereby a crystal was obtained. The thus obtained crystal was washed with methyl alcohol and then dried to obtain 1 g. of 1-hydroxy-4-('2-carbophenoxyphenylazo)-N- dodecyl-Z-naphthamide, yield about 85 percent, m.p. 164

SYNTHESIS EXAMPLE 2 pler ofexemplificution (2) 1:

The following test example show a comparison-iii efficiency between couplers employed in the presentinv'ention and other couplers.

TEST EXAMPLE Time of initiation Amount of 01', crystal- Control couplers l B lizntion used, ml. min.

(w com-10.21125 Couplers ofthc present invention Exemplification I) ml. min. Exemplification (2) 10 ml. 30 min. Exemplification (7) 10 ml. 60 min.

As is clear also from the above-mentioned test example, it is understood that the colored cyan couplers employed in the present invention are longer in time ofinitiation of crystallization than other colored cyan couplers of this kind, and hence are markedly high in solubility for coupler solvents.

The production of light-sensitive color photographic materials by use of the couplers represented by the aforesaid structural formulas may be carried out according to the prior art process. For example, the coupler is dissolved in a waterimmiscible high boiling solvent having a boiling point of above 180 C., such as dibutyl phthalate, tricresyl phosphate, dibutyl laurate or the like, either singly or, if necessary, in admixture with such low boiling solvent as ethyl acetate, butyl acetate, butyl propionate or the like. Thereafter, the solution is mixed with an aqueous gelatine solution containing a surface active agent, is emulsified by means ofa high speed rotary mixer or a colloid mill, is directly added to a silver halide photographic emulsion, and is then coated onto a suitable support such as film base, or the like, followed by drying, whereby a light-sensitive color photographic material can be obtained. In this .case, the amount of the coupler employed is desirably within the range of l0-l00 g. per mole of silver halide, but is optionally variable according to the purpose of application, without being limited to said range. Further, when used in combination with a colorless cyan coupler, in the above-mentioned case, the coupler of the present invention is further enhanced in solubility and comes to be quite easily dispersible in the silver halide photographic en'iulsion.

Light-sensitive silver halide color photographic materials obtained in the above manner do not suffer from crystallization of couplers and are excellent in transparency. When these materials are subjected, after exposure, to ordinary developing treatment, the resulting dye images have desirable spectral absorption characteristics, good transparency and excellent photographic properties.

The present invention is illustrated below with reference to examples.

EXAMPLE 1 One part of the coupler of exemplification (2) was dissolved in 5 parts of D.B.P. with stirring at 80 C. and was added to 100 parts of a 10 percent aqueous gelatine solution kept at 60 C., and the mixed solution was further charged with 2 parts of a 10 percent aqueous sodium alkylbenzenesulfonate solution. Subsequently, the liquid was stirred at about 65 C. for 5 minutes by use of a high speed rotary mixer. This operation was repeated five times at intervals of 1 minute to prepare a coupler dispersion. 13.5 parts of the thus prepared coupler dispersion was added at 35 C. to 100 parts of a light-sensitive silver iodobromide emulsion containing a red light-sensitive sensitizing dye, and the mixture was stirred and was then coated onto a film support, followed by drying, whereby a red light-sensitive color photographic material was obtained.

Separately, 1 part of a control coupler of the structural formula (C) shown below was dissolved in 10 parts of D.B.P. and was treated in the same manner as above to prepare a coupler dispersion. In this case, it is necessary that the temperature at which the coupler is dissolved in the coupler solvent should be strictly maintained at above C. and the temperature of the aqueous gelatine solution at the time of stirring should be strictly maintained at above 70 C. The thus prepared coupler emulsion was treated in the same manner as above to obtain a red light-sensitive color photographic material. Control coupler (C):

The thus obtained two kinds of light-sensitive color photographic materials were exposed to red light-through an optical wedge and were treated with a color developer of the following composition:

Color developer:

N,N-Diethyl-p-aminoaniline sulfate Sodium sulfite Sodium carbonate (monohydrate) 5 Hydroxylamine hydrochloride Potassium bromide Water to make 1,000m (pH 10.8 :01)

Subsequently, the materials were further treated with a bleaching solution and a fixing solution of the compositions shown below to remove undeveloped silver halide and byproduced reduced silver.

Bleaching solution:

From the color photographic material using the coupler of exemplification (2), there were simultaneously obtained a cyan colored negative image and a red positive image comprising residual coupler. The film was quite excellent in transparency, and the red positive image had a sufficiently red color. However, the color photographic material using the control coupler of the structural formula (C) gave a cyan colored negative image and a reddish orange positive image comprising unreacted residual coupler which were hazy and somewhat opaque. This is considered ascribable to partial crystallization and insufficient dispersibility of the control coupler.

The absorption maximum wave length and photographic speed of a film positive image, obtained by subjecting each of said two color photographic materials to exposure and then to bleaching and fixing, are shown below.

Absorption maximum Photographic A mixture comprising 1 part of the coupler of exemplification (2) and 3 parts of l-hydroxy-N-[6-(2,4-di-tertamylphenoxy)-butyl]-2-naphthamide was dissolved with stirring at 80 C. in parts of di-n-butyl phthalate and was added to 100 parts of a percent aqueous gelatine solution kept at 60 C., and the mixed solution was further charged with 2 parts of a 10 percent aqueous sodium alkylbenzene-sulfonate solution. Subsequently, the liquid was stirred at about 65 C. for 5 minutes by use of a high speed rotary mixer. This operation was repeated five times at intervals of 1 minute to prepare a coupler dispersion.

A mixture comprising 1 part of the control coupler of the structural formula (C) and 3 parts of l-hydroxy-N-[8-(2,4-ditert-amylphenoxy)-butyl]-2-naphthamide was dissolved in 10 parts of butyl phthalate and was treated in the same manner as above to prepare a coupler dispersion. In this case, it is necessary that the temperature at which the coupler is dissolved in the coupler solvent should be strictly maintained at above 80 C. and the temperature of the aqueous gelatine solution at the time of stirring should be strictly maintained at above 70 C.

Each 10 parts of the thus prepared coupler dispersions were individually added to 100 parts of a light-sensitive high speed silver iodobromide emulsion containing a red light-sensitive sensitizing dye, and the mixtures were treated in the same manner as in Example 1 to obtain two kinds of light-sensitive color photographic materials.

in the same manner as in Example 1, the thus obtained two kinds of color photographic materials were subjected to exposure, color development, bleaching and fixing to simultaneously obtain cyan colored negative images and red and reddish orange positive images. The film using the coupler (2) was good in transparency, whereas the film using the control coupler (C) was opaque and was extremely hazy, and the difference between the two materials was greater than in the case of Example 1. a

The absorption maximum wave length and photographi speed of a film positive image, obtained by subjecting each of said two photographic materials to exposure and then to bleaching and fixing, are shown below.

Absorption maximum Photographic The coupler of exemplification (7) was treated in the same manner as in Exampllel to prepare a red light-sensitive photographic material. 1115 material was treated in the same manner as in Example 1 to obtain simultaneously a cyan colored negative image and a red color positive image. This film was excellent in transparency and the red color positive image had a sutficiently red color. Further, the film was satisfactory in photographic speed.

EXAMPLE 4 The coupler of exemplification (9) was treated in the same manner as in Example 1 toprepare a red light-sensitive photographic material. This material was treated in the same manner as in Example 1 to obtain simultaneously a cyan colored negative image and a red color positive image. This film was excellent in transparency and the red positive image had a sufficiently red color. Further, the film was satisfactory in photographic speed.

What we claim is:

1. A light-sensitive silver halide color photographic material, characterized by containing a compound represented by the formula wherein is an integer in the range of 0-4, y is 0 or 1, R is phenyl radical, alkyl or alkenyl radical having four to 15 carbon atoms in either straight or branched chain, alkyl-substituted phenylradical, alkyl-substituted phenoxyphenyl radical, alkylsuccinimide radical or alkoxycarbonylaklyl radical, and R is an aryl or aralkyl radical which may be substituted with at least one member selected from the group consisting of halogen, lower alkyl or lower alkoxy.

2. A light-sensitive silver halide color photographic emulsion which contains as cyan color coupler a compound of the formula

Claims (1)

1. 2. A light-sensitive silver halide color photographic emulsion which contains as cyan color coupler a compound of the formula