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Publication numberUS3510306 A
Publication typeGrant
Publication dateMay 5, 1970
Filing dateJun 8, 1966
Priority dateJun 9, 1965
Also published asDE1547842A1, DE1547842B2, DE1547842C3
Publication numberUS 3510306 A, US 3510306A, US-A-3510306, US3510306 A, US3510306A
InventorsTsuda Momotoshi, Yoshida Makoto
Original AssigneeFuji Photo Film Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Developing process for color photography
US 3510306 A
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Description  (OCR text may contain errors)

OPTICAL DENSITY LII y 1970 MAKOTO-YOSHIDA ETAL 3,510,306

' DEVELOPING PROCESS FOR COLOR PHOTOGRAPHY Filed June 8, 1966 WAVE LENGTH mmvrozzs MAKOTO YOSHIDA BY MOMOTOSHI TSUDA ATTORNEYS United States Patent Int. Cl. misc 7/36 US. Cl. 96-55 6 Claims ABSTRACT OF THE DISCLOSURE The invention is directed to an improved color photographic developing process in which a coupler of the formula Y Q-oo omo 0 NH is reacted with the oxidation product of an aromatic primary developer. The couplers of this invention are yellow couplers capable of forming yellow dyes, having excellent spectral absorption characteristics for providing ideal yellow images and have good silver removing properties.

The present invention relates to color photography and more particularly to a color photographic developing process using a color developing solution containing an improved coupler.

The use of such a coupler as forms dye images by the reaction thereof with the oxidation product of an aromatic primary amine developer in a color photographic development is known and there are many patents concerned with such couplers. Such a coupler will be coupled with the oxidation product of an aromatic primary amine to form a dye which is insoluble in water or a usual developing solution, whereby dye images can be left in the photographic emulsion layer. Such a coupler may be added in a developing solution or may be incorporated in a photographic emulsion layer before exposure. The coupler in this invention is of the type which is added to a developing solution.

This type of coupling process is usually a subtractive color process, wherein the couplers capable of forming cyan, magenta and yellow dyes are used.

Couplers for color photography are required to form, by color development, dyes having desired spectral absorption characteristics.

Ideally speaking, in particular, a yellow coupler must absorb completely blue lights and transmit completely green and red lights. However, many of the conventionally used couplers are deficient in such characteristics. Further, in the case of processing a photographic emulsion layer containing a yellow coupler, it is, after a first develop ment, exposed in blue light, subjected to a yellow color development, and then bleached and fixed to provide yellow images. But in this case it frequently happens that the reduced silver remains in the bleaching step caused by the slow oxidation of the reduced silver and the silver remains in the yellow image without being removed completely in the fixing step. Hereinafter, the phenomenon is called insufficient silver removal. This reduces extremely the transparency of the yellow image.

An object of this invention is to provide a color photographic developing process using an improved yellow coupler capable of forming a yellow dye having the ex- 3,510,306 Patented May 5, 1970 cellent spectral absorption characteristics for providing ideal yellow images and having good silver-removing @woomoounwherein X represents a halogen atom, an alkyl group, a trifluoromethyl group, an alkoxy group, an acylamino group or an aryloxy group; Y represents a hydrogen atom or above-mentioned group X; and Z represents a hydrogen atom or a halogen atom.

The above alkyl group may be, for example, methyl, ethyl, and propyl groups. The above-mentioned alkoxy group may be, for example, methoxy, ethoxy and propoxy groups. The acylamino group may be, for example, acetamino, propionamino, benzoylamino, toluenecarboamino, methanesulfoamino, benzenesulfonamino, and toluenesulfonamino groups. The aryloxy group may be, for example, phenoxy and tolyloxy groups.

It has been known that benzoylacetanilide is useful as a yellow coupler but the dye image obtained by using the yellow coupler has a bad silver-removing property and reduced spectral absorption characteristics.

Furthermore, 2-methylbenzoylacetanilide is described in I. of the American Chemical Society, vol. 79, page 2920, but the silver-removing property of the coupler is bad and, as shown in the accompanying drawing, the spectral absorption characteristics of the thus obtained colored image are unsuitable.

The accompanying drawing contains a single figure which is a graphical plot of the absorption curves of a material of this invention and other materials.

In the drawing there are shown comparatively the spectral absorption curve A of a dye image formed by the oxidizing coupling of Z-methylbenzoylaceto-(Z-chloro) anilide 'which is a typical coupler used in this invention and a color developer, 4-N,N-diethylaminoaniline; the spectral absorption curve B of the dye image obtained from a control coupler, benzolacetanilide and the above mentioned color developer; and the spectral absorption curve C of the dye image obtained from another control coupler, Z-methylbenzoylacetanilide and the above-mentioned color developer. In the graph, the vertical axis is graduated for Optical Densityand the horizontal for wavelength of light.

From the curves it will be understood that the dye image obtained from the coupler of this invention has less undesirable components which absorb in the green range and has very excellent absorption characteristics.

Moreover, it will be also understood that the coupler of this invention has very preferable property in silver removal as shown below.

That is, the silver-removing property is shown numerically by the ratio of the silver density, measured by using a red filter, to the sum of the densities of the dye image and silver image, measured by using a blue filter, as follows red light density (D blue light density (D =numerical value this invention and 4-N,N-diethylaminoaniline; the dye image (E) obtained from 2 methylbenzoylaceto-(4-(4- toluenesulfonamido) anilide and the above-mentioned developer; and the dye image (F) obtained from 3-methylbenzoylaceto-(2-methoxy)anilide and the above-men- 4' cellent transparency of the thus obtained dye image, which is very profitable for color reproduction.

The reason that the dye images obtained from the couplers of this invention have the spectral absorption characteristics and very good silver-removing property may tioned developer. The results are as [fOllOWSZ 5 be considered to be based on the chemical structure thereof in that the benzoyl nucleus has a methyl group and the anilide nucleus has as substituents at least one of the DB group consisting of halogen atoms, alkyl groups, trifluoro- Dye image 1 0 L 5 2 0 methyl groups, alkoxy groups, acylamino groups or aryloxy groups. 8: 2; 8: H2 81%; In particular, as is clear from the examples below, the 0.36 0. 0.28 0. 26 coupler having a methyl group at .the 2-position of the 8: 8: i3 3: gig I benzoyl nucleus and one of the above-mentioned substitu- 0. 23 0.20 0.18 0.16 15 ents at the 2-position of the anilide nucleus is excellent. The use of the couplers shall not be limited to natural color photography but they may be used for obtaining From the results it will be clear that the couplers used mono-color images or two-color images. in this invention give very good silver removing property. Examples of the yellow couplers useful in this invention The good silver-removing property shows up in the exare as follows:

Melting Formula N0. Coupler formula point, C.

1 -C0CH3OONH- 94-95 2 C O CH2CONH H3 CIJCHZ a- @COCH2CONHC1 I CH; 01

4 coomo0m1 82 I I CH3 F I s- C 2 ON 15s (3H3 Cl 6 Cm-QOOOHZ ON Q 154 CH3 7-- @coemoonn-Q 121-122 I (3E3 @113 8.- O z N 57-58 I (7H3 OF3 0- -eoonzconn- 141 I CH3 F 10 CHF'Q-COCHZGONHG 141 11 0 H2 0N F 92 I CH '12 CHE-Queenie ONE-C} Melti Formula No. Coupler formula point, C.

13 CH3- -o 01120 ONHQ-Cl 147 I or 14 CHQQC 0 CHzO 0NHQCHS 14s 15 @c 0 01120 ONHQ 73-74 CH3 BI 16 c 0 01140 0NH 92 I H3 7 0 02115 17 -00 OH4O0NH NHs or-cm 142 l CH3 o1 1s 0 0 CH2CNH-C H3 158 19 QCOCHNONHQ 11s I I I 7 CH3 Cl 82 2o COOH2CONEP I @151 0 CH4 21 9-0 0 C 2 ONHF 121 22 c0 01140 0NH-0- 9s JJH;

2a CH3 o 0 01120 ONHNHC 0 CH3 164 24 -CO H2 NH- 129 l 5H3 Cl 25 OOCH2CONHC The above couplers may be prepared, for example, as

follows PREPARATION 1 Z-methylbenzoylaceto-(Z-chloro) anilide(Formula 1) Into a 1 liter three-necked flask equipped with a stirrer, a thermometer and an outlet for ethanol were charged 1 mole of ethyl-2-methylbenzoylacetate, 1 mole of o-chloroaniline and 250 ml. of Xylene. The system was heated to 140-150 C. in an oil bath with stirring to distill off byproduct ethanol. After about 3 hours, 80% of ethanol was distilled oif. The reaction was then stopped and the product was cooled, poured in 300 ml. of petroleum ether, and allowed to stand for one night in a cold place to precipitate a white crystalline product which was filtered by suction, washed with 1000 ml. of petroleum ether and then recrystallized using 2000 ml. of ligroin. The yield was 82% and the melting point of the crystal was 9495 C.

PREPARATION 2 Z-methylbenzoylaceto-(2-fluoro) anilide(Formula 4) The same procedure as in Preparation 1 was repeated using o-fluoroaniline instead of o-chloroaniline to provide a white crystalline product which was recrystallized :by using methanol. The yield for the product was 55% and the melting point thereof was 82 C.

PREPARATION 3 4-methylbenzoylaceto- (2-fluoro) anilide-- (Formula 12) The procedure as in Preparation 1 was repeated using 1 mole of ethyl-4-methylbenzoylacetate, 1 mole of ofluoroaniline, and 300 ml. of xylene to provide'a white" crystalline product which was recrystallized by using methanol. The yield was 49% and the melting'point of the crystal was 109 C.

PREPARATION 4 2-methylbenzoylaceto-(2-ethoxy) anilide-(Formula 16) The same procedure as in Preparation 1 was repeated using o-ethoxyaniline instead of o-chloroaniline to give a White crystalline product which was recrystallized by using acetonitrile. The yield of the product was 48% and the melting point thereof was 92 C.

PREPARATION 5 Z-methylbenzoylaceto-(4-(4-toluenesulfonamide) anilide--Formula 17) The same procedure as in Preparation 1 was repeated using 4-(toluenesulfonamido)aniline instead of o-chloroaniline to provide a white crystalline product which was recrystallized by using methanol. The yield of the product was 53% and the melting point thereof was C.

PREPARATION 6 3 -methylbenzoylaceto- Z-methoxy) anilide- (Formula 20) The same procedure as in Preparation 1 was repeated using 1 mol of ethyl-3-methyl-benzoyl acetate, 1 mol of' o-anisidine and 300 ml. of xylene to provide a white crystal, which was recrystallized by using a mixed solvent of ligroin and ethanol (1:1). The yield for the prodnet was 75% and the melting point thereof was 82 The invention will further be described with reference to the following examples.

EXAMPLE 1 the material was subjected to the following color development as usual:

First development 24 C.--5 min. Water washing-2 min.

Reversal blue exposure200 GMC. Yellow color deve1opment5 min. Water washing-2 min. Bleaching-2 min.

Water washing2 min.

Fixing-2 min.

Water washing2 min.

By this procedure, a positive image of yellow dye having very good transparency was obtained. The spectral absorption curve of the dye image is shown in the accompanying drawing as Curve A.

' EXAMPLE 2 The same test sample as in Example 1 was subjected to the same diflferential exposure as in the example and then color developed as in the example using Z-methylbenzoylaceto-(Z-ethoxy)anilide (Formula 16) instead of wherein X represents a member selected from the group.

'3-methylbenzoylaceto-(2-chloro)anilide (Formula 1) to provide a positive image of the yellow dye having an absorption maximum of'438 nm. and very good transparency.

EXAMPE 3 The same test sample as in Example 1 was subjected to ,diflferential exposure and, using a yellow color developing solution having the following composition, was color developed as in Example 1:

Developing solution Bythe procedure, a positive image of yellow dye having an absorption maximum of 445 nm. and very good transparency was produced.

EXAMPLE 4 The same procedure as'in Example 1 was repeated using as the coupler 4 methylbenzoylaceto-(2-fluoro) anilide (Formula 12) instead of Z-methylbenzoylaceto- (2-ch1oro)anilide to give a positive image of yellow dye having an absorption maximum of 448 nm. and very good transparency.

EXAMPLE 5 The same procedure as in Example 1 was repeated using as the coupler 2-methylbenzoylaceto(4-(4-toluenesulfonamido)anilide (Formula 17) instead of 2-methylbenzoylaceto-(2-chloro) anilide to provide a positive image of yellow dye having an absorption maximum of 442 nm.

and very good transparency.

What we claim is: 1. In a color photographic developing process wherein a developer solution containing a coupler and an aromatic primary amine developer is applied to a silver halide photographic emulsion, forming dye images by the reac "tion of the coupler with the oxidation product of the aromatic primary amine developer, the improvement comprising color developing by application of a solution containing a coupler represented by the general formula:

Q-ooomoomrconsisting of a halogen atom, an alkyl group, a trifluoromethyl group, an alkoxyl group, an acylamino group and an aryloxy group; Y represents a member selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a trifluoromethyl group, an alkoxyl group, an acylamino group and an aryloxy group and Z represents a member selected from the group consisting of a hydrogen atom and a halogen atom.

2. The color photographic developing process as claimed in claim 1 wherein said alkyl group is selected from the group consisting of methyl, ethyl and propyl.

3. The color photographic developing process as claimed in claim 1 wherein said alkoxyl group is selected from the group consisting of methoxy, ethoxy and propoxy.

4. The color photographic developing process as claimed in claim 1 wherein said acylamino group is selected from the group consisting of acetamino, propionamino, benzoylamino, toluenecarboamino, methane-sulfoneamino, 'benzenesulfoneamino and toluenesulfonamino.

5. The color photographic developing process as claimed in claim 1 wherein said aryloxy group is selected from the group consisting of phenoxy, tolyloxy.

6. The color photographic developing process as claimed 5 in claim 1 wherein said coupler has a methyl group at the 2-position of the benzoyl nucleus and is substituted by one of the members X, Y and Z at the 2-position of the anilide nucleus.

1 0 References Cited UNITED STATES PATENTS 6/1950 McQueen 96100 FOREIGN PATENTS 595,314 12/1947 Great Britain.

I. TRAVIS BROWN, Primary Examiner

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2513190 *Feb 18, 1948Jun 27, 1950Du PontPolymeric color formers
GB595314A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4201584 *Sep 19, 1978May 6, 1980Agfa-Gevaert N.V.Silver halide elements containing yellow forming color couplers for silver halide photography
US4842979 *Nov 30, 1987Jun 27, 1989Fuji Photo Film Co., Ltd.Black color heat-sensitive diazo microcapsule recording material with benzoylacetic amide coupler
Classifications
U.S. Classification430/376, 430/388
International ClassificationG03C7/36
Cooperative ClassificationG03C7/362
European ClassificationG03C7/36B