US3778277A - Light-sensitive color photographic material with bis-type yellow color coupler - Google Patents

Abstract

A LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING A YELLOW CUOUPLER OF THE GENERAL FORMULA

Z-CO-CH2-CO-C(-X)(-Y)-CH2-(A)N-CH2-C(-X)(-Y)-CO-CH2-CO-Z

WHEREIN X IS AN ALKYL GROUP, Y IS AN ALKYL, ALKOXY OR ARALKYL GROUP, Z IS AN AROMATIC AMINO GROUP LINKED TO THE CHAIN THROUGH AN AMIDE LINKAGE. A IS A DIVALENT ALIPHATIC, AROMATIC OR HETEROCYCLIC RESIDUE AND N IS O OR 1.

Description

United States Patent Ofice 3,778,277 Patented Dec. 11, 1973 US. Cl. 96-100 8 Claims ABSTRACT OF THE DISCLOSURE A light-sensitive silver halide color photographic material containing a yellow coupler of the general formula wherein X is an alkyl group, Y is an alkyl, alkoxy or aralkyl group, Z is an aromatic amino group linked to the chain through an amide linkage. A is a divalent aliphatic, aromatic or heterocyclic residue and n is or 1.

This invention relates to a light-sensitive color photographic material, particularly one which contains a novel bis-type yellow coupler.

Generally, a light-sensitive color photographic material is subjected after exposure, to color development, whereby the coupler is reacted with an oxidation product of the color developer to form a dye. It is well known that in the above case, an u-acylacetamide derivative is used as the coupler for forming a yellow image. This yellow coupler is desired to be such that is not only displays sufiicient dispersability and suificient resistance to diffusion ina photographic emulsion but also is high particularly in color purity of yellow dye formed by the color development, i.e. it gives an absorption spectral curve which shows a relatively moderate declination on the shorter wavelength region than the absorption maximum but shows a sharp declination on the longer wavelength region. Further, the yellow coupler is required to form, by the color development, a yellow dye in a high yield. When such yellow coupler is used, the layer of light-sensitive color photographic material can be made thinner, so that the photographic material is enhanced in resolution and the resulting color image is improved in sharpness. Thus, the yellow coupler satisfying the above mentioned conditions is quite useful as a coupler for use particularly in a multi layer light-sensitive color photographic material.

However, none of the conventional yellow couplers satisfy the above-mentioned requirements, so that the resulting light-sensitive color photographic materials have not been suflicient in photographic properties.

In order to overcome such drawback of the prior art, German Pat. No. 1,049,231, for example, has proposed light-sensitiive color photographic materials containing yellow couplers having the Formula I,

COCHzCO-R (S O CH O OR wherein R is an aromatic amine, and Q is an aliphatic, aromatic or heterocyclic residue bonded directly to the CO group.

Typical examples of the couplers of the general Formula I which are disclosed in said German patent are as follows:

(A) OCH:

COCHaCONH C1BHI70 come ONH com o o cmc ONHQ COOH OOH

COOH

CnHssCONH iOCHiC ONE 0 rzHas CQCHnCONH OOH COOH

OCHiOONHQ coomooNrrQ l OOH H94 COOH O CHIC O NH max. M max.

wherein D is a color density :at the absorption maximum wavelength, and D +70 my. is a color density at the absorption maximum wavelength-F70 m i.

Yellow dye formed from the exemplified coup er:

As is clear from Table 1, in the case of the exemplified couplers (A), (B) and (C), which are of such a type that two carboacetamide groups were directly bonded by means of CO groups to the benzene ring (aromatic nucleus) to form one bis-type yellow coupler, the color purity of a yellow image obtained by the color development thereof is low (the value S is large) and a great improvement thereof is also impossible. Further, in the case of the exemplified coupler (D), which is of such a type that two carboacetamide groups have directly bonded by means of CO groups to the n-tetramethylene chain 'to form one bis-type yellow coupler, the color purity of a yellow image obtained by the color development thereof is considerably favorable (the value S is small) but is still unsatisfactory.

In order to overcome the drawback concerning the above-mentioned color purity, we made extensive studies to find that yellow dyes obtained from bis-type yellow couplers of the general Formula II shown below are excellent in color purity, and light-sensitive color photographic materials incorporated with said yellow couplers have excellent properties.

General Formula H:

X CHP-(J-COCHiCO-Z CHr- C OCHIC O-Z wherein X is an alkyl group, Y is an alkyl, alkoxy or aralkyl group, Z is an aromatic amino group, A is a divalent organic group, and n is or 1.

Typical examples of the bis-type yellow couplers of the general Formula II are as follows:

CH: (?HI +C O CHzC O NH NBC 0 Cn u Cl CH: Hr-(lJ-C O CHrC O NH NHC 0611 23 CaHb CH C OCHQC ONE 5 NHCOCHzO (Q Ca 1 CHg--C OCHaC ONH- (D 15 11 NHCOCH;0-(t) 0 H CH CH2+-C O CH7C ONH- NBC 0 C 171121 CI CH CHz+-C O CHrC ONH NHCOCaHu CH CHr--(-C O CI'IIO ONH O OCHgC OOCuHzs CH CI CH3 CH:+C 0 CI-IzC O NH 0 O CHgC 0 00 1115 Cl C'H3 CHr-C-C O CHzC O NH NH 50 zh 5 0 NH C1 CH l H -+-C O CHaC ONH OIL-Q 0 CH3 on? -o 0 01120 0 NH@ E 92 a $112 5 0 IITH H2): CH

$Hz COCH2CONH C Ha omitomeo NH NH0 0 C E?! Cl CH3 rel-(1 00 011.00 NH NHCO C11H23 G1 CH3 CH2-J3-C 0 OHzCONH C1 CHa 01-12-45-413 O CHzCONH These bis-type yellow couplers are synthesized according to the procedures set forth in the following synthesis examples:

SYNTHESIS EXAMPLE 1,

To a solution of 24 g. of methyl acetoacetate in 500 cc. of benzene was added 4.6 g. of metallic sodium in the form of flakes, and the resulting mixture was heated under reflux with stirring for 20 hours to form monosodium methylacetoacetate. To this salt was added at room temperature a solution of 25 g. of a,0c,e,e-tetlamethylpimelic acid chloride in 30 cc. of benzene, and the resulting mixture was reacted under reflux. The liquid reaction mixture was cooled, washed with water and a aqueous NH, solution, and then sufiiciently washed with water. Subsequently, the benzene solution layer was recovered, and the benzene was removed by distillation to obtain 16 g. of a pale yellow liquid, yield 50%. This liquid was methyl-a,a,e,.e-tetrarnethylpimelyl-bisacetate.

A solution comprising 16 g. of said methyl-a,ot,e,etetramethylpimelyl-bisacetate, 100 cc. of xylene and 40 g. of 2-chloro-5-[u-(dodecyloxycarbonyl) methoxycarbonyl] aniline was boiled, and methanol formed and the xylene were removed by azeotropic distillation. Timeafter, the liquid reaction mixture was dried under reduced pressure, and the resulting residue was recrystallized from a mixed solvent comprising n-hexane, water and methanol to obtain 28 g. of white crystals, M.P. 50-54" C., yield 53%.

Elementary analysis.-Calcd. (percent): C, 64.57; H, 7.99; N, 2.64; Cl, 6.69. Found (percent): C, 64.86; H, 8.25; N, 2.54; Cl, 6.90. The thus obtained product is the coupler of exemplification (4).

SYNTHESIS EXAMPLE 2 8.21; N, 5.54; Cl, 7.35. The thus obtained product is the coupler of exemplification (1).

SYNTHESIS EXAMPLE 3 To a solution of 12 g. of methyl acetoacetate in 300 cc. of benzene was added 2.3 g. of metallic sodium in the form of fine flakes, and the resulting mixture was heated under reflux with stirring for 20 hours to form monosodium methylacetoacetate. To this salt was added at room temperature a solution of 24 g. of ,B-(4-nitrophenyl)-a,a-dimethylpropionyl chloride in 50 cc. of benzene, and the resulting mixture was reacted un-der reflux for 1 hour. Thereafter, the liquid reaction mixture was washed with Water and a 10% aqueous ammonia solution, and then sufiiciently washed with water. Subsequently, the benzene solution layer was recovered, and the benzene was removed by distillation to obtain 16 g. of methyl-fl-(4-nitrophenyl)-u,ot-dimethylpropionyl acetate in the form of a pale yellow resin, yield 55% A solution comprising 28 g. of said methyl-p-(4-nitrophenyl)-ot,a-dimethylpropionyl acetate, 16 g. of 2,5-dichloroaniline and cc. of xylene was boiled, and methanol formed were removed with the xylene by azeotropic distillation. The liquid reaction mixture was cooled, and then sufiiciently washed with an aqueous dilute hydrochloric acid solution and with water in this order. Subsequently, the xylene solution layer was recovered, and the xylene was removed by distillation under reduced pressure to obtain 33 g. of ,6-(4-nitrophenyl)-u,ot-dimethylpropionylaceto-2,S-dichloroanilide in the form of a yellowish brown resin, yield 80%. A solution of 41 g. of the thus obtained ,B-(4-nitrophenyl) a,m-dimethylpropionylaceto-2,5-dichloroanilide in 300 cc. of ethyl alcohol Was hydrogenated at 50 C. and at normal pressure in the presence of 4 g. of a Raney nickel catalyst. Thereafter, the liquid reaction mixture was filtered, and the filtrate was vaporized to dryness to obtain as the residue 31 g. of 13-(4- aminophenyl) a,a-dimethylpropionylaceto-2,5-dichloroanilide in the form of a yellow resin, yield 80%.

A solution of 39 g. of this ,8-(4-aminophenyl)-a,a-dimethylpropionylaceto-2,5-dichloroanilide in 400 cc. of aeetonitrile is charged with a solution of 9 g. of adipic acid chloride in 30 cc. of acetonitrile, and then heated under reflux for 30 minutes. Subsequently, the liquid reaction mixture Was dried under reduced pressure, and the residue was recrystallized from a mixed solvent comprising n-hexane, methanol and water to obtain 22 g. of a desired product in the form of a pale yellow transparent resin, yield 50%.

Elementary analysis.Calcd. (percent): C, 60.83; H, 5.34; N, 6.45; Cl, 16.33. Found (percent): C, 61.05; H, 5.65; N, 6.25; CI, 16.10. The thus obtained product is the coupler of exemplification (5) From the above-mentioned bis-type yellow couplers used in the present invention, yellow dyes excellent in color purity are obtained. When represented in terms of the aforesaid values S, for example, the color purities of the yellow couplers are as shown in Table 2.

TABLE 2 Absorption maximum wavelength Coupler 1) From Table 2, it is understood that a yellow dye obtained by the color development of the bis-type yellow coupled having the general Formula II is extremely small in value S, i.e. the absorption spectral curve of the said dye has sharply declined on the longer wavelength region of the absorption maximum wavelength, and thus the color purity thereof is excellent. Further, the bis-type yellow coupler used in the present invention is high in color developing elficiency as is clear also from the fact that it contains in one molecule two coupling points capable of reacting at the time of color development with the oxidation product of the color developer. When the yellow coupler of the present invention is used, the thickness of emulsion layer can be made thinner by more than 50%, so that the light-sensitive color photographic material is improved in resolution and the resulting color image is improved in sharpness.

For the preparation of a light-sensitive color photographic material by using the bis-type yellow coupler of the general Formula II, there may be adopted any of the known procedures. For example, the coupler is dissolved in a high boiling solvent having a boiling point of more than 175 C. such as tricresyl phosphate or dibutyl phthalate, or a low boiling solvent such as butyl acetate or butyl propionate, or, if necessary, in a mixture of said solvents, and the resulting solution is mixed with an aqueous gelatine solution containing a surface active agent. Subsequently, the mixed solution is emulsified by means of a high speed rotary mixer or a colloid mill to form a dispersion. This dispersion is added directly to a silver halide photographic emulsion, which is then coated on a suitable support such as a film base or a baryta paper and dried to remove a major proportion of the low boiling solvent, whereby a light-sensitive color photographic material can be prepared. Alternatively, the above-mentioned dispersion is once cold set and finely cut, subjected to water washing or the like treatment to remove the low boiling solvent, and then added to a silver halide photographic emulsion. Subsequently, the emulsion is coated on said support and then dried to prepare a light-sensitive color photographic material.

The emulsion used in the above may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide and silver chlorobromoiodide emulsions, and may contain a chemical sensitizer, e.g. sulfur sensitizer, and a noble metal salt. The emulsion may additionally contain ordinary photographic additives such as antifoggant, stabilizer, anti-stain agent, anti-irradiation agent, physical property-improving high polymer additive, coating aid, etc. Further, the emulsion may have been incorporated with a known cyanine or merocyanine dye as an optical sensitizer.

The light-sensitive color photographic material prepared in the above manner is exposed, developed with a developer containing a p-phenylenediamine type developing agent, and then bleached, fixed and desilvered to obtain a high density yellow dye image excellent in color purity (spectral absorption characteristic) and high in transparency. This yellow dye image is excellent also in light fastness and is quite satisfactory.

The present invention is illustrated in further detail below with reference to examples, but the scope of the invention is not limited to these examples.

EXAMPLE 1 20 grams of the coupler of exemplification (3) was added to a mixed solvent comprising 20 ml. of dibutyl phthalate and 60 ml. of butyl acetate, and completely dissolved therein at 80 C. This solution was mixed with 10 ml. of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate produced by Du Pont) and 200 ml. of a 5% aqueous gelatine solution, and the mixed solution was subjected to a colloid mill to form a dispersion. The thus formed coupler dispersion was added to 1,000 ml. of a high sensitivity silver iodobromide emulsion (5 mol percent AgI), which was then coated on a polyester film base and dried to prepare a light-sensitive color photographic material having a stable film.

The thus prepared photographic material was exposed according to an ordinary procedure, and then developed at 20 C. for minutes with a developer of the following composition:

N,N-diethyl-2-methyl-p-pheny1enediamine hydrochloride 2.5 Anhydrous sodium sulfite 2.0 Sodium carbonate (monohydrate) 82.0 Potassium bromide 2.0

Water to make 1,000 ml.

G. Potassium ferrocyanide Potassium bromide 50 Water to make 1,000 ml.

The treated photographic material was washed with water for 5 minutes and then fixed for 5 minutes with a fixing solution of the following composition:

Sodium thiosulfate (pentahydrate) 250 Water to make 1,000 mi.

Thereafter, the photographic material was washed with water for 20 to 25 minutes and then dried to obtain a clear yellow dye image having an absorption maximum at 444 m which was high in color purity, favorable in sharpness and excellent in light fastness.

EXAMPLE 2 10 grams of the coupler of exemplification (4) was added to a mixed solvent comprising 10 ml. of tricresyl phosphate and 30 ml. of butyl acetate, and completely dissolved therein at 60 C. This solution was mixed with 5 ml. of a 10% aqueous Alkanol B solution and 200 ml. of a 5% aqueous gelatine solution, and the mixed solution was subjected to a colloid mill to form a dispersion. The thus formed dispersion was added to 500 ml. of a gelatine silver iodobromide (5 mol percent AgI) emulsion, which was then coated on a cellulose triacetate film base and dried to prepare a light-sensitive photographic material.

The thus prepared photographic material was exposed, and then developed at 20 C. for 10 minutes with a developer of the following composition:

G. Metol 3.0 Anhydrous sodium sulfite 10.0 Hydroquinone 6.0 Anhydrous sodium carbonate 50.0 Potassium bromide 1.0

Water to make 1,000 ml.

The developed photographic material was subjected to ordinary stopping, hardening and water-washing treatments, subjected to secondary exposure by use of a white light and then developed at 20 C. for 12 minutes with a developer of the following composition:

N,N-diethyI-Z-methyl-p-phenylenediamine hydrochloride 5.0 Anhydrous sodium sulfite 2.0 Sodium carbonate (monohydrate) 82.0 Potassium bromide 1.0

Water to make 1,000 ml.

Subsequently, the photographic material was subjected to ordinary stopping, fixing, water-washing and bleaching treatments, washed with running water for 20 minutes and then dried to obtain a yellow positive dye image having an absorption maximum at 445 m which was high in transparency, favorable in clarity (color purity) and excellent in light fastness.

EXAMPLE 3 16 a xenon lamp. The residual ratios of the dyes at an optical The light-sensitive color photographic material as density of 1.0 were as set forth in Table 3. claimed lIl claim 3, wherem said yellow coupler 1s 01 TABLE 3 on,

Percent 5 CHr-+C OCHzC ONH C I Coupler so hours 100 hours Ha NHCO C Exorrfipllficatlon: 60 38 01 87 Hr-(i --C oolno oNH From Table 3, it is clearly understood that the couplers of the present invention have excellent properties which cannot be anticipated from the couplers disclosed in Ger- 1 7. The light-sensitive color photographic material as claimed in claim 3, wherein said yellow coupler is man Pat. No. 1,049,231.

What is claimed is: I 1. A light-sensitive silver halide color photographic "COCH'CONH :sfiznal contain ng a yellow coupler of the general fors CH; oocmco 00mm.

H; X c1 (5 1 CH: om-s-ooomconn c )n X OOCHgCOOCrzHza i 0 CHRC 8. A light-sensitive silver halide color photographic material containing a yellow coupler selected from the group consisting of wherein X is an alkyl group, Y is an alkyl, alkoxy or C11 aralkyl group, Z is an aromatic amino group linked to the chain through an amide linkage, A is a divalent ali- CH' COCHOONH phatic, aromatic or heterocyclic residue and n is 0 or 1. NHCOC H 2. The light-sensitive color photographic material as claimed inclaimo 1 wherein A is phenyl, -CH C] y CH: I -Nn-c o,- cru)ic ONH m-+-oocmoonn t V 1 CH: 01' 40 NHCOCnHu -(CHI): NH-c O-CH:-0OCHz-C O-NH(CH:)2-

' CgHr,

CHg- -COCH:CONH (t)C5Hn NHCOOH O @0511 C1 i CgHs Hr-J!-COCH:CONH (1;)C5H11 NHCOCHQO (1;)CsHu a I o n n 3. The hght-sensrtive color photographic material as H:

claimed in claim 1 wherein A is phenylene or alkylene.

CH )--COCH CONE- 4. The hght-sensitrve color photographlc material as a- 2 H clalmed in claim 3 wherein A 1s por m-phenylene 3 HCOCHH 5. The light-sensitive color photographlc material as claimed in claim 3, wherein said yellow coupler is 01 H -Al-COCHgCONHQ Hs Cl NHCOGnHfl CH: 01 CH -h-OOCHzCONH CH1 cm-o-ooomoonrr NHC 0 C H H OOCHgCOOCuHu c H! C f l I nr--ooomooNn l,

NHCOCnHzl O OCH COOCnHn CH:- -C OCHaC ONH- Q cm--- come ONH- 2): CHI

2-0-0- 0-0-0- MLMQ a 0 CH: a): CH8

and

NORMAN G. TORCHIN, Examiner R. L. SCHILLING, Assistant Examiner CHI CH, a COcH,CoNH@ NBC 0 CuHn NBC 0 CnHn G1 CH:

References Cited UNITED STATES PATENTS 5/1972 I Wama et a1 96-400 6/1972 Iwama et a1 96-100 FOREIGN PATENTS 1/1959 Germany 9655