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Publication numberUS3767411 A
Publication typeGrant
Publication dateOct 23, 1973
Filing dateOct 20, 1971
Priority dateOct 20, 1970
Also published asDE2152336A1
Publication numberUS 3767411 A, US 3767411A, US-A-3767411, US3767411 A, US3767411A
InventorsArai A, Iwano H, Kishimoto K, Shimamura I
Original AssigneeFuji Photo Film Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Color photographic light-sensitive material forming novel cyan images
US 3767411 A
Abstract
A color photographic light-sensitive material having at least one silver halide emulsion layer containing a cyan coupler of the formula:
Images(1)
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Description  (OCR text may contain errors)

United States Patent 1 1 Kishimot o et al.

[ 51 Oct. 23, 1973 [2!] Appl. No.: 190,866

Primary Examiner-Norman G. Torchin Assistant Examiner-R. L. Schilling Mion,

Att0rneySughrue, Rothwell, Macpeak vZinn and 57 I ABSTRACT v A color photographic light-sensitive material having at least one silver halide emulsion layer containing a cyan coupler of the formula:

wherein X represents a member selected from the group consisting of a hydrogen atom and a halogen atom; Y represents a member selected from the group consisting of RCONH-, RNHCO-, or RNHCONH-; the substituted position of said Y being limited to the mposition and the p-position; R represents an alkyl group having more than 10 carbon atoms; n is an integer of one to two; Y may be the same or different if n is an integer of two, but in this case, if the p-position has been substituted with Y, the other Y has been substituted, at the m-position; Z represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a methyl group, a methoxy group and an ethoxy group; and m is an integer one to two; said Z may be the same or different, if n is an integer two.

5 Claims, 1 Drawing Figure l. COLOR PHOTOGRAPI-IIC LIGHT-SENSITIVE MATERIAL FORMING NOVEL CYAN IMAGES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a color photographic lightsensitive material having an improved novel cyan color forming layer containing a napththolic cyan coupler with a long chain alkyl group, in a silver halide emulsion layer, the said cyan coupler forming the dye exhibiting an absorption maximum at a wavelength region of 635 to 700 nm, when the silver halide emulsion layer containing the cyan coupler is developed with an ordinary color developer containing a p-phenylene diamine as a color developing agent.

2. Description of thePrio'r Art When a color photographic light-sensitive material having on a support the silver halide emulsion, containing the coupler with an alkyl-substituted phenoxyacetyl group as a well known ballasting oil-solubili'zing group, such as the coupler having the following structure (I),

Nncocnio@z-oinn (IE1: H

CONH

- 565 nm in the coupler (II), 625 nm in the coupler (III),

However,a coupler with a long chain alkyl as the balon Q NHCOC'Hz() n in c o macaroni- 3 NH 0 O C11'H:s(n)

(III) and 540 nm in the coupler (IV), respectively. It is clear, however, that these absorption maximum wavelengths are too short for color reproduction as a cyan coupler, used for three-color subtractive process and such couplers as mentioned above are not preferable for such purpose.

Furthermore, the compound of the following structure (V) having a chlorine atom at the coupling position of the coupler (II),

V NBC 0 C Has(n) I s (V) as well as the coupler (II), gives a colored dye image having an absorption maximum at too short a wavelength side for color reproduction and is thus undesirable, as well.

SUMMARY OF THE INVENTION The cyan color image of the color photographic lightsensitive material of this invention has an absorption maximum in the region of wavelength from 635 to '[00 nm, preferably from 640 to 670 nm and is quite preferable in color reproduction.

This invention provides a color photographic lightsensitive material, composed of a red-sensitive silver halide emulsion layer containing a naphtholic cyan coupler with a long chain alkyl as a ballasting group, said cyan coupler giving the color image, having an absorption maximum wavelength at a region of from 635 to 670 nm, preferably from 640 to 670 nm, when the silver halide emulsionlayer having the cyan coupler is developed with a color developer with a p-phenylene diamine color developing agent.

DETAILED DESCRIPTION OF THE INVENTION The cyan coupler used in the present invention is represented by the following general formula (VI):

Coupler (VIII);

OH @jCONHQ-CONHWHMn Coupler (IX):

ONHCuHuOI) ONH nHaU Coupler (X C ONHCmHu(l1) Coupler (XI):

Coupler (XII):

GQNHQNHCO 0,111,501

Coupler (XIII):

coNHQNacocnHMm CH1 Coupler (XIV):

on 001m o 0 NHQNH c 0 0,111,501) I 00,11.

In addition, among the couplers illustrated above, the coupler having RN HCO- as a ballasting group is more preferable than the coupler having RCONH-. Wherein, R represents a long chain alkyl group.

The cyan coupler in this invention is used as a solution thereof such as in an ordinary solvent for couplers as dibutyl phthalate, tricresyl phosphate, etc. The solvent may also be used together with an auxiliary solvent, such as ethyl acetate, propyl acetate, etc. The coupler solution is dispersed into a gelatin-containing silver halide emulsion at the state of emulsification by a known way and the photographic emulsion is coated on a support and dried. The binding agent for the gelatin-containing silver halide emulsion may be gelatin alone, or gelatin containing a water-soluble polymer. That is to say, gelatin as the binding agent may contain a water-soluble polymer; such as polyvinyl pyrrolidone or a copolymer of maleic acid and acrylamide, but it is preferable that at least 50 wt percent of the total binder be gelatin. Also, the support used in this invention may be a transparent film base, such as triacetyl cellulose, polyethylene terephthalate, polystyrene, and the like or an opaque support, such as baryta-coated paper, polyolefin-coated paper, synthetic paper, or an opaque or translucent plastic base.

The light-sensitive material of this invention is colordeveloped by a color developer containing a p-phenylene-diamine color developing agent and then subjected to the subsequent processings.

The p-phenylenediamine type color developing agent used in this invention is preferably a compound represented by the following general formula (XV), although it is not limited to such compound of the general formula (XV):

or a salt thereof (XV) wherein R, represents a hydrogen atom or a methyl group and R, and R represent a lower alkyl group or a substituted lower alkyl group, such as a methyl group, a B-hydroxyethyl group, a B-methylsulfoaminoethyl group, a 4-sulfobutyl group and a butyl group, etc.

Now, the typical examples of the color developing agent having the above formula (XV) are shown below, although the said color developing agent of this invention is not limited to these:

0 Compound (XVI) Compound (XVII) C2116 HzNN\ -H2S ot-imo canon Compound (XVIII) /C:H5 I- IzN-N\ 3am s ormo I CzHqNIISO CIIa CH3 Compound (XIX) /C|Hfl(l'l) H2N C|HaSO3H Compound (XX) I /C2H1s H2N N\ -HzSO4 Compound (XXI) /VC2H5 HzNN\ Has 04 zHs In addition, the superior effects of this invention become more remarkable by finding proper conditions from such factors as the kind of coupler to be used, the manner of producing the light-sensitive material containing the coupler (such as aratio of the amount of the silver halide emulsion and the amount of the couplercontaining emulsion, the thickness of the emulsion lected by filtration to provide -65 g of yellow fine crystals of crude l-hydroxy.-2-N-{[092'- nitrophenyl}]naphthamide having a melting point of 203205 C. I

2. Preparation of l-hydroxy-2-N-[{2'-aminophenyl}]naphthamide: A mixture consisting of 30 g of l-hydroxy-2-N-[{2-nitrophenyl}lnaphthamide. 200 ml of pyridine, and a small amount of 10 percent-palladium carbon was shaken for 6 hours in a high-pressure vessel at a reaction temperature of 40 C under a hydrogen pressure of atoms and then the reaction mixture was filtered and concentrated in vacuo.

The residue was dissolved in a small amount of hot ethanol and cooled, whereby crystals were formed. The crystals thus formed, were collected by filtration and washed with hot ethanol to provide 10 g of crude lhydroxy-Z-N-(2'-aminophenyl)naphthamide having a melting point of 22l-222.5 C.

3. Preparation of 1-hydroxy-2-[N-{2-(2,4-di-tertiary.amyl)-phenoxyacetylamino}phenyllnaphthamide (I):

A half amount of the solution of 10 g of 2,4-di-tamylphenoxyacetic acid chloride in 100 ml of acetone was added dropwise with stirring to a solution of 9 g of l-hydroxy-2-N-(2-aminophenyl)naphthamide in 300 ml of acetone under ice cooling. Thereafter, a 3.3 g of triethylamine was added to the mixture and then the remaining acid chloride solution was added to the solution followed by stirring for further 20 minutes, whereby an oily product was formed. The reaction mixture was cooled and allowed to stand overnight. The crystals formed were collected by filtration, dissolved in a 10 percent aqueous potassium hydroxide solution, and acidified with concentrated hydrochloric acid. The formed crystals were collected by filtrating, and then I recrystallized from a mixture of ethanol and pyridine to layer coated, etc.), andthe kind of the color developing agent used. v I

The manner of producingthe couplers of this invention and comparison couplers are shown below. First of all, the examples of producing the compounds (I) and (V), which are the comparison couplers are illustrated below.

state, ethanol was added little by little to the product, the coagulated crystal was crushed into small pieces, cooled to room temperature, washed with ethanol, and then the yellow crystal was immersed in ethanol. After refluxing for about 15 minutes on a steam bath. The crystals thus managed, were colprovide 8 g of the coupler (I) appearing as colorless crystals having a melting point of l68-l7l C.

Elementary analysis as C I-l O N Calculated C.- 76.10% H: 7.25% Found c; 75.75% H: 7.33%

Synthesis 2 1-hydroxy-4-chloro-2[N-(stearoylamino)phenyllnaphthamide (V):

A half amount of a cooled solution of l l g of strearoyl chloride in 30 ml of acetone was added dropwise to a solution of 1 l g of l-hydroxy-4-chloro-2-N-(2'- aminophenyl)naphthamide in 300 ml of acetone under stirring. Thereafter, 3.7 g of triethylamine and then the remaining acid chloride solution were added to the mixture and thenthe resulting mixture was stirred for 50 minutes.

The crystals formed were collected by filtration. The filtrate was concentrated under a reduced pressure and was cooled to form crystals, which were collected by filtration. The combined crystals were washed with water, dissolved in a mixture of a 10 percent aqueous sodium hydroxide solution and ethanol (1:1) and acidified with concentrated hydrochloric acid to form crystals. The crystals obtained were recrystallized from ethanol to provide 6.1 g of the coupler (V) having a melting point of l57.5l58.0'C.

Calculated Found H: 8.l3% H: 8.32%

Now, the procedures for obtaining the typical couplers (VII), (VIII), (X), and (XII) described above are shown below.

Synthesis 3 l-Hydroxy-2-[N-(3-N-n-hexadecylcarbamoyl)- pheny1]naphthamide (VII):

1. Preparation of m-nitrobezoyl cetylamide:

In the presence of 19 g of triethylamine, 35 g of mnitrobenzoyl chloride was reacted with 50 g of cetylamine in acetone.

After the reaction mixture was concentrated, the crystals formed were collected. The crymtals were recrystallized from ethanol to give 62.5 g of mnitrobenzol cetylamide appearing as colorless flaky crystals having a melting point of 9495 C.

Elementary analysis:

Calculated C: 70.80% H: 9.74% Found C: 70.69% H: 9.68% 2. Preparation of m-aminobenzoyl cetylamide:

62.5 g of m-nitrobenzoyl cetylamide was dissolved in 140 ml of ethanol and the solution was hydrogenated for one hour at 50 C under hydrogen pressure and palladium-carbon catalyst with stirring. While the reaction mixture was in a hot state, it was filtered to remove the catalyst and the crystals obtained were recrystallized from ethanol to provide 40 g of the above compound having a melting point of 78 C.

Elementary analysis:

Calculated c: 76.70% H: 11.11% N: 7.78% Found c: 76.76% H: 11.14% N: 7.49%

3. Preparation of 1-hydroxy-2-[N-(3-N-n-hexadecylcarbamoyl)-phenyl]naphthamide (VI I):

A mixture of 40 g of m-aminobenzoyl cetylamide and 29.5 g of l-hydroxy-Z-naphthoic acid phenyl ester was heated for 3 hours at l70l80 C in an oil bath under reduced pressure and then the reaction product was recrystallized from ethanol to provide 43 g of the objective material having a melting point of l4l-l41.5 C.

Elementary analysis:

Calculated C: 77.03% H: 8.68% N: 5.29% Found C: 77.19% H: 8.40% N: 5.39%

Synthesis 4 l-Hydroxy-Z-[N-(4'-n hexadecylcarbamoyl)- phenyllnaphthamide (VIII):

By a similar method to that of Synthesis 3, the coupler (VIII) could be readily produced with a good yield. By recrystallizing the crude product from ethanol, 45 g of the colorless crystals of the coupler (VIII) having a melting point of 162 C was obtained.

Elementary analysis:

Calculated c: 77.03% H: 8.68% N: 5.29% Found c: 77.20% H: 8.67% N: 5.01%

Synthesis 5 l-Hydroxy-2-[N-(2'-methoxy-5-nhexadecylcarbamoyl)phenyl]naphthamide (X):

24 g of 3-amino-4-methoxybenzoyl cetylamide was heated with an equimolar amount of l-hydroxy-Z- naphtoic acid phenyl ester by same manner as in Synthesis 3 and the coupler (X) could be obtained readily with a good yield.

By recrystallizing from ethanol, light brown crystals having a melting point of 92l02 C were obtained. Further recrystallization of the above product from ethanol, gave 14.5 g of the coupler (X) appearing as a colorless crystal having a melting point of 108 C.

Elementary analysis:

Calculated C: 75.00% H: 8.57% N: 5.00% Found C: 74.89% H: 8.79% N: 5.24%

Synthesis 6 Elementary analysis:

Calculated Found A better understanding of the present invention will be gained from the following examples, which are simply illustrative and not limitative of the present invention.

Example 1 3.9 g of l-hydroxy-2-[N-(3-n-hexadecylcarbamoyl)- phenyl]-naphthamide (VII) was dissolved in a mixture of 5 ml of tricresyl phosphate and 5 ml of ethyl acetate as an auxiliary solvent and the solution thus obtained as dispersed by emulsification in 50 g of 10 percent aqueous gelatin solution in the presence of an alkyl-benzensulfonate type surface active agent. 23 g of the prepared emulsion was added to g of a silver iodo-bromide emulsion that had been post-ripened.

The smulsi on was coated on a film base by an ordinary manner and dried. The light-sensitive film was light-exposed and developed for 5 minutes in a developing solution having the following composition: 2-methyl-4-[(N-B-hydroxyethyl-N-ethyl)I- aminoaniline sulfate (XVI) 2.5 g Anhydrous sodium sulfite 2.0 g Sodium carbonate (monohydrate) 82.0 g Potassium bromide 2.0 g

Water was added up to 1,000 ml.

Potassium ferricyanide Potassium bromide Water was added up to 1,000 ml.

The film was washed with water for 10 minutes and fixed in a bath having the following composition:

Sodium thiosulfate Water was added up to 1,000 ml By washing the photographic film with water and then drying it, a sharp blue-green image having an abf I a 3,767,411

sorption maximum at 655 nm and less unnecessary absorption was obtained.

I BRIEF DESCRIPTION OF THE DRAWING EXAMPLE 2 .color developing agent (XIX) instead of the colordeveloping agent (XVI) in Example 1 and subjected to the subsequent processings as in Example I to provide a sharp blue-green image having an absorption maximum at 650mm.

EXAMPLE 3 A photographic light-sensitive film was prepared by the same process as in Example 1 using the coupler (IX) instead of the coupler (VII) used in Example 1. After light exposure, the photographic film was developed in a color developing bath having the same composition as that of Example 1, except that the color developing agent (XXI) was used instead of the color developing agent (XVI) and then subjected to the subsequent processings as in Example 1 to provide a sharp blue-green image having a spectral absorption maximum at 650 nm.

EXAMPLE 4 A photographic light-sensitive film was prepared by the same procedure as in Example 2 using the cyan coupler (X). After light exposure, the photographic film was developed in a color developing solution having the same composition as that of Example 2, except that the color developing agent (XVII) was used in place of the color developing agent (XIX) and then subjected to the subsequent processings as in Example 1 to provide a sharp cyan color image having a spectral absorption maximum at 692 nm.

EXAMPLE 5 The same film as used in Example 4 was developed in the developing bath having the same composition as that in Example 4, except that the color developing agent (XVIII) was used in place of the colordeveloping agent (XVII) and then subjected to the subsequent processings as in Example 1 to provide a sharp cyan color image having the spectral absorption maximum at 696 EXAMPLE 6 A photographic light-sensitive film was prepared by the same manner as in Example 1, except that the coupler (XIV) was used in place of the coupler (VII). After light exposure, the film was developed in a developing bath having the same composition as in Example 1, except that the color developing agent (XX) was used in place of the color developing agent (XVI) and then subjected the subsequent processings as in Example l to provide a cyan dye image having the spectral absorption maximum at a longer wavelength region of 684 nm.

DETAILED DESCRIPTION OF THE DRAWING The example of the cyan color image produced by the photographic light-sensitive image of this invention is shown as the curve (1) in the FIGURE and the absorption maximum of the cyan color image was at 655 nm. This value isparticularly suitable for color positive films, color reversal films and color papers, but it is clear that the spectral absorption curves of the cyan color images forming from the comparison examples, shown by the curve (2) and the curve (3) in theFIG- URE are not preferable for the purposes of color positive films and the like. In particular, as shown by the curve (2), the spectral absorption curve of a color image obtained from the coupler II having the long chain alkyl group as the ballasting group illustrates clearly that the absorption maximum is in the shorter wavelength side, to make it difficult to obtain correct color reproduction. Also, it has been confirmed that a desirable absorption pattern cannot be obtained throughout the whole region, even if the ratio of the color and the silver halide and the kind of the color developing agent are varied.

The color photographic light-sensitive material of this invention is characterized by using l-hydroxy-Z- naphthanilide type cyan coupler having a long chain alkyl group as a ballasting group and provides a color image having an absorption maximum at the wavelength regions of 635-700 nm, and a sharp curve of spectral absorption for cyan color, which is not expected by an ordinary technique. Usually, the absorption maximum of a color image formed by using a lhydroxy-2-naphthanilide type cyan coupler having an oil solubilizing group is at a wavelength region longer than 700 nm as shown by the curve (3) in the FIGURE. On the other hand, a color image in a case of using a l-hydroxy-2-naphthanilide type cyan coupler having a long chain alkyl group as the ballasting group has an absorption maximum or excess absorption in a shorter wavelength region than 630 nm or shows absorption in a region of longer than 700 nm, a wide absorption curve near the range of absorption maximum wavelength, or much undesirable absorptions, which make the use of such a cyan coupler undesirable. These examples are shown as the curve (2) in the FIGURE mentioned above and reported by Hans I-I. Credner in the text described before.

As mentioned before, the spectral absorption character of the cyan dye image by the photographic lightsensitive material of this invention, such as being present in a region of 635-700 nm in the absorption maximum wavelength, is suitable for the cyan coupler, using a red-light sensitive silver halide emulsion layer, of color positive film, color reversal film, and color paper.

Moreover, the cyan coupler used in this invention can be easily produced with a low cost.

Although the present invention has been adequately described in the foregoing specification and examples included therein, it is readily apparent that various changes and modifications can be made without departing from the spirit and scope thereof.

What we claim is:

l. A color photographic light-sensitive material having at least one silver halide emulsion layer containing a cyan coupler represented by the following general formula, said cyan coupler giving a cyan color image having the absorption maximum wavelength at 640-670 nm when the emulsion layer is colordeveloped by a color developer containing a pphenylene diamine type color developing agent:

at the m-position; Z represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a methyl group, a methoxy group and an ethoxy group; and m is an integer of one or two; said Z may be the same or different if n is an integer two.

2. The color photographic light-sensitive material of claim 1, wherein said p-phenylenediamine type color developing agent or salt thereof is represented by the formula:

wherein R represents a member selected from the group consisting of a hydrogen atom and a methyl group; R and R represent a member selected from the group consisting of an alkyl group having one to four carbon atoms, a B-hydroxyethyl group, a B-methylsulfoaminoethyl group and a 4-sulfobutyl group.

3. The color photographic light-sensitive material of claim 1, wherein said cyan coupler is:

and said p-phenylenediamine type color developing agent is:

4. The color photographic light-sensitive material of claim 1, wherein said cyan coupler is:

C O NHC raHas @jCONHQ and said p-phenylenediam ine type color developing agent is:

5. The color photographic light-sensitive material of claim 1, wherein said cyan coupler is:

C ONHCmHu(n) and said p-phenylenediamine type color developing agent is:

CaHs

HaN N H2804

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3488193 *Jul 11, 1966Jan 6, 1970Agfa Gevaert NvSilver halide emulsions containing naphthol color couplers
US3615604 *Feb 18, 1969Oct 26, 1971Agfa Gevaert AgSilver halide color photographic material containing cyan-forming color coupler
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4250251 *Jul 11, 1979Feb 10, 1981Eastman Kodak CompanyCoupler solvent particles for forming a microcrystalline dye having broadened infrared absorption spectra
US4282312 *Dec 18, 1979Aug 4, 1981Fuji Photo Film Co., Ltd.Color image forming process
US4288532 *Feb 13, 1980Sep 8, 1981Fuji Photo Film Co., Ltd.Color photographic materials containing cyan color-forming couplers
US4690889 *May 10, 1985Sep 1, 1987Fuji Photo Film Co., Ltd.Silver halide color photographic light-sensitive material containing novel cyan dye forming coupler
US4920041 *Jan 12, 1989Apr 24, 1990Fuji Photo Film Co., Ltd.Aromatic primary amine developer with hydroxy component containing a carbonyl-type group
US5258270 *Oct 4, 1991Nov 2, 1993Fuji Photo Film Co., Ltd.Silver halide color photographic material
US5354646 *Mar 7, 1994Oct 11, 1994Konishiroku Photo Industry Co., Ltd.Developer contains hydroxylamine compound and para-phenylenediamine derivative
US5380638 *Oct 2, 1992Jan 10, 1995Fuji Photo Film Co., Ltd.Colorfast, naphthol substituted with amidophenylamide group
EP0112162A2Dec 13, 1983Jun 27, 1984Konica CorporationLight-sensitive silver halide photographic material
Classifications
U.S. Classification430/552, 430/553, 430/484
International ClassificationG03C7/34, C09B53/00
Cooperative ClassificationG03C7/344
European ClassificationG03C7/34N