Color photographic print material

Details Color photographic print material Color photographic print material

2003-07-02

2004-10-19

Letscher, Geraldine (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Radiation sensitive product

Identified radiation sensitive composition with color...

C430S552000, C430S553000, C430S546000, C430S567000, C430S631000, C430S384000, C430S385000

Reexamination Certificate

active

06806042

ABSTRACT:

This invention relates to a colour photographic print material having a novel cyan coupler.
Colour photographic print materials are in particular materials for reflection prints or displays, which most usually exhibit a positive image. They are thus not a recording material like colour photographic films. They predominantly comprise negative-working materials.
Colour photographic print materials conventionally contain at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler.
U.S. Pat. No. 5,686,235 disclosed cyan couplers which, once developed with the standard paper developer CD3, yield cyan dyes which are distinguished by good light and dark stability.
However, these couplers have the disadvantage that the dyes are inadequate with regard to colour reproduction.
The couplers have a 2-acylamino-5-phenylsulfonylmethylcarbonylaminophenol structure and may be substituted on the methyl group by alkyl and on the phenyl residue by various groups.
The object of the invention was to overcome the above-stated disadvantage. This is surprisingly achieved with the novel cyan couplers defined below, while retaining the advantages of the prior art coupler.
However, colour reproduction with the new couplers is still inadequate for very demanding applications, such as for example professional photography.
A further object of the invention was accordingly to eliminate this disadvantage too. This is surprisingly achieved with the novel cyan coupler defined below if it is used together with a small quantity of an oil former.
The present invention accordingly provides a print material having a support, at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler and at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, characterised in that the red-sensitive layer contains at least one oil former, the cyan coupler is of the formula
in which
R
1
means a hydrogen atom or an alkyl group,
R
2
means an alkyl, aryl or hetaryl group,
R
3
means an alkyl or aryl group,
R
4
means an alkyl, alkenyl, alkoxy, aryloxy, acyloxy, acylamino, sulfonyloxy, sulfamoylamino, sulfonamido, ureido, hydroxycarbonyl, hydroxycarbonylamino, carbamoyl, alkylthio, arylthio, alkylamino or arylamino group or a hydrogen atom and
Z means a hydrogen atom or a group eliminable under the conditions of chromogenic development,
and the ratio by weight of oil former to cyan coupler is less than 1:1.
The following meanings preferably apply:
R
1
=an alkyl group;
R
2
=unsubstituted or substituted phenyl, thienyl or thiazolyl group;
R
3
=alkyl group;
R
4
=hydrogen atom;
Z=Cl.
The oil former according to the invention may comprise a high-boiling organic solvent and/or a polymer.
The cyan coupler is particularly preferably of the formula
in which
R
5
means a hydrogen atom or an alkyl group,
R
6
means OR
7
or NR
8
R
9
,
R
7
means an unsubstituted or substituted alkyl group with 1 to 6 C atoms,
R
8
means an unsubstituted or substituted alkyl group with 1 to 6 C atoms,
R
9
means a hydrogen atom or an unsubstituted or substituted alkyl group with 1 to 6 C atoms,
R
10
means an unsubstituted or substituted alkyl group and
Z means a hydrogen atom or a group eliminable under the conditions of chromogenic development
and wherein the total number of the C atoms of the alkyl groups R
7
to R
10
in a coupler molecule is 8 to 18.
The alkyl groups can be straight chain, branched or cyclic and the alkyl, aryl and hetaryl groups can be substituted, for example, by alkyl, alkenyl, alkyne, alkylene, aryl, heterocyclyl, hydroxy, carboxy, halogen, alkoxy, aryloxy, heterocyclyloxy, alkylthio, arylthio, heterocyclylthio, alkylseleno, arylseleno, heterocyclylseleno, acyl, acyloxy, acylamino, cyano, nitro, amino, thio or mercapto groups,
wherein a heterocyclyl represents a saturated, unsaturated or aromatic heterocyclic radical and an acyl represents the radical of an aliphatic, olefinic or aromatic carboxylic, carbamic, carbonic, sulphonic, amidosulphonic, phosphoric, phosphonic, phosphorous, phosphinic or sulphinic acid.
Preferably the alkyl groups can be substituted, for example, by alkyl, alkylene, hydroxy, alkoxy or acyloxy groups and most preferably by hydroxy or alkoxy groups. Preferred substituents for aryl and hetarylgroups are halogen, in particular Cl and F, alkyl, fluorinated alkyl, cyano, acyl, acylamino or carboxy groups.
Suitable Cyan Couplers are:
Synthesis of Coupler I-10
Synthesis of the Phenolic Coupler Intermediate
A solution of 185 g (0.87 mol) of 3,4-dichlorobenzoyl chloride 2 in 50 ml of N-methylpyrrolidone is added dropwise with stirring to 165 g (0.87 mol) of 2-amino-4-chloro-5-nitrophenol 1 in 500 ml of N-methylpyrrolidone. Continue stirring for 1 hour at room temperature and then for 2 hours at 60-65° C. After cooling, slowly combine with 500 ml of water and suction filter. Stir twice with water and then twice with methanol and suction filter.
Yield 310 g (98%) of 3
A mixture of 310 g (0.86 mol) of 3, 171 g of iron powder, 2.2 l of ethanol and 700 ml of N-methylpyrrolidone is heated to 65° C. while being stirred. The heating bath is removed and 750 ml of conc. hydrochloric acid are added dropwise within 2 hours. The mixture is then refluxed for 1 hour. After cooling, 1 l of water is added, the mixture suction filtered and washing performed with 2 N hydrochloric acid, then with water until the outflowing water is colourless. The residue is stirred together with 1.5 l of water, the mixture neutralised by addition of sodium acetate and suction filtered. Stir twice more with 1.5 l of methanol and suction filter.
Yield 270 g (95%) of 4
Synthesis of the ballast residue
320 g (3.6 mol) of 45% sodium hydroxide solution are added dropwise within 1 hour with stirring to a mixture of 520 g (3.6 mmol) of 4-chlorothiophenol 5 and 652 g (3.6 mol) of 2-bromobutyric acid ethyl ester 6 in 1 l of ethanol. The reaction is strongly exothermic, the temperature being kept at 75-80° C. by cooling, and the mixture is then refluxed for 1 hour. A further 400 g (4.5 mol) of sodium hydroxide solution are slowly added dropwise (weakly exothermic). After refluxing for a further 2 hours, the mixture is cooled and 1 l of water is added. Extraction is then performed twice with 250 ml of toluene, the combined organic phases are dried and evaporated in the rotary evaporator. The viscous oil 7 (830 g, still contains toluene) is further reacted without purification.
760 ml of hydrogen peroxide (35%) are added dropwise to a solution of 830 g (3.6 mol) of compound 7 and 10 ml of sodium tungstate solution (20%) in glacial acetic acid: the first 300 ml initially with cooling at 35-40° C. and, after removal of the cooling, the remaining 360 ml at 90-95° C. Once addition is complete, stirring is continued for 1 hour at this temperature. Excess peroxide is destroyed by addition of sodium sulfite. The reaction mixture is combined with 2 l of ethyl acetate and 2 l of water, the organic phase is separated and the aqueous phase extracted twice with 700 ml portions of ethyl acetate. The combined organic phases are washed twice with 700 ml portions of water, dried and evaporated under a vacuum. The residue is dissolved in 300 ml of hot ethyl acetate, cooled and, at the onset of crystallisation, combined with 1 l of hexane. The mixture is then suction filtered when cold and rewashing performed with a little hexane. 835 g (88%) of the compound 8 are obtained.
131 g (0.5 mol) of 8 and 111 g (0.55 mol) of dodecyl mercaptan 9 in 300 ml of 2-propanol are combined with stirring with 90 g (1 mol) of sodium hydroxide solution (45%). After the addition of 2.5 g of tetrabutylammonium bromide and 2.5 g of potassium iodide, the mixture is refluxed

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