GB2351812A - A colour photographic copier material - Google Patents

Abstract

A colour photographic copier material comprises 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. In the at least one red-sensitive layer, the copier material contains at least one pyrazoloazole cyan coupler of formula (I) <EMI ID=1.1 HE=26 WI=70 LX=603 LY=1280 TI=CF> <PC>(wherein<BR> R<SP>11</SP>, R<SP>12</SP>, X<SP>11</SP>, Y<SP>11</SP> and n have the meanings given in the description)<BR> and a two-equivalent yellow coupler associated with the at least one red-sensitive layer or where the red-sensitised silver halide emulsion is associated with the at least one blue-sensitive silver halide emulsion layer.

Description

A-G 6747-Forei_gn Countries JCAlkluNT 2351812 -I- A colour photographic

copier material This invention relates to a colour photographic copier material which comprises at least one pyrazoloazole as a cYan coupler.

In particular, colour photographic copier materials are materials for opaque images or displays, and generally comprise a positive image. They are thus not recording materials like colour photographic films.

Pyrazoloazoles are cyan couplers, which are known from IP-A 64-554 and EP 717 315 for example, which provide very clear cyan dyes with relatively short- wave absorption bands and very high extinctions and which therefore enable savings of silver halide to C) be made. Moreover, the cyan dyes of these couplers exhibit very good stability on storage with the exclusion of light.

A disadvantage of these couplers is that they give rise to a colour shift of blue and cyan 0 colour shades. - The object of the present invention is to eliminate this disadvantage so as to be able to utilise the advantages of these couplers.

Surprisingly, it has now been found that this object can be achieved for a material of the 1 type cited at the outset, which comprises at least one red-sensitive silver halide emulsion layer which comprises at least one cyan coupler, at least one green-sensitive silver halide emulsion layer which comprises at least one magenta coupler, and at least one blue-sensitive silver halide emulsion layer which comprises at least one yellow coupler, which material contains, in the at least one redsensitive layer, at least one pyrazoloazole cyan coupler of formula (I) A-G 6747-Forei-gn Countries X 12)n Y 11 N wherein R" and R 12, independently of each other, represent an electron- attracting group, Xii represents H or a group which can be split off by reaction with developer oxidation product, y1i represents a group for the completion of a nitrogen-containing heterocycle, with V the proviso that a group represented by R 12 is bonded to a carbon atom of the heterocycle, and n represents I or 2, characterised in that a two-equivalent yellow coupler is associated with the at least one red-sensitive layer or a red-sensitised silver halide emulsion is associated with the at least one layer which comprises a yellow coupler.

If a two-equivalent yellow coupler is associated with the at least one red-sensitive layer, the yellow coupler is preferably used in the at least one red-sensitive layer. In particular, the amount of yellow coupler in the red-sensitive layer ranges from 1 to 10 mol % of the amount of cyan coupler of formula (I).

The two-equivalent yellow coupler which is used in the red-sensitive layer preferably exhibits a rate of coupling which is not more than five times the rate of coupling of the t a pyrazoloazole cyan coupler. The rate of coupling is determined by the method described in J. Phot. Sci. 36, (1988), page 14.

A-G 6747-Foreign Countries Two-equivalent yellow couplers almost always couple significantly more rapidly than cyan couplers. It would have been expected that a cyan layer composed according to the invention would exhibit a colour shift from low to high densities, with the low densities being strongly shifted towards yellow or green. 5 Surprisingly, however, this does not occur.

0 The preferred two-equivalent yellow couplers are acetanilides, particularly pivaloyl acetanilides and malonic anilides, the volatile groups of which are linked to the coupler molecule via 0 or N and which are substituted in the ortho position of the anilide component by chlorine, alkoxy or aryloxy.

Two-equivalent yellow couplers which are quite particularly preferred correspond to formula (H): is R21 R 2-4 R 1 26 R22-C-CO-CH-CONH - 1 1 (H) 1 H23 R25 wherein R21 denotes an alkyl, which preferably comprises 1 to 4 C atoms, particularly methyl, R22 denotes an alkyl, which preferably comprises 1 to 4 C atoms, particularly methyl, R23 denotes a hydrogen atom or an alkyl, which preferably comprises 1 to 4 C atoms, particularly methyl,or A-G 6747-Foreign Countries R22 and R23 together denote the remaining members of a cyclopropyl radical, R24 denotes chlorine or alkoxy, R25 denotes -NHCO-R2-7, -S02NH-R27, -NHS02-R27, -COOR27, Cl, Br or alkoxy, R26 denotes a hydrogen or chlorine atom, R27 denotes a substituent, particularly a ballast group, and Q denotes the remaining members of a substituted irnidazole, imidazolidinedione, oxazolidinedione or triazolidinedione ring, wherein the alkyl groups can be further substituted.

Numerous possibilities exist for the joint incorporation in one layer of a cyan coupler according to the invention and a yellow coupler: these compounds can be incorporated C) in a common emulsion in at least one coupler solvent, or in two separate emulsions, which optionally each comprise at least one coupler solvent, If a red-sensitised silver halide emulsion is associated with the at least one blue sensitive layer, said emulsion should provide, over the entire density range for red exposure, an amount of yellow density which corresponds to I to 30 %, preferably 3 to %, of the cyan density.

The term "associated" means that the red-sensitised silver halide emulsion is situated in the blue-sensitive layer or in a layer adjacent thereto, so that the developer oxidation A-G 6747-Forei-Rn Countries I- -5- product (DOP) which is formed in this layer on development only couples with one coupler, namely the yellow coupler, in the at least one blue- sensitive layer.

The red-sensitised silver halide emulsion is preferably situated in the at least one blue- sensitive layer itself.

In this situation, the invention can be put into effect by employing a silver halide emulsion which is both blue- and red-sensitised, or by mixing two separate blue- or red-sensitised silver halide emulsions with each other. Finally, the red-sensitised silver halide emulsion can also be used in a separate layer together with the yellow coupler.

The red-sensitised silver halide emulsion which is associated with the blue-sensitive layer is selected in particular so that it approximately corresponds to the red-sensitivity of the layer which contains the cyan coupler, This can be effected via the amount of sensitiser or can also be effected via the grain size, for example.

Suitable blue sensitisers correspond to formula (111) R _X 31 X7qR 31 3 38 C H R N (j) N R 32 / 37 R 33 R 34 35 R 36 OEID M wherein R31 to R33 and R36 to R38 denote H, alkyl, alkoxy, halogen, 2-thienyl, 3- thienyl, 1-pyrrolyl, 2-pyrrolyl, phenyl, I-indolyl, 2-furanyl, 3-furanyl or carbazolyl, R34 and R35 denote alkyl, sulphoalkyl, carboxyalkyl, A-G 6747-Foreign Countries -(CH2)siSO2N--COR39i -(CH2)nSO2N-SO2R395 -(CH2),CON-SO2R39 or -(CH2),,CON- C-OR39, X31 and X32 denote 0, S, SC, NR303 M denotes a counterion, n denotes a number from 2 to 4, and R39 andR30 denote a Cl-C4 alkyl, or R31 and R32 or R32 and R33, R36 and R37 or R37 and R38,represent the remaining members of a condensed-on benzene or naphthalene ring.

Preferred blue sensitisers correspond to formula (TV) R41 S X41 N H N R45 R42 (CIFIA R R43 (CH2)m 44 1 E) 1 o m (M S03 S03 wherein R41 and R43 denote hydrogen, R42 denotes a halogen, particularly chlorine or fluorine, or 2-thienyl, 3- thienyl, I pyrrolyl, 2-furanyl, 1 -indolyl or phenyl, or R4, and R42 together, or R42 and R43 together, denote the remaining members of a condensed-on benzene or naphthalene ring, R44 denotes hydrogen, A-G 6747-Foreign Countries IZ45 denotes a halogen, particularly chlorine or fluorine, phenyl, 2- thienyl, 3-thienyl, Ppyrrolyl, 2-furanyl, 1-indolyl, or R44 and R45 together denote the remaining members of a condensed-on benzene or naphthalene ring, X41 denotes S or 0, m denotes a counterion, particularly triethylammonium, and 10 1 and m denote a number from 2 to 4.

Suitable red-sensitisers correspond to formula (V) R50 R 60 R5 X51 CH X52 N -i R 1 -- - c R -: \ e R59 58 i 52 R53 R 54 R / N - R, (V) m R 56 57 is wherein X51, X52, R51 to R58 and M have the same meanings as R31 to R38, X31 and X32 in formula M, Rsq denotes H, an alkyl, a halogen, dialkylarnino or thio, and R50 and R60 denote H or an alkyl. 25 The red-sensitisers preferably correspond to formula (VI) A-G 6747-Foreign Countries H3 C CH3 R 61 S -c C H X 61 R 62 N (j) N R 68 R 63 R 64 m R65 R66 R67 wherein 5 R64, R65 X6i and M have the same meanings as R34, R352 X32 and M in formula III, C R61, R62, R63, R66, R67 and R68, independently of each other, denote H, CH3, OCH3, Cl, 1-pyrrolyl, 1-indolyl, 2-thienyl, 3-thienyl, 2-furanyl, 3- furanyl, N-carbazolyl or phenyl, or R61 and R62, or R62 and R63, as well as R66 and R67 or R67 and R68, together denote the remaining members of a benzo, 1,22 naphtho or 2,3-naphtho ring.

The term "alkyF' in the sense of the present Application should be understood to mean linear or branched, straight chain or cyclic, substituted or unsubstituted hydrocarbon groups. Alkyl groups comprising 1 to 32 C atoms are preferred. Open-chain alkyl groups which are particularly suitable include methyl, ethyl, n-propyl, n- butyl, n-octyl, n-dodecyl, n-hexadecyl and n-octadecyl groups, and branched alkyl radicals which are particularly suitable include 2-hexyIdecyl, 2-octyIdodecyl and 2- ethylhexyl radicals.

Cycloalkyl groups are preferred amongst the alkyl groups, particularly 4t-butyl, cyclohexyl, and 2,6-di-t-butyl4-methylcyclohexyl groups. The term "alkenyF' in the sense of the present Application should be understood to mean linear or branched, cyclic or straight chain, substituted or unsubstituted, unsaturated ^hydrocarbon radicals, such as ethenyl, 2-propenyl, isopropenyl and oleyl radicals. The term "aryl" in the sense of the present Application should be understood to mean aromatic hydrocarbon radicals, preferably phenyl or naphthyl. These can be either substituted or unsubstituted.

A-G 6747-Foreign Countries The term "hetaryl" in the sense of the present Application should be understood to mean aromatic systems which contain at least one hetero atom. These are preferably 5 or 6-membered ring systems which can exist as monocyclic or as condensed ring systems. They can comprise both substituted and un-substituted rings systems. N, S and 0 0 are particularly suitable hetero atoms. A ring system preferably contains between I and 3 hetero atoms, which can be identical or different hetero atoms. In condensed ring systems, a plurality of identical or different systems can be condensed, such as hetaryl groups with arylene groups. Typical examples include: pyridine, pyridazine, pyrin-iidine, pyrazine, oxazole, isoxazole, thiazole, 3,4-oxadiazole, 1,2, 4-oxadiazole, imidazole, 1,2,3-triazole and 1,2,4-tri-azole, particularly furane, pyrrole, thiophen and indole.

The term "alkoxy" in the sense of the present Application should be understood to mean radicals of formula OR', wherein R' represents an alkyl radical according to the definition given above.

The term "aryloxy" in the sense of the present Application should be understood to mean radicals of the OR" type in which R" represents an aryl radical according to the definition given above.

An acyl radical in the sense of the present Application can be an aliphatic, olefinic or aromatic carboxylic, carbonic, carbarric, sulphonic, amidosulphonic, sulphinic, phosphoric, phosphonic or phosphonous acid radical.

Suitable substituents in the sense of the present Application include aryl, alkyl, alkoxy, aryloxy, acyl, acyloxy, acylamino, hetary], alkynyl, hydroxy, cyano, carboxy and sulpho groups, and halogens, preferably fluorine, chlorine or bromine. An electron-attracting group in the sense of the present Application is a carboxy, 30 carbamoyl, acyloxy, oxycarbonyl, halogenated alkoxy, halogenated aryloxy, aryloxy, acyl, sulphonyl, sulphinyl, sulphonyloxy, sulphonylmethyl, sulphamoyl, tetrazolyl, A-G 6747-Foreign Countries pyrrolyl, phosphonyl, halogenated alkyl, halogenated aryl, cyano, alkylsulphonylmethyl, arylsulphonylmethyl or a nitro group, all of which may optionally be substituted, as well as a halogen atom.

Cleavage groups X11 can be a halogen, e.g. chlorine, N-heteroaromatic compounds which are linked via the N and which are optionally substituted, e.g. pyrrazoles, imidazoles, triazoles, or non-aromatic heterocycles, e. g. hydantoins, oxazolidinediones, aliphatic or aromatic mercaptans which are bonded via S, e.g. mercaptopropionic acid, 2acylaminophenylmercaptans, or aliphatic or aromatic hydroxy 10 compounds which are bonded via 0, e.g. ethylene glycol or ethyl p-salicylate.

The compounds of formula (1) which are preferably used are those of formula (I-A) X1 2 Z12 R13'-,! N - N (I-A) N - N --\ R 14 wherein R13 andR14, independently of each other, have the meanings of R, 1 or R12, X12 has the meaning of X I,, and Z12 represents H or a substituent.

Some particularly preferred compounds of formula (1) or (I-A) are listed in the following Table.

R13 R14 X12 Z12 PI cl H H t-C5 H, O-CH-CH-NH-CO- t-C5H, 1 ( 1;M 3 1-2 -S-CH2-CH2-COOH H t-C5H17 0-(CH JZ-NH-CO- -0-cl t-C5H11 P3 cl H t-CsH, O-CH-CH-NH-CO- -O-CN t-C5HI, 1-4 ci H H a t-C,H,-O-O-CH-CH-NH-CO9 cl 1-5 CH--"'NH-CO- -NH-S0i-iCH H 3 3 17 H3 R13 R14 -X F21- ZM 1-6 C16H33-0-CO-CH2-CH2-NH-CO- F F H H F > F F 1-7 0 C12H25-SO2-C3H6-NH-CO-CF3 H t (D v -2 n CA C4H 0 10-CH 2 3 1-8 C13H77--OW-G-NH-CO- cl Cl H H 1 1 1-9 Cl.H7-OCO-CH-NH-CO- cl H H 1 (-;3 m 7-1 1-10 CISH37-N-H-SO2 NH-CO-) H H R14 Z12 PI 1 P4H9A CN H H > CH3 C -CO-YH-NH-CO C H A C4H9 b.

4 9 ITI 1-12 H H t-C5H, O-C4Hi-NH-CO-CH-NH-CO N 0 1 t-C5H11 9 s5.

(D 1 C n n 1-13 C H7-OCO-CH-NH-CO- NWS0i-C H i H 13 2 8 17 CO0C2H5 - cl W --o - 1 1-14 C8H 17 H H C4H?-CHCHF-NH-CO NH-CO- N 2t'S H-SOF-40 0C4H9 1-15 t-C4 H--NH-CO- Copolymer aus H H CO0C4 Hq -14 R 13 X12 z und NH-CO 50/50 Gew,% 1- 16 -CN -0-NH-CO-C 17 H35 -S-CH2-CH2-COOH H 1-17 CH3 H H C H t_ CH3C NH-CO- --Q 2 H5 3 NH-CO1H-0- 5-t-C,Hll H3 1-18 O-CO-CH-NH-CO- cl H H 1 cl Ri3M7 -( 1 1-19 H33 Cjj-0-CO-CH-NH-CO- 'ec 4H9 1-20 N H H H2AI-O-CO-&NH-CO- A-G 6747-Foreign Countries Suitable yellow couplers of formula (II) are the following:

0 0 c 12H 25 0 HN H N " SO 2 0 0 1 H,, H 0 0 1CH 3 H 3C" N -) C N FI:C H >r 3 H CHY, Cl HC C H, CH3 0 Cl o N f 0 0 'N so 2 0 (11-2) Cl H H 02 S, N Y e2H5 N S02 0 0 0 H 0 -" U 11 N H 3 C>r 'rH 0 3 CH3 N N 3 N 0 C161A 3 (n) p _ j __j N H 0, E, O---- 0 C18H 37 (n) N NH H 2C 0C2H5 c (U-3) (H4) NH' S02-Cl.H33(n) 0 O-Cl4H 29 0 0 0 0 cl H3C >C J N Z1.1 1 "[LN i HCH H Cl 3.C 3 0 'CL 7C H 3 H Cl 1 - Ozz: N yo S02 OH A-G 6747-Foreign Countries (11-6) COOC,,H33(n) cooc 12 H.,p) 0 0 00 1 H 3C N- "'RH cl H 3C:1- H m 3CC7H 3 H C N 3 CH3 N H cl o:/ 0 1 0 -ro 0C2H5 H3C 0 CH3 cl 0 0 HN-I-f 11 9 Sol-C,2H,(n) (CHJ,CC-CRCNH-0 C CH 3 t-C 0 0 0 0Z N 1 11 H,C N" "ro NH-C.CH-02b-t-C,H, HC H OCH3 CH H C 0 2H5 3 N 3 0-' 'Yo CH3 N-N C.H,(n) (11-9) (11-10) A-G 6747-Foreigp Countries Suitable compounds of formula (rV) are the following, in which 1 and m = 3 and which comprise triethyl ammonium as the counterion:

X3 R21 R22 R23 R24 R25 Iv- 1 S H 2-thienyl H H cl IV-2 S H 3-thienyl H H cl W3 5 H Ppyrrolyl H H cl IV-4 S H 2-furyl H H F IV-5 S H 1-indolyl H H cl IV-6 S H benzo H cl IV-7 S H cl 1 H H cl IV-8 S H 1,2-naphtho H cl IV-9 0 H 2,3-naphtho H phenyl X3 R21 1 R22 R23 R24 R25 rv-10 0 1,2-naphtho H benzo TV-11 S H cl H H 1 phenyl IV-12 S H benzo benzo IV-13 0 H benzo 1,2-naphtho IV-14 S H 2-thienyl H H 2-thienyl IV- 15 S H 3-thienyl H H 3-thienyl IV-16 S H Ppyrroly] H H Ppyrrolyl IV-17 S H Pindolyl H H Pindolyl A-G 6747-Foreign Countries 18- Suitable red-sensitisers are the following:

V-1 H3C CH3 S C H CHZ-S N I@ JPN C2 H 5 C2H5 V-2 H3C CH3 S /-CH CHZ:S N G) N H (eH) 2 5 1 2 3 so C) 3 V-3 H 3 C CH 3 H 3C', S C H CHZ::-S N@ CH 3 1 1 U2t15 C5 H,, 0Tos (1) V-4 H3C CH3 S C 0J /- H CHZ:-S CH3 N (D N 1 H C # H C2 5 2 5 A-G 6747-Foreign Countnes V-5 H 3C CH3 CH 3 S /-CH CH S N CH3 1 C+) IN - U2t15 C2H5 0Tos V-6 H3C H H3C 'aN q) CH3 S CH S N C2H5 C2H5 V-7 H3C CH3 IS /-c CH S IN () 1 IN -Q (CH)_ UM2)3 2 3 cl E) 1 0 S 3 bU3 9 HN(C2H 1 A-G 6747-Foreign Countries W8 H 3 C CH 3 S /-CH CH S CN (CH 2)3 (CH33 1 1 c) bo so 3 3 HN(C 2 H J3 C9 H3C CH 3 S CN /-CH CH S /N (CHI (CH)3 2 So so 3 HN(C2HJ3 mlo H 3 C CH 3 S 1 S /-CH CH S N Q N 01 1 H (CH) C2 5 1 2 3 - W3 () A-G 6747-Foreigpi Countries V-11 H 3 C CH 3 s />- C Hi CH s N @ s N (CH2)3 U2H5 I G S03 V-12 H3C CH3 -S />-C CH 0 N o+ N C::6 1 1 --z: cl (CH 2)3;H 2)3 S03 so 3 9 H N C2 H 5)3 V-13 H 3C C H 3 s />-C4'--,CH 0 N @ N (CH 2)3 (CH 2)3 1 so 3 603(9 HN (C2 H 5)3 A-G 6747Foreign Countries V-14 H3 C CH3 S / -CH C H N (i) CH3 CH 3 0 W, Nb C2H5 (;2H5 V- 15 H3C CH3 S -C CH -- 0 IN CH3 N C2H5 C2H5 0Tos V-16 H35 C CH3 S S-Q 1 C -t, N p 0 1 a N U() cal A-G 6747-Foreign Countries V-17 H 3C CH3 S /-c CH N () N 1 N CY15 Examples of colour photographic copier materials include colour photographic paper, colour reversal photographic paper and semi -transparent display material. A review is given in Research Disclosure 37038 (1995), Research Disclosure 38957 (1996) and

Research Disclosure 40145 (1997).

Photographic copier materials consist of a support on which at least one light-sensitive silver halide emulsion layer is deposited. Thin films and foils are particularly suitable as supports. A review of support materials and of the auxiliary layers which are deposited on the front and back thereof is given in Research Disclosure 37254, Part 1 (1995), page 285 and in Research Disclosure 38957, Part XV (1996), page 627.

Colour photographic copier materials usually contain at least one redsensitive, at least one green-sensitive and at least one blue-sensitive silver halide emulsion layer, and optionally contain intermediate layers and protective layers also.

Depending on the type of photographic copier material, these layers may be arranged 1 0 differently. This will be illustrated for the most important products:

Colour photographic paper and colour photographic display material usually comprise, in the following sequence on their support: a blue- sensitive, yellow-coupling silver halide emulsion layer, a green- sensitive, magenta coupling silver halide emulsion layer, and a red- sensitive, cyan-coupling silver halide emulsion layer. A yellow filter layer is not necessary.

A-G 6747-Foreign Countries Departures from the number and arrangement of the light-sensitive layers may be effected in order to achieve defined results. For example, colour papers may also comprise intermediate layers which are sensitised differently and via which the gradation can be influenced.

The essential constituents of the photographic emulsion layer are the binder, the silver halide grains and colour couplers.

Information on suitable binders is given in Research Disclosure 37254, Part 2 (1995), page 286, and in Research Disclosure 38957, Part H.a (1996), page 598.

Information on suitable silver halide emulsions, their production, ripening, stabilisation and spectral sensitisation, including suitable spectral sensitisers, is given in Research 0 is Disclosure 37254, Part 3 (1995), page 286, in Research Disclosure 37038, Part XV (1995), page 89, and in Research Disclosure 38957, Part V.A (1996), page 603.

In addition, pentamethine cyanins can be used as red sensitisers for the red-sensitive layer which comprise naphthothiazole, naphthoxazole or benzthiazole as basic terminal groups, which are substituted with a halogen or with methyl or methoxy groups, and which can be bridged by a 9,11-alkylene linkage, particularly a 9,11- neopentylene linkage. The methine chain can additionally comprise other substituents. Pentamethines which have only one methyl group on their cyclohexene ring can also be used. The red sensitiser can be super-sensitised and stabilised by the addition of heterocyclic mercapto compounds.

In addition, the red-sensitive layer can be spectrally sensitised between 390 and 590 rim, preferably at 500 rim, so as to effect better differentiation of red tones.

A-G 6747-Foreign Countries The spectral sensitisers can be added in dissolved form or as a dispersion to the photographic emulsion. Both the solutions and the dispersions can contain additives such as wetting agents or buffers.

The spectral sensitiser or a combination of spectral sensitisers can be added before, during or after the preparation of the emulsion.

Photographic copier materials either contain silver chloride-bromide emulsions comprising up to 80 mole % AgBr, or silver chlodde-bromide emulsions comprising more than 95 mole % AgCl.

Information on colour couplers is to be found in Research Disclosure 37254, Part 4 (1995), page 288, in Research Disclosure 37038, Part H (1995), page 80, and in

Research Disclosure 38957, Part X.B (1996), page 616. For copier materials, the

1 maximum absorption of the dyes formed from the couplers and from the colour developer oxidation product preferably falls within the following ranges: yellow couplers 440 to 450 rim, magenta couplers 540 to 560 rim, cyan couplers 640 to 670 rim.

The yellow couplers which are usually employed in copier materials in association with a blue-sensitive layer are, almost without exception, two-equivalent couplers of the pivaloyl acetanilide and cyclopropylcarbonyl acetanilide series.

The magenta couplers which are used in copier materials are, almost without exception, those from the series comprising ani li nopyrazol ones, pyrazolo[5,1-c](1, 2,4)triazoles or pyrazolo[1,5-bl(1,2,4)triazoles.

The light-insensitive intermediate layers which are generally disposed between layers of different spectral sensitivity may contain media which prevent the unwanted diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer which has a different spectral sensitivity.

A-G 6747-Foreign Countries -26 Suitable compounds (white couplers, scavengers or DOP scavengers) are described in Research Disclosure 37254, Part 7 (1995), page 292, in Research Disclosure 37038,

Part Ill (1995), page 84, and in Research Disclosure 38957, Part X.D (1996), page 621 et seq.

The photographic material may additionally contain compounds which absorb UV light, brighteners, spacers, filter dyes, formalin scavengers, light stabilisers, anti C oxidants, Dmi,, dyes, plasticisers (latices), biocides and additives for improving the dye, coupler- and white stability and to reduce colour fogging, and other substances.

Suitable compounds are given in Research Disclosure 37254, Part 8 (1995), page 292, in Research Disclosure 37038, Parts IV, V, VI, VH, X, M and M (1995), pages 84 et seq., and in Research Disclosure 38957, Parts VI, VIII, DC, X (1996), pages 607, and

610 et seq.

The layers of colour photographic materials are usually hardened, i.e. the binder used, preferably gelatine, is crosslinked by suitable chen-fical methods.

Suitable hardener substances are described in Research Disclosure 37254, Part 9 (1995), page 294, in Research Disclosure 37038, Part XII (1995), page 86, and in

Research Disclosure 38957, Part H.B (1996), page 599.

After image-by-image exposure, colour photographic materials are processed by different methods corresponding to their character. Details on the procedures used and 0 the chemicals required therefor are published in Research Disclosure 37254, Part 10 (1995), page 294, in Research Disclosure 37038, Parts XVI to XXIH (1995), page et seq., and in Research Disclosure 38957, Parts XVIR, M, XX (1996), page 630 et seq., together with examples of materials.

A-G 6747-Foreip-,n Countries Light stabilisers which are suitable for use in the layer which contains the pyrazoloazole cyan coupler of formula (I) are those which are described in EP 544 316, EP 544 317 and EP 545 305 for use with pyrazoloazole cyan couplers.

The preferred light stabilisers correspond to formula (IX) c) R92 R R91.- ', A --I (M1 R- X 91 R93 0 wherein R91 denotes an alkyl, alkenyl or aryl group, R92 and R93, independently of each other, denote a hydrogen atom or an alkyl or alkoxy group compfising up to 16 C atoms, R94 denotes a hydrogen atom or an alkyl group, particularly a methyl group, R95 denotes a Cl -C3 alkylene group, and X91 denotes an oxygen atom or a free electron pair, wherein the alkyl groups can be further substituted.

A-G 6747-Foreign Countries Light stabilisers of formula R92 R 0- N-\SO 2 R 93 R94 are preferred. 5 Other suitable light stabilisers are those of formula (VIR) OR 81 R 83 R 82 1 - R c1 R 82 83 R 82 wherein R81 represents H, or an alkyl, alkenyl, aryl or acyl, R82 represents H, or an alkyl, alkoxy, aryloxy, acylarnino, alkylarnino, arylarrno, hydroxy or hetaryl, and R83 represents H, or an alkyl, alkenyl, aryl, acyl or chlorine, wherein a plurality of R92 and R83 radicals can be the same or different.

A-G 6747-Foreign Countries Typical examples of compounds of formulae (VIII) and (IX) are:

IX-1 0 N-O-O-C,3H27-' 2'\ IX-2 0 O-CH-CH-C H 20\____j -Q 2 1 8 17 CH 3 C6H 13 IX-3 0 O-CH-CH-C H 2 2149 C211 5 IX-4 C2 H 5 02 O-CH2 k;t";4H9 \--/ -Q- O-CH-CH-C H 2 1 4 9 C2H5 Vili- 1 0 H N O-CH- c O-C8H 17 2 Ctl A-G 6747-Foreign Countides VIII-2 H3C CH3 H7C3 0 O-C3H7 H7C3 0 H3 C CH3 O-C3H7 VIR-3 0 1C4H9 t-H9C4 C4Hg-t H C,' 0 9 4 VIU-4 O-C4H9 t-H17C8 N(C4H9)2 VW-5 C3Hf' HO OH H3C CH3 CH3 CH3 A-G 6747-Foreign Countries VW-6 t-H 9C4 C4 Hq-t CH 3 17 HO OH CH 3 H 3 c VM-7 t-H 9C4 HO 0 0 H 3 c 0 -j 2 VIU-8 0 OCH 3 0-1 C16H 33 0 OCH 3 VIR-9 0 C2 HS NH-SO 2 7 O-C 12H 25 u, C2H5 AG 6747-Foreign Countries Oil-formers, which are particularly suitable for use with pyrazoloazole cyan couplers of formula (I) because they improve the absorption properties and stability to light of the corresponding dyes, are those of formula (V11) 0 HO (-NH-)n S02+NW) M-9 (VID (R71)o (R72)p wherein R71 represents an alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylamino, arylamino, acyl, acylamimo, acyloxy, hetaryl, halogen, nitro or cyano, 10 R72 represents OH or has the same meaning as R71, n, m, independently of each other, represent 0 or 1, 0 represents 0, 1, 2, 3, 4 or 5, with the proviso that the compound as a whole contains at least 16 C atoms.

Some examples of formula (VII) which are particularly preferred according to the invention are listed below. 20 H VII-1 H0-0-N-SO2--0-0-C12 H25 H -0 HO N S02 VII-2 HN \ CO-CH-C4 H9 1 U2H5 A-G 6747-Foreign Countries H HO N SO 2 O-CH2CH-C 6 H 13 1 VE-3 c H cl cl H_G HO SO-N O-CH-CH-C H VU-4 2 2 1 10 21 c 8 H 17 H 0 H0-0-N-50 2 C-0-tCH 2o 3 NH H 3C CH3 VE-5 H H-C04CH2-2+0 N CH 3 HO -0-N S02 H V11-6 HO -p S0i-N -C C12H25-' (mixture of isomers) H 3C VH-7 HO-.S02---O-CH-CO-O-C6H 13 j U 12 H 25 OH 1 HO-0--O-O-CH 2 CH-C 12 H 25 VH-8 S02 - A-G 6747-Foreign Countries HO so 2 _0_C4Hq-t VII-9 0 N-f CH2 O-C H H 12 25 0 VU-10 H0_&S0 0-f CH -CH 2 2+_N-C-CH2 2 4 +2 C H 16 13 V11- I I HO-- Soi- -0-CH2 CH-CA7 (mixture of isomers) C) CI Compounds of formulae (1) and (11) according to the invention can be used in the customary amounts in the photographic material. Compounds of formula (1) are preferably used in amounts from 20 to 2000 MgIM2 Of the photographic material, particularly from 50 to 500 mem 2 of the photographic materials. Compounds of formula (VU) are preferably used in a ratio by weight ranging from 20:1 to 1:10 to compounds of formula (1), and are used in particular in a ratio by weight from 10: 1 to 1:5, most preferably in a ratio by weight from 5:1 to 1:2.

Compounds of formulae (1) and (VII) according to the invention are preferably used in a red-sensitised silver halide emulsion layer or directly adjacent to a red-sensitised silver halide emulsion layer. In particular, compounds of formulae (1) and (VII) are used in the same layer.

In one preferred embodiment, the at least one red-sensitive layer additionally comprises at least one N,N-di substituted p-arninophenol ether of formula (IX).

A-G 6747-ForeigLi Countries Examples

Example 1

A colour photographic recording material suitable for a rapid processing procedure was produced by depositing the following layers in the given sequence on a film base comprising paper coated on both sides with polyethylene. The quantitative data are given with respect to 1 M2 in each case. The corresponding amounts of AgN03 are quoted for silver halidedeposition. 10 Layer structure 101 Layer 1: (substrate layer) 0. 10 g gelatine 15 Layer 2: (blue-sensitive layer) blue-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.75 gm), comprising 0.4 g AgN03, 20 spectrally sensitised with 0.6 mg of compound IV-6 1.25 g gelatine 0. 50 g yellow coupler GB-1 0.30 g tricresyl phosphate (TCP) 25 0. 10 ing stabiliser ST- 1 A-G 6747-Foreign Countries Layer 3: (intermediate layer) 0. 10 g gelatine 0,06 g DOP scavenger SC-1 0.06 g DOP scavenger SC-2 0. 12 g TCP Layer 4: (green-sensitive layer) green-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.45 [im) comprising 0.2 g AgN03, spectrally sensitised with 0. 12 mg of compound GS-1 1. 10 g gelatine 0. 10 g magenta coupler PP- 1 0. 10 g magenta coupler PP-2 0. 15 g stabiliser ST-2 0.20 g stabiliser ST-3 0.20 g TCP 0.02 g isotetradecanol Layer 5: (UV protection layer) 1.05 g gelatine 0.20 g UV absorber UV-1 0.05 g UV absorber UV-2 0.22 g UV absorber UV-3 0.06 g DOP scavenger SC-1 0.06 g DOP scavenger SC-2 0.25 g TCP A-G 6747-Foreign Countries Layer 6: (red-sensitive layer) red-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.48 gm) comprising 0.28 g AgNO3, spectrally sensitised with 0.04 mg of compound V-1 and stabilised with 0.56 mg stabiliser ST-4 1.00 g gelatine 0.40 g cyan coupler BG- 1 0.40 g TCP Layer 7: (UV protection layer) 1.05 g gelatine 0. 20 g UV absorber UV- 1 0.05 g UV absorber UV-2 0.22 g UV absorber UV-3 0. 15 g TCP Layer 8: (protective layer) 0.90 g gelatine 0.05 g optical brightener W-1 0.07 g polyvinylpyrrolidone 1.20 nil silicone oil 2.50 mg of a spacer material comprising polymethyl methacrylate, average particle size 0.8 gm 0. 30 g instant hardener H- 1 A-G 6747-Foreign Countries Layer structure 102 Layer structure 102 only differed from layer structure 101 in layer 6.

Layer 6: (red-sensitive layer) red-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.48 gm) comprising 0.20 g AgN03, spectrally sensitised with 0.03 mg of compound V-1 and stabilised with 0.4 mg stabiliser ST-4 1.00 g gelatine 0.30 g cyan coupler P9 0.40 g TCP 15 Layer structure 103 Layer structure 103 only differed from layer structure 101 in layer 2.

Layer 2: (blue-sensitive layer) blue-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.75 pin) comprising 0.40 g AgN03) spectrally sensitised with 0.6 m. of compound W-6; addition of a red 0 sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % brorrdde, average grain diameter 0.65 Rm) comprising 0.02 g AgN03 spectrally sensitised with 0.005 mg of compound V-1 and stabilised with 0.05 m. ST-4 0 A-G 6747-Foreigp Countries 1.25 g gelatine 0.50 g yellow coupler GB-1 0. 10 g stabiliser ST- 1 0.30 g TCP Layer structure 104 Layer structure 104 only differed from layer structure 102 in layer 2.

Layer 2: (blue-sensitive layer) bluesensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.75 gm) comprising 0.40 g AgN03, spectrally sensitised with 0.6 mg of compound IV-6; addition of a red sensitive silver halide emulsion (99,5 mole % chloride, 0.5 mole % bromide, average diameter 0.65 gm) comprising 0.05 g AgN03, spectrally sensitised with 0.01 mg of compound V-1 and stabilised with 0. 1 ma ST-4 0 1.25 g gelatine 0. O g yellow coupler GB- 1 0.30 g TCP 0. 10 g stabiliser ST-1 Layer structure 105 Layer structure 105 only differed from layer structure 102 in layer 4.

Layer 4: (green -sensitive layer) green-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.45 gm) comprising 0.2 g AgN03, spectrally sensitised with 0.12 mg of compound GS-1 1 A-G 6747-ForeigLi Countries 1. 10 9 gelatine 0. 15 g magenta coupler PP-3 0 0.05 g stabiliser ST-2 0.10 g stabiliser ST-3 0.4 g TCP layer structure 106 Layer structure 106 only differed from layer structure 105 in layer 2.

Layer 2: (blue-sensitive layer) blue-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.75 ptm) comprising 0.40 g AgN03, spectrally sensitised with 0.6 mg of compound IR-6; addition of a red sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.65 im) comprising 0.05 g AgN03, spectrally sensitised with 0.0 1 mg of compound V- 1 and stabilised with 0. 1 mg ST-4 1.25 g gelatine 0.50 g yellow coupler GB- 1 0.30 g TCP 0. 10 g stabiliser ST- 1 A-G 6747-Foreign Countries The following compounds were used in Example 1:

H3C0 \ (3 0 t-C 4 Hg'jl"r'j NH NH C17H35 GB-1 0 NYO H '1 0 3C CH3 t-C4Hg cj 1 PP-1 N, N N-H N C13H 27 t-C4 Hg\._/C] PP-2 N, N N-H N (CH AF-S02C12H25 t-C4 Hq\------/C1 N, N N-H N= PP-3 HCOCH 2CH 2CO0C14H 29 A-G 6747-Foreign Countries -42 OH NH 2 H5 t-C5HI, BG-1 cl 5-" ' co J 0 J: f 1 C2H t_c5H11 cl O-CO 0----COCH3 1 SC-1 -CH t- BH17 t_ 8H17 OH CH 3 CH 0 UM - CH3 U 0C6 H13 SC-2 C6H130 0 CH3 CH3 OH OH C4H,-s N uv-i C:):N N e4Hg"t A-G 6747-Forein Countdes OH H3C1,,,( H3 0 0 SI C4 Hq N H 3C N N OH UV-2 HO OH -1, 1. C4H9 OH C4Hg-t N UV-3 Cl ",]:a "N -0 N C4 Hq-t 0 N H-1 G k N 0 soe 3 OH t-Hg C4 OH OH ST-1 CH 3 a::: 1 C4 Hq-t CH 3 CH 3 - - n 1,5 A-G 6747-Foreign Countnes CH3 H 3C HO CH OH ST-2 1 t-C4M9 C3 H7 t-C4H9 ST-3 '_Cl3H270-0-N /-\ S02 /-SH -[:::::s cl NHS02 N ST-4 0 C2H5 0 />-CH=C-CH-GS-1 N (CHI kCHI 1 c) i SO (D S03 3 e HN(C2 H J3 W-1 SO,Na NH Ny NH S03Na 1 y 1 1 N(CH2CH2OH)2 Na03S N -,, N 1 N A1,1 N S03Na (HOCH2CH2)2N Na03S NH J11, N:'I'NH--'7 S03Na A-G 6747-Foreigp Countries Processin A negative comprising a MacBeth colour chart exposure was transferred to the specimens by a customary printer. The filtering in the course of this procedure was c) selected so that grey area N5 of the Macbeth chart was reproduced on the copy as a neutral grey of density 0.7. Processing was effected as described below, using the AP94 process (Agfa). Colour areas # 18 (cyan), # 6 (bluish green), # 2 (light skin) and # 1 (dark skin) were subsequently measured on the copy (Gretag SPM 100-ID and the respective difference AE {CieLab system colour difference between the original and the print} was recorded.

a) Colour develoMr - 45 see - 35'C triethanolamine 9.0 g N,N-diethylhydroxylarnine 2.0 g bis(2-sulphoethyl)-hydroxylamine, disodium salt 2.0 g diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methanesulphonami doethyl -aniline sulphate 5.0 g potassium sulphite 0.2 g triethylene glycol 0.05 g potassium carbonate 22 g potassium hydroxide 0.4 g ethylenediaminetetraacetic acid, di-Na salt 2.2 g potassium chloride 2.5 g 1,2-dihydroxybenzene-3,4,6-trisulphonic acid, trisodium salt 0.3 g made up to 1000 mI with water; pH 10.0 A-G 6747-Foreign Countries b) Bleach-hardener - 45 sec - 35'C ammonium thiosulphate 75 g sodium hydrogen sulphite 13.5 g 0 ammonium acetate 2,0g ethylenediarainetetraacctic acid (iron ammonium salt) 57 g % aqueous ammonia 9.5g made up to 1000 m]. with vinegar; pH 5.5 c) Washing -2 min - 33'C d) Dnin Layer structure AE AE AE AE # 18 # 6 # 2 # 1 101 10.9 17.9 9.0 17.8 comparison 102 14.3 19.1 10.1 19.0 comparison 103 11.1 17.7 9.1 17.5 invention 104 10.6 17.3 9.2 18.1 invention 14.3 19.5 10.4 19.0 comparison 106 10,7 17.6 8.8 17.7 invention It can be seen from the Table that the impairment of the colour reproduction for # 18 which was due to the use of a pyrroloazole cyan coupler was considerably improved by the measure according to the invention. An improvement in the difference measured for 0 # 6 and in that measured for the skin tones can also be seen.

A-G 6747-Foreijzn Countries Example

Layer structure 201 Layer structure 201 only differed from layer structure 101 in layer 6.

Layer 6: (red-sensitive layer) red-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % 10 bromide, average grain diameter 0.48 gm) comprising 0.28 g AgN03 spectrally sensitised with 0.04 mg of compound V1 and stabilised with 0.50 g stabiliser ST-4 1.00 g gelatine is 0.30 g cyan coupler 1-9 0.04 g yellow coupler GB-2 0.40 g TCP Layer structure 202 Layer structure 202 only differed from layer structure 101 in layer 6.

Layer 6: (red-sensitive layer) red-sensitive silver halide emulsion (99.5 mole % chloride, 0.5 mole % bromide, average grain diameter 0.48 gm) comprising 0.28 g AgN03, 0 spectrally sensitised with 0.04 mg of compound V-1 and stabilised with 0.50 g stabiliser ST-4 A-G 6747-Foreign Countries 1.00 g gelatine 0.30 g cyan coupler 1-9 0.0 1 g yellow coupler GB-2 0.40 g TCP 5 The following compound was used in Example 2 in addition to those used in Example C12 H 25 U H 0 0 la Cl -1 t-C 4 9--' NH GB-2 0 YO H 3C 0 CH 3 The samples were exposed and evaluated as described in Example 1.

Layer structure AE AE AE AE # 18 #6 #2 # 1 101 10.9 17.9 9.0 17.9 comparison 102 14.3 19.1 10.1 19.0 comparison 201 11.1 17.7 9.1 18.4 invention 202 10.8 18,1 9.8 18.6 invention It can be seen from the Table that the impairment of the colour reproduction for # 18 and # 6 which was due to the use of a pyrazoloazole cyan coupler was considerably improved by the measure according to the invention. An improvement in the skin tone area can also be seen.

A-G 6747-Foreign Countries Example 3

Layer structures 301, and 302 and 303, were produced as for layer structures 101, and 201 and 202, respectively, with the sole exception that 0. 15 g1M2 of magenta coupler PP-3 was used in layer 4 instead of the coupler mixture. The samples were exposed, processed and evaluated as in Example 1. It was shown here also that the addition of a yellow coupler is capable of significantly improving the colour reproduction for # 18 and # 6.

Layer structure AE AE AE AE # 18 #6 #2 # 1 301 10.9 17.7 9.3 17.7 comparison 14.3 19.5 10.4 19.1 comparison 302 10.6 18.1 10.3 18.5 invention 303 11.3 17.( 10.4 18.2 invention Example The layer structures of Examples 1 and 2 shown in the Table were exposed to red light and processed as described in Example 1. They were stored in the dark for 42 days at 15 WC and 60 % relative humidity and the percentage decrease in the maximum density was determined.

Layer structure AD.,,, [%] 101 -28 comparison 102 -12 comparison 104 -11 invention 202 -12 invention It was shown that the stability in the dark of the cyan image was considerably improved by the addition of the pyrazoloazole cyan coupler, and that the measures for improving the colour reproduction did not have a negative effect on stability.

0 A-G 6747-Foreign Countries Example 5

Layer structures 5011502 5 Layer structures 501 and 502 only differed from layer structures 104 and 102, respectively, in layer 6, to which 0. 02 g of compound IX-1 was added in each case.

Layer structures 5031504 10 Layer structures 503 and 504 only differed from layer structures 104 and 202, respectively, in layer 6, in which 0. 20 g of TCP was replaced by 0.20 g of compound VII-7 in each case.

Layer structures 5051506 Layer structures 505 and 506 only differed from layer structures 503 and 504, respectively, in layer 6, to which 0. 1 g of compound IX- 1 was added in each case.

These layer structures were exposed to red light behind a neutral wedge filter and were processed as described inExample 1. They were subsequently irradiated at 1OXI()6 luxhour with light from a xenon lamp, which was normalised to daylight, and the percentage decrease in density of the initial cyan density D = 1.0 was determined.

Layer structure ADmax 104 -61 202 -60 501 -40 502 -40 503 -35 504 -36 505 -28 506 -27 A-G 6747-ForeigLi Countries This example shows that the stability to light of pyrazoloazole cyan dyes can be considerably improved by the use of suitable dye stabilisers such as LM-1 and/or compounds of formula (V11).

A-G.6747-Foreip_,n Countries

Claims (1)

1. Claims

   1. A colour photographic copier material which comprises at least one redsensitive silver halide emulsion layer which comprises at least one cyan coupler, at least one green-sensitive silver halide emulsion layer which comprises at least one magenta coupler, and at least one blue-sensitive silver halide emulsion layer which comprises at least one yellow coupler, which copier material comprises, in the at least one red-sensitive layer, at least one pyrazoloazole cyan coupler of formula X 12 I R R N I -N Y wherein R" and R 12, independently of each other, represent an electron attracting group, X11 represents H or a group which can be split off by reaction with developer oxidation product, Y11 represents a group for the completion of a nitrogen-containing heterocycle, with the proviso that a group represented by R 12 is bonded to a carbon atom of the heterocycle, and n represents I or 2, characterised in that a two-equivalent yellow coupler is associated with the at least one red-sensitive layer or a red-sensitised silver halide emulsion is associated with the at least one blue-sensitive silver halide emulsion layer.

   A-G 6747-Foreign Countries 2. A colour photographic copier material according to claim 1, characterised in that the two-equivalent yellow coupler is situated in the at least one redsensitive layer and corresponds to formula (II) 5 R21 R-24 R26 1 R2i--C-CO-CH-CONH H23 Con) R25 wherein R21 denotes an alkyl, 10 R22 denotes an alkyl, R23 denotes a hydrogen atom or an alkyl, or R22 and R23 together denote the remaining members of a cyclopropyl radical, R24 denotes chlorine or alkoxy, R25 denotes -NHCO-R27, -S02NH-R27, -1MS02-R27, -COOR27, Cl, Br or alkoxy, R26 denotes a hydrogen or chlorine atom, 0 R27 denotes a substituent, and Q denotes the remaining members of a substituted imidazole, imidazolidinedione, oxazolidinedione or triazolidinedione ring, A-G 6747-Foreign Countries wherein the alkyl groups can be further substituted.

   3. A colour photographic copier material according to claim 1, characterised in that it contains. in the at least one blue-sensitive layer, a blue sensitiser of formula (IE):

   X 31 32 C H N +0 N R37 R R33 R34 35 R36 wherein R -, e 1 1 1 to R33 and R36 to R38 denote H, alkyl, alkoxy, halog n, 2-thienyl, 3- thienyl, 1-pyrrolyl, 2-pyrrolyl, phenyl, 1-indolyl, 21-furanyl, 3-furanyl or carbazoly), R34 and R35 denote alkyl, sulphoalkyl, carboxyalkyl, -(CH-,),-,SO,N--COR-,9, -(CH,),,SO,N-SO-,R39, -(CH-),CON-SO2R39 or -(CH,),CON-COR39, X-,, and X32 denote 0, S, Se,:,,TR-,0, m, denotes a counterion.

   n denotes a number from 2 to 4. and R-,q and R-.0 denote a C] -C4 aikvl, or R -, 1 and R-., or R-,-, and R.-,3, R-,6 and R 7 or R37 and R-,s, represent the 715 members of a condensed-on benzene or naphthalene ring remai t 0' A-G 6747-Foreign Countnes 4. A colour photographic copier material according to claim 1, characterised in that the red sensitiser in the at least one blue-sensitive layer corresponds to formula (V) RSO R60 R 511 X51 /-CH CH X52 R N e 1 L R \ 59 N 58 R53 R 54 m R55 R 56 R57 (V) wherein Xs 1 and X52 represent 0, S, S c or NR30, R51 to R53 and R56 to R58 represent H, alkyl, alkoxy, halogen, 2-thieny], 3-thieny], 1-pyrrolyl, 2-pyrroly], phenyl, 1-indolyl, 2-furanyl, Muranyl or carbazolyl, R54 and R55 denote alkyl, sulphoalkyl, carboxyalkyl, -(CH2)nSO2N--COR39, -(CH2),S02N-S02R39, -(CH2WON-SO2R39 or -(CH2),CON-COR39, m denotes a counterion, n denotes a number from 2 to 4, and Rj50 and R60 denote H or a C I -C4 alkyl, R30 and R39 denote a Cl -C4 alkyl, and Rs, and R52 or R52 and R53, R56 and R57 or R57 and Rs8, represent the rernaliling members of a condensed-on benzene or naphthalene ring.. 25 A-G 6747-Foreign Countries - 56 S. A colour photographic copier material according to claim 1, characterised in 0 that it contains, in the at least one blue-sensitive layer, a blue sensitiser of formula (M:

   R41 S X 41 />- C = 1 N H N R),P: 1 R45 42 (CHA R R43 (CH 44 1 2 m (IV) E) c) m S03 S03 wherein R4] andR43denote hydrogen, R42 denotes a halogen, particularly chlorine or fluorine, or 2-thienyl, 3 thienyl, Ppyrrolyl, 2-furanyl, 1 -indolyl or phenyl, or R4] andR42together, or R42and R43together, denote the remaining members of a condensed-on benzene or naphthalene ring, R44 denotes hydrocen, 0 R45 denotes a halogen, particularly chlorine or fluorine, phenyl, 2- thienyl, 3 0 thienyl, Ppyrrolyl, 2-furanyl, I-Indolyl, or R44 and R45 together denote the remaining members of a condensed-on benzene or naphthalene ring, X41 denotes S or 0, m denotes a counterion, particularly triethyl ammonium, and A-G 6747-Foreign Countries 1 and m denote a number from 2 to 4.

   6. A colour photographic copier material according to claim 1, characterised in that the red sensitiser in the at least one bluesensitive layer corresponds to 5 formula (VI):

   H3C CH3 R /-C' CH: X61 61) IS c R62 N N R 68 R 63 R R 64 65 R, m R 66 67 (VI) wherein R64 and R65 denote alkyl, sulphoalkyl, carboxyalkyl, -(CH2),,S02N--COR69, -(CH2)nS02N-S02R69, -(CH2),,CON-SO2R69 or -(CH2),, CON-COR69, R61 i R625 R.63, R66, R67 and R68, independently of each other, denote H, CH3, OCH3, Cl, 1-pyrrolyl, Pindolyl, 2-thienyl, 3-thienyl, 2-furanyl, 3- furanyl, N-carbazoly] or phenyl, or R61 and R62, or R62 and &3, as well as R66 and R67 or R67 and R68, together denote the remaining members of a benzo, 1,2-naphtho or 2,3-naphtho ring, A-G 6747-Foreign Countries X61 denotes 0 or S, m denotes a counterion, and R69 denotes a Cl-C4 alkyl. 5 7. A colour photographic copier material according to claim 1, characterised in 0 that it contains, in the at least one red-sensitive layer, an N,N- substituted p- an-nophenol ether of formula W R92 R94 Rg,O-, N 1 (1x), R 6-5- S --X 9, H93 wherein R91 denotes an alkyl, alkenyl or aryl group, R92 and R93. independently of each other, denote a hydrogen atom or an alkyl or alkoxy group comprising up to 16 C atoms, R94 denotes a hydrogen atom or an alkyl group, R95 denotes a C I -C3 alkylene group, and X() denotes an oxygen atom or a free electron pair, wherein the alkyl groups can be further substituted.

   8. A colour photographic copier material according to claim 7, characterised in 0 that the p-an-iinophenol ether corresponds to formula A-G 6747-ForeiLn Countries R92 R910- N\ S02 R R 93 94 wherein R91 denotes a Cl-C2o alkyl, R94 denotes hydrogen or methyl, and 0 R92 and R93 have the meanings cited in claim 7, wherein the total number of carbon atoms in the R91, R92 and R93 radicals is at least 8.

   9. A colour photographic copier material according to claim 1, characterised in that the compounds of formula (I) constitute the compound of formula (I-A) represented below:

   X 1. 2, Z12 R13 N, N (PA) N-N-k R14 wherein RI 3 andR14, independently of each other, have the meanings of R, 1 or R12, X12 has the meanin. of X],, and Z12 represents H or a substituent.

   10. A colour photographic material according to claim 1, characterised in that it 0 additionally contains compounds of formula (VHI), A-G 6747-Foreign Countries OR 81 R83 R8:> 1 (VIIII), R83 R 113 R 82 wherein Rg, represents H, or an alkyl, alkenyl, aryl or acy], R82 represents H, or an alkyl, alkoxy, aryloxy, acylamino, alkylamino, arylan-dno, hydroxy or hetaryl, and R83 represents H, or an alkyl, alkenyl, aryl, acyl or chlorine, wherein a plurality of R82 and R83 radicals can be the same or different.