DE10230979B3 - Color photographic copying material, for making positive print from color negative with scanning or analogue copier, uses 2-acylamino-5-(organylthio-phenylsulfonyl)-alkylcarbonylamino)-phenol as cyan coupler with solvent-soluble polymer - Google Patents

Abstract

In copying material with red-, green- and blue-sensitive silver halide emulsion layer(s) containing cyan, magenta and yellow coupler(s) respectively on a base, the red-sensitive layer contains (co)polymer(s) (A) that is insoluble in water and soluble in organic solvent and the cyan coupler is a 2-acylamino-5-(alpha-(alkyl- or arylthio-phenylsulfonyl)-alkylcarbonylamino)-phenol (I). In copying material with red-, green- and blue-sensitive silver halide emulsion layer(s) containing cyan, magenta and yellow coupler(s) respectively on a base, the red-sensitive layer contains (co)polymer(s) (A) that is insoluble in water and soluble in organic solvent and the cyan coupler is a 2-acylamino-5-(alpha-(alkyl- or arylthio-phenylsulfonyl)-alkylcarbonylamino)-phenol of formula (I): R1 = H or alkyl; R2 = alkyl or (het)aryl; R3 = alkyl or aryl; R4 = alk(en)yl, alkoxy, aryloxy, acyloxy, acylamino, sulfonyloxy, sulfamoylamino, sulfonamido, ureido, hydroxycarbonyl, hydrocarbonylamino, carbamoyl, alkylthio, arylthio, alkylamino, arylamino or H; Z = H or a group labile under chromogenic development conditions. An Independent claim is a method of making a positive print from a color negative by exposing image information onto the cited copying material, followed by appropriate processing.

Description

The invention relates to a color photographic Copy material with a new type of cyan coupler.

Color photographic copy materials are especially materials for Supervision pictures or displays, which are usually a positive one Have picture. They are therefore not a recording material like color photographic Movies. Mostly these are negative working materials.

Color photographic copy materials usually contain at least one red-sensitive, at least one cyan coupler containing silver halide emulsion layer, at least one green sensitive, at least a silver halide emulsion layer containing a magenta coupler and at least one blue-sensitive, at least one yellow coupler containing silver halide emulsion layer.

Out US 5,686,235 A and US 6 261 755 B1 cyan couplers have become known, which after development with the standard paper developer CD3 result in cyan dyes which are characterized by good light and dark stability.

However, these couplers have the Disadvantage that the dyes are inadequate in color rendering.

The couplers have a 2-acylamino-5-phenylsulfonylmethylcarbonylamino-phenol structure and can on the methyl group by alkyl and on the phenyl radical by different Groups can be substituted.

The object of the invention was the above to overcome the described disadvantage. Surprisingly This succeeds with the novel cyan coupler defined below. The advantages of the known coupler are retained.

Especially with very strong lighting with UV-containing light and very high demands on the stability and the Color rendering, e.g. to be found in galleries is light stability still unsatisfactory with the new couplers.

Another object of the invention was therefore to remedy this disadvantage. Surprisingly, this succeeds with the novel cyan coupler defined below in combination with special polymers which, for. B. from EP 280 238 A2 . EP 382 444 A2 and DE 2 535 497 A1 are known.

entspricht, worin
R¹ ein Wasserstoffatom oder eine Alkylgruppe,
R² eine Alkyl-, Aryl- oder Hetarylgruppe,
R³ eine Alkyl- oder Arylgruppe,
R⁴ eine Alkyl-, Alkenyl-, Alkoxy-, Aryloxy-, Acyloxy-, Acylamino-, Sulfonyloxy-, Sulfamoylamino-, Sulfonamido-, Ureido-, Hydroxycarbonyl-, Hydroxycarbonylamino-, Carbamoyl-, Alkylthio-, Arylthio-, Alkylaminooder Arylaminogruppe oder ein Wasserstoffatom und
Z ein Wasserstoffatom oder eine unter den Bedingungen der chromogenen Entwicklung abspaltbare Gruppe bedeuten.The invention thus relates to a copying material with a support, at least one red-sensitive, at least one cyan coupler, at least one green-sensitive, at least one magenta coupler and at least one blue-sensitive, at least one yellow coupler silver halide emulsion layer, characterized in that the red-sensitive layer contains at least one water-insoluble and contains homopolymer or copolymer soluble in organic solvents and the cyan coupler of the formula

corresponds to what
R ^{1 represents} a hydrogen atom or an alkyl group,
R ^{2 is} an alkyl, aryl or hetaryl group,
R ^{3 is} an alkyl or aryl group,
R ^{4 is} 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 represents a hydrogen atom or a group which can be split off under the conditions of chromogenic development.

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 homo- or copolymer of the invention in the following simply "that Polymer "called.

worin
R⁵ ein Wasserstoffatom oder eine Alkylgruppe,
R⁶ OR⁷ oder NR⁸R⁹,
R⁷ eine unsubstituierte oder substituierte Alkylgruppe mit 1 bis 6 C-Atomen,
R⁸ eine unsubstituierte oder substituierte Alkylgruppe mit 1 bis 6 C-Atomen,
R⁹ ein Wasserstoffatom oder eine unsubstituierte oder substituierte Alkylgruppe mit 1 bis 6 C-Atomen,
R¹⁰ eine unsubstituierte oder substituierte Alkylgruppe und
Z ein Wasserstoffatom oder eine unter den Bedingungen der chromogenen Entwicklung abspaltbare Gruppe bedeuten
und wobei die Gesamtzahl der C-Atome der Alkylgruppen R⁷ bis R¹⁰ in einem Kupplermolekül 8 bis 18 beträgt.The cyan coupler particularly preferably corresponds to the formula

wherein
R ^{5 represents} a hydrogen atom or an alkyl group,
R ⁶ OR ⁷ or NR ⁸ R ⁹ ,
R ^{7 is} an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms,
R ^{8 is} an unsubstituted or substituted alkyl group with 1 to 6 C atoms,
R ^{9 represents} a hydrogen atom or an unsubstituted or substituted alkyl group with 1 to 6 C atoms,
R ^{10 is} an unsubstituted or substituted alkyl group and
Z represents a hydrogen atom or a group which can be split off under the conditions of chromogenic development
and wherein the total number of carbon atoms of the alkyl groups R ⁷ to R ¹⁰ in a coupler molecule is 8 to 18.

i

Suitable cyan couplers are:

i

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 is added to 165 g (0.87 mol) of 2-amino-4-chloro-5-nitrophenol 1 in 500 ml of N-methylpynolidone with stirring N-Methylpyrrolidone added dropwise. Stir for 1 hour at room temperature, then 2 hours at 60 - 65 ° C. After cooling, slowly add 500 ml of water and vacuum. Mix twice with water, then twice with methanol and suction.
Yield 310 g (98%) 3

A mixture of 310 g (0.86 mol) 3, 171 g iron powder, 2.2 l ethanol and 700 ml N-methylpyrrolidone is heated to 65 ° C. with stirring. The heating bath is removed and within 2 hours 750 ml of conc. Dropped in hydrochloric acid. The mixture is then heated under reflux for 1 hour. After cooling, 1 l of water is added and suction filtered, washed with 2 N hydrochloric acid and then with water until the drain water is colorless. The residue is stirred with 1.5 l of water, neutralized by adding sodium acetate and suction filtered. Stir twice more with 1.5 l of methanol and suction.
Yield 270 g (95%) 4

Synthesis of the ballast residue

To a mixture of 520 g (3.6 mol) 4-chlorothiophenol 5 and 652 g (3.6 mol) ethyl 2-bromobutyrate 6 in 1 l ethanol are stirring 320 g (3.6 mol) 45% strength sodium hydroxide solution was added dropwise within 1 hour. The reaction is highly exothermic, the temperature is increased by cooling Kept at 75 - 80 ° C, then will 1 hour under reflux heated. Another 400 g (4.5 mol) of sodium hydroxide solution are slowly added dropwise (weakly exothermic). After a further 2 hours of reflux, the mixture is cooled and 1 l of water added. Subsequently is extracted twice with 250 ml of toluene, the combined organic Phases are dried and concentrated on a rotary evaporator. The viscous oil 7 (830 g, contains toluene) is further reacted without purification.

To a solution of 830 g (3.6 mol) of Compound 7 and 10 ml of sodium tungstate solution (20%) in glacial acetic acid 760 ml of hydrogen peroxide (35%) are added dropwise: the first 400 ml initially under cooling at 35 - 40 ° C, after removal cooling, the remaining 360 ml at 90 - 95 ° C. After completion the addition is stirred for 1 hour at this temperature. Excess peroxide is destroyed by adding sodium sulfite. The reaction mixture is mixed with 2 l of ethyl acetate and 21 water, the organic phase is separated and the aqueous Phase extracted twice with 700 ml of ethyl acetate. The United organic phases are washed twice with 700 ml of water each, dried and concentrated in vacuo. The residue is dissolved in 300 ml of ethyl acetate dissolved hot, cooled and when crystallization begins, 1 l of hexane is added. Then will vacuumed cold and washed with a little hexane. There will be 835 g (88% o) of compound 8 obtained.

131 g (0.5 mol) 8 and 111 g (0.55 mol) dodecyl mercaptan 9 are mixed in 300 ml 2-propanol with stirring with 90 g (1 mol) sodium hydroxide solution (45%). After adding 2.5 g of tetrabutylammonium bromide and 2.5 g of potassium iodide, the mixture is heated under reflux for 11 hours. After cooling, 350 ml of water are added, with about 60 ml of conc. Hydrochloric acid is adjusted to pH 1-2. The mixture is then extracted twice with 100 ml of ethyl acetate, the combined organic phases are washed three times with 150 ml of water each time, dried and concentrated. The residue is stirred with 500 ml of hexane and suction filtered at 0-5 ° C. After recrystallization tion from 500 ml of hexane / ethyl acetate (10: 1) gives 177 g of 10 (82%, mp: 82 ° C).

128 g (0.3 mol) 10 and 1 ml dimethylformamide are in 300 ml of toluene at 65 ° C. heated. At this temperature, 75 ml (1 mol) of thionyl chloride added dropwise within 1 hour. After a further 5 hours it is in a vacuum concentrated. The highly viscous oil (11, 134 g) is used without further purification.

Synthesis of coupler I-10

100 g of crude product 11 (approx. 0.2 mol) in 100 ml of N-methylpyrrolidone are added dropwise to 5 to 10 ° C. to 66 g (0.2 mol) of 4 in 200 ml of N-methylpyrrolidone. The mixture is first stirred at room temperature for 2 hours and then at 60 ° C. for 2 hours. The reaction mixture is filtered hot, the filtrate is mixed with 500 ml of acetonitrile, cooled to 0 ° C., suction filtered and washed with 50 ml of acetonitrile. The product is mixed with 500 ml of methanol and 1 l of water, stirred, suction filtered, then washed with 300 ml of water and dried.
Yield: 120 g (81%) I-10

The red-sensitive layer preferably contains Silver halide crystals with a chloride content of at least 95 mol%, this being in particular silver chloride, silver chloride bromide, Silver chloride iodide or silver chloride bromide iodide crystals. Silver chloride bromide emulsions are particularly preferred with a chloride content of at least 95 mol% and in particular of at least 97 mol%.

The silver halide crystals of the copy material according to the invention and particularly those of the red sensitive layer are preferred doped with iridium. The iridium can be used in any known way Crystals are installed. It is preferred as a complex salt in dissolved Form at any time during emulsion preparation, especially before crystal formation is complete.

In a preferred embodiment iridium (III) and / or iridium (IV) complexes are used, with complexes with chloro ligands are preferred. Hexachloro-iridium is particularly preferred (III) and Hexachloro-Iridium (IV) complexes. The possibly counterions to the iridium complex ions necessary for charge balance have no influence on the effect according to the invention and can can be freely chosen.

In an advantageous embodiment contains the polymer has no acid groups, also called acid groups. Among acid groups are substituents such as carboxylic acid groups, sulfonic acid or to understand acidic phenol groups.

For the water-insoluble, in organic solvents soluble Homo- or copolymer is preferably a vinyl polymer or a polyester.

Vinyl polymers can in particular contain the following monomer units:
Acrylic acid esters such as B. methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 5-octyl acrylate, tert-octyl acrylate, tert-octyl acrylate 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfurylacrylate, hydroxyl acrylate, tetrahydroxyl 5-methylacrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxyacrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate,? -Methoxypolyethylene glycol acrylate (number of units n = 9), 1-bromo -2-methoxyethyl acrylate and 1,1-dichloro-2-ethoxyethyl acrylate.
Methacrylic acid esters such. B. methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclo hexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methyl methacrylate, octyl methacrylate, sulfonate -Ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxymethyl methacrylate, 4-hydroxymethyl methacrylate, 4-hydroxymethyl methacrylate, 4-hydroxymethyl methacrylate methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2 -Butoxyethoxy) ethyl methacrylate,? -Methoxypolyethylene glycol methacrylate (number of units n = 6) and allyl methacrylate.
Vinyl esters such as B. vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate and vinyl salicylate.
Acrylamides such as B. acrylamide, methylacrylamide, ethyl acrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide acrylyl, (2)
Methacrylamides such as B. methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide (β-cyanoethyl) methacrylamide (β-cyanoethyl) methacrylamide (β-cyanoethyl methacrylamide).
Olefins such as e.g. B. dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene and 2,3-dimethylbutadiene.
Styrene compounds such as B. styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, iso-propylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene and vinylbenzoic acid methyl ester.
Vinyl ethers such as B. methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether.
Other monomers such. B. butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, vinyl methacrylate, methacrylate methacrylate, methacrylate methacrylate, methacrylate methacrylate, methacrylate methacrylate, glycidyl methacrylate, methacrylate methacrylate, methacrylate methacrylate, glycidyl methacrylate, methacrylate methacrylate, methacrylate methacrylate

The copolymers according to the invention contain two or several different monomers, e.g. B. the above, by their selection the properties of the polymer, e.g. B. its Coupler dissolving power can be. To improve color formation, the copolymers can also use monomers contain with acidic groups as long as the copolymer does not water soluble becomes.

Suitable monomers with acidic groups are z. B. acrylic acid, methacrylic acid, itaconic, maleic acid; Monoalkylitaconsäuresalze such as monomethyl itaconates, monoethyl itaconates, monobutyl itaconates; Monoalkylmaleinsäuresalze such as monomethyl maleates, monoethyl maleates, monobutyl maleates; Citraconic acid, styrene sulfonic acid, vinyl benzyl sulfonic acid, vinyl sulfonic acid; Acryloyloxyalkylsulfonic acids such as acryloyloxymethylsulfonic, acryloyloxyethylsulfonic, acryloyloxypropylsulfonic; methacryloyloxyalkylsulfonic such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic, methacryloyloxypropylsulfonic acid; Acrylamidoalkylsulfonic acids such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methyleutanesulfonic acid; Methacrylamidoalkylsulfonic acids such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid; 2-methacrylamido-2-methylbutanesulfonic acid and Alkali metal salts, e.g. B. of Na and K, or ammonium salts of the acids.

The proportion of water-soluble is preferably Monomers on the polymer at most 40 mol%, in particular at most 20 mol% and particularly preferably at most 10 mol%. Is particularly preferred no water soluble Comonomer used.

Of the vinyl monomers mentioned are methacrylic acid esters and acrylamides and especially alkyl acrylamides are particularly preferred.

In a particularly advantageous embodiment In the invention, the polymer is a polyalkylacrylamide.

The polyester of the invention can by condensation a polyhydroxy alcohol with a polycarboxylic acid or a polycarboxylic acid derivative be preserved.

Examples of suitable polyhydroxy alcohols are glycols or polyalkylene glycols having the structure HO-R ¹ -OH, where R ^{1 is} a hydrocarbon chain, in particular an alkylene chain having 2 to about 12 carbon atoms, and polycarboxylic acids are, for example, compounds of the structure HOOC-R ² -COOH or their derivatives, where R2 is a single bond or a hydrocarbon chain with 1 to about 12 carbon atoms.

Suitable examples of polyhydroxy alcohols are z. B. ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylol propane, 1,4-butanediol, isobutylene diol, 1,5-pentanediol, neo-pentylglycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, Glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol and sorbitol.

Suitable examples of polycarboxylic acids are e.g. B. oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanoic acid, decanedicarboxylic acid, undecandi carboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isopimelic acid, cyclopentadiene-maleic anhydride adduct and rosin-maleic anhydride adduct.

The molecular weight of the polymer according to the invention is preferably between 1,000,000 and 2,000, in particular between 400,000 and 5,000 and particularly preferably between 150,000 and 10,000.

Instead of a polymer according to the invention can advantageously also be a mixture of two or more polymers are used, the mixture also other than the inventive polymers can contain, as long as their proportion is so low that the advantages of the invention remain.

Suitable polymers according to the invention are listed below. In the case of copolymers, the molar proportions of the different monomers are indicated. If not specified, the proportion of each monomer is the same.
P-1 polyvinyl acetate
P-2 polyvinyl propionate
P-3 polymethyl methacrylate
P-4 polyethyl methacrylate
P-5 polyethyl acrylate
P-6 polyheptyl acrylates
P-7 polybutyl acrylate
P-8 polybutyl methacrylate
P-9 polyisobutyl methacrylate
P-10 polyisopropyl methacrylate
P-11 polyoctyl acrylate
P-12 polyhexadecyl acrylate
P-13 polyhexyl acrylate
P-14 polyisobutyl acrylate
P-15 polyisopropyl acrylate
P-16 poly-3-methoxybutyl acrylate
P-17 poly-2-methoxyethyl acrylate
P-18 poly-4-methoxyphenyl acrylate
P-19 poly-3-methoxypropyl acrylate
P-20 polymethyl acrylate
P-21 polydecyl methacrylate
P-22 polydodecyl methacrylate
P-23 polydiethylaminoethyl methacrylate
P-24 polyethyl methacrylate
P-25 polyhexadecyl methacrylate
P-26 polyhexyl methacrylate
P-27 polydimethylaminoethyl methacrylate
P-28 poly-3,3-dimethylbutyl methacrylate
P-29 poly-3,3-dimethyl-2-butyl methacrylate
P-30 poly-3,5,5-trimethylhexyl methacrylate
P-31 polyoctadecyl methacrylate
P-32 polytetradecyl methacrylate
P-33 polypentyl acrylate
P-34 polypentyl methacrylate
P-35 polyethylethoxycarbonyl methacrylate
P-36 poly-N-sec-butylacrylamide
P-37 poly-N-tert-butylacrylamide
P-38 polyethylene ethyl acrylate
P-39 polycyclohexyl methacrylate
P-40 poly-tert-butyl methacrylate
P-41 poly-iso-butyl chloroacrylate
P-42 poly-N-tert-butyl methacrylamide
P-43 polymethylphenyl acrylate
P-44 polybenzyl acrylate
P-45 poly-sec-butyl acrylate
P-46 poly-tert-butyl acrylate
P-47 poly-2-tert-butylphenyl acrylate
P-48 poly-4-tert-butylphenyl acrylate
P-49 poly-2-methylbutyl acrylate
P-50 poly-3-methylbutyl acrylate
P-51 poly-1,3-dimethylbutyl acrylate
P-52 poly-2-methylpentyl acrylate
P-53 polyphenyl acrylate
P-54 polypropyl acrylate
P-55 poly-m-toluenyl acrylate
P-56 poly-o-toluenyl acrylate
P-57 poly-p-toluenyl acrylate
P-58 poly-N-butyl acrylamide
P-59 poly-N, N-dibutylacrylamide
P-60 poly-N-iso-hexylacrylamide
P-61 poly-N-iso-octylacrylamide
P-62 poly-N-methyl-N-phenylacrylamide
P-63 polybenzyl methacrylate
P-64 poly-2-N-tert-butylaminoethyl methacrylate
P-65 poly-sec-butyl methacrylate
P-66 ethylene glycol sebacic acid polyester
P-67 vinyl acetate-vinyl alcohol copolymer (95/5)
P-68 butyl acrylate-acrylamide copolymer (95/5)
P-69 stearyl methacrylate acrylic acid copolymer (90/10)
P-70 methyl methacrylate-styrene copolymer (90/10)
P-71 methyl methacrylate-ethyl acrylate copolymer (50/50)
P-72 butyl methacrylate-methyl methacrylate-styrene copolymer (50/30/20)
P-73: vinyl acetate-acrylamide copolymer (85:15)
P-74 Diacetone Acrylamide Methyl Methacrylate Copolymer (50/50)
P-75 methyl vinyl ketone iso-butyl methacrylate copolymer (55/45)
P-76 ethyl methacrylate butyl acrylate (70/30)
P-77 Diacetone Acrylamide Butyl Acrylate Copolymer (60/40)
P-78 methyl methacrylate styrene diacetone acrylamide copolymer (40/40/20)
P-79 butyl acrylate-styrene-diacetone acrylamide copolymer (70/20/10)
P-80 methyl methacrylate-styrene-vinyl sulfonamide copolymer (70/20/10)
P-81 butyl acrylate-methyl methacrylate-butyl methacrylate copolymer (35/35/30)
P-82 methyl methacrylate-butyl methacrylate-iso-butyl methacrylate-acrylic acid copolymer (37/29/25/9)
P-83 butyl methacrylate acrylic acid copolymer (95/5)
P-84 methyl methacrylate-acrylic acid copolymer (95/5)
P-85 butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35/35/25/5)
P-86 Cyclohexyl methacrylate-methyl methacrylate-propyl methacrylate copolymer (37/29/34)
P-87 methyl methacrylate-butyl methacrylate copolymer (65/35)
P-88 vinyl acetate-vinyl propionate copolymer (75/25)
P-89 butyl methacrylate-styrene copolymer (90/10)
P-90 N-tert-butylacrylamide-methyl methacrylate copolymer (60/40)
P-91 N-tert-butylacrylamide-ethyl acrylate copolymer (50/50)
P-92 methyl methaerylate-hexyl methacrylate copolymer (70/30)
P-93 poly-N- (1,1-dimethyl-3-oxobutyl) acrylamide
P-94 poly-N-octyl methacrylamide
P-95 N, N-diethylacrylamide butyl acrylate copolymer (40/60)
P-96 N, N-diethylacrylamide-2-butoxyethyl acrylate copolymer (65/35)
P-97 N-tert-butyl acrylamide-butyl acrylate copolymer (60/40)
P-98 N-tert-octylacrylamide-2-ethylhexyl acrylate copolymer (65/35)
P-99 N, N-dibutylacrylamide-dibutyl maleic acid copolymer (75/25)
P-100 N-tert-butyl acrylamide-butyl acrylate copolymer (45/55)
P-101 N-Octyl-N-ethyl acrylamide-ethyl acrylate copolymer (45/55)
P-102 N-butyl methacrylamide-2-ethylhexyl acrylate copolymer (90/10)
P-103 N, N-dibutyl methacrylamide propyl acrylate copolymer (80/20)
P-104 N- (2-phenylethyl) acrylamide-butyl acrylate copolymer (25/75)
P-105 N-Acryloylmorpholine-2-ethoxyethyl acrylate copolymer (40/60)
P-106 N-methyl-N'-acryloylpiperazine butyl acrylate copolymer (15/85)
P-107 N-Acryloylpiperidine-2-butoxyethyl acrylate copolymer (40/60)
P-108 N- (1,1-dimethyl-3-hydroxybutyl) acrylamide-2-ethylhexylethacrylate copolymer (75/25)
P-109 N-Acryloylpiperidine Butyl Acrylate Copolymer (50/50)
P-110 N- (p-hydroxyphenyl) acrylamide butyl acrylate copolymer (25/75)
P-111 N- [3- (dimethylamino) propyl] acrylamide-butyl acrylate copolymer (35/65)
P-112 N-methyl-N'-methacryloylpiperazine-2-ethoxyethyl acrylate copolymer (40/60)
P-113 N-tert-butylacrylamide-butyl acrylate-2-ethoxyethyl acrylate copolymer (55/25/20)
P-114 1,6-hexanediol ascorbic acid sebacic acid polyester
P-115 diethylene glycol adipic acid polyester
P-116 trimethylolpropane adipic acid phthalic acid polyester
P-117 diethylene glycol trimethylol propane adipic acid polyester
P-118 ethylene glycol adipic acid polyester
P-119 ethylene glycol-1,4-butanediol adipic acid polyester
P-120 1,4-bis (β-hydroxyethoxy) benzene-sebacic acid polyester
P-121 ethylene glycol azelaic acid polyester
P-122 1,4-butanediol adipic acid polyester

The weight ratio of polymer to cyan coupler can be varied within a wide range, preferably between 0.01 g polymer to 1 g coupler to 10 g polymer to 1 g coupler, especially between 0.1 g polymer to 1 g coupler to 0.5 g polymer to 1 g coupler. The Cyan coupler is preferably emulsified with the polymer and the emulsified red-sensitive Layer added.

In an advantageous embodiment of the invention the red-sensitive layer additionally a high-boiling organic solvent. Also the weight ratio of organic solvent the polymer can be varied within a wide range, preferably lies it between 0.02 g of solvent to 1 g polymer to 100 g solvent to 1 g of polymer, in particular between 0.5 g of solvent to 1 g of polymer 3 g solvent to 1 g polymer. The organic solvent also preferably serves as an emulsifying aid, e.g. to the viscosity at the Emulsification of cyan couplers and adjust polymer.

Suitable high-boiling, organic solvent are z. B. alkyl phthalates, phosphonic, organophosphate, citric acid esters, benzoic, Amides, fatty acid esters, trimesic, Alcohols, phenols, aniline derivatives and hydrocarbons.

Examples of particularly suitable high-boiling organic solvents are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethyl-hexyldiphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, Diethyldodecanamide, N-tetradecyclpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctyl acetate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, N, N-dibutyl-2-butoxy-5-t-octylaniline, paraffin, Dodecylbenzene, diisopropylnaphthalene, Tetradecanol, bis (2-ethylhexyl) sebaccate, dibutyl adipate, diisononyl adipate, Octylpyrrolidone, 2,4-di-tert-butylphenol and epoxidized linseed oil.

In a particularly advantageous embodiment the invention is the cyan coupler with the polymer and the high-boiling organic solvent emulsified and the emulsifier added to the red-sensitive layer.

To manufacture the above Emulgate becomes the cyan coupler according to the invention in the polymer and optionally in a mixture of polymer and high-boiling organic solvent solved or dispersed. These solutions or dispersions are then in an aqueous binder solution, usually a gelatin solution, emulsifies and lie in the photographic layers after incorporation and drying them as fine droplets in a diameter between 0.05 and 0.8 μm in the layers. Further Methods for manufacturing the Emulgate can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

The invention also relates to a process for creating a positive supervisory image of one Color negative, with the image information exposed on a copy material and then the material processed according to its type, characterized in that that the previously described copying material used becomes.

In a preferred embodiment of the method according to the invention the color negative is digitized and the exposure with a scanning copier, particularly preferably carried out with a laser imagesetter.

In a further advantageous embodiment of the method according to the invention the exposure is carried out with an analog copier, especially preferably with a copier, with the over 1000 copies per hour, can be exposed.

Examples of color photographic copy materials are color photographic paper, color reversal photographic paper, semi-transparent display material and color photographic materials with deformable base e.g. made of PVC. An overview can be found in Research Disclosure 37038 (1995), Research Disclosure 38957 (1996) and Research Disclosure 40145 (1997).

The photographic copying materials consist of a support on which at least one light-sensitive silver halide emulsion layer is applied. Thin films are particularly suitable as supports and foils. An overview of carrier materials and auxiliary layers applied to their front and rear sides is shown in Research Disclosure 37254, Part 1 (1995), p. 285 and in Research Disclosure 38957, Part XV (1996), p. 627.

The color photographic copy materials usually contain at least one red sensitive, green sensitive and blue sensitive Silver halide emulsion layer and optionally intermediate layers and protective layers.

Depending on the type of photographic copy material can these layers can be arranged differently. This is for the most important Products shown: color photographic paper and color photographic Display material show in the order given below usually on the carrier one blue-sensitive, yellow-coupling silver halide emulsion layer, a green sensitive, purple-coupling silver halide emulsion layer and a red-sensitive, cyan-coupling Silver halide emulsion layer; is a yellow filter layer not mandatory.

Deviations in number and arrangement The photosensitive layers can be used to achieve certain Results are made. For example, color papers can also be different contain sensitized intermediate layers over which the gradation is influenced can be.

Essential components of the photographic Emulsion layers are binders, silver halide grains and Color couplers.

Find information about suitable binders Research Disclosure 37254, Part 2 (1995), p. 286 and in Research Disclosure 38957, Part II.A (1996), p. 598.

Information on suitable silver halide emulsions, their production, maturation, stabilization and spectral sensitization including Suitable spectral sensitizers can be found in Research Disclosure 37254, Part 3 (1995), p. 286, in Research Disclosure 37038, Part XV (1995), p. 89 and in Research Disclosure 38957, Part V.A (1996), P. 603.

Pentamethine cyanines with naphthothiazole, naphthoxazole or benzothiazole as basic end groups can also be used as red sensitizers for the red-sensitive layer, which can be substituted by halogen, methyl or methoxy groups and bridged by 9,11-alkylene, in particular 9,11-neopentylene. The N, N'-substituents can be C ₄ -C ₈ alkyl groups. The methine chain can also carry substituents. Pentamethines with only one methyl group on the cyclohexene ring can also be used. The red sensitizer can be supersensitized and stabilized by adding heterocyclic mercapto compounds.

The red-sensitive layer can additionally between 390 and 590 nm, preferably spectrally sensitized at 500 nm be so as to bring about an improved differentiation of the red tones.

The spectral sensitizers can be found in dissolved Form or as a dispersion of the photographic emulsion can be added. Both solution as well as disperse Additions, such as wetting agents or buffers.

The spectral sensitizer or one Combination of spectral sensitizers can be before, during or after be added to the emulsion preparation.

Photographic copy materials included either silver chloride bromide emulsions with up to 80 mol% AgBr or Silver chloride bromide emulsions with over 95 mol% AgCl.

Find information about the color couplers Research Disclosure 37254, Part 4 (1995), p. 288, in Research Disclosure 37038, Part II (1995), p. 80 and in Research Disclosure 38957, Part X.B (1996), p. 616. The maximum absorption of the the couplers and the color developer oxidation product Dyes lies for Copy materials preferably in the following areas: Yellow coupler 440 to 450 nm, purple coupler 540 to 560 nm, cyan coupler 625 to 670 nm.

Allocated in copy materials to a blue-sensitive layer commonly used yellow coupler are almost all two-equivalent couplers the pivaloylacetanilide and cyclopropylcarbonylacetanilide series.

The usual in copy materials Purple couplers are almost always those from the series of anilinopyrazolones, the pyrazolo [5,1-c] (1,2,4) triazole or the pyrazolo [1,5-b] (1,2,4) triazole.

The usually between layers different spectral sensitivity arranged non-photosensitive Intermediate layers can Contain agents that are undesirable Diffusion of developer oxidation products from a photosensitive in another light-sensitive layer with different spectral Prevent awareness.

Suitable connections (white couplers, Scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292, in Research Disclosure 37038, Part III (1995), p. 84 and in Research Disclosure 38957, Part X.D (1996), pp. 621 ff.

The photographic material can furthermore UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _Min dyes, plasticizers (latices), biocides and additives to improve the coupler and dye stability, to reduce the color fog and for Reducing yellowing and other included. Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292, in Research Disclosure 37038, Parts N, V, VI, VII, X, XI and XIII (1995), p. 84 ff and in Research Disclosure 38957, parts VI, VIII, IX and X (1996), p. 607 and 610 ff.

The layers of color photography Materials are common hardened, i.e., the binder used, preferably gelatin, is made by suitable chemical processes are networked.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294, in Research Disclosure 37038, Part XII (1995), page 86 and in Research Disclosure 38957, Part II.B (1996), p. 599.

After imagewise exposure, color photographic Materials differ according to their character Processed. Details of procedures and chemicals required for this are in Research Disclosure 37254, Part 10 (1995), p. 294, in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), p. 630 ff together with exemplary materials published.

emulsions

Preparation of the silver halide emulsions

Micrate emulsion (EmM1) (doping-free micrate)

The following solutions are prepared with demineralized water:

Solutions 02 and 03 are simultaneously added to solution 01 at 40 ° C over a period of 30 minutes at a constant feed rate at pAg 7.7 and pH 5.3 with vigorous stirring. During the precipitation, the pAg value by metering in a NaCl solution and the pH value by metering in H ₂ SO ₄ into the precipitation tank are kept constant. An AgCl emulsion with an average particle diameter of 0.09 μm is obtained. The gelatin / AgNO ₃ weight ratio is 0.14. The emulsion is ultrafiltered at 50 ° C. and redispersed with so much gelatin and water that the gelatin / AgNO ₃ weight ratio is 0.3 and the emulsion contains 200 g AgCl per kg. After redispersion, the grain size is 0.13 μm.

Red sensitive emulsion EmR1

The following solutions are prepared with demineralized water:

Solutions 12 and 13 are simultaneously added at 40 ° C. over a period of 75 minutes at a pAg of 7.7 to the solution 11 presented in the precipitation kettle with vigorous stirring. The pAg and pH are checked in the same way as for the precipitation of the EmM1 emulsion. The feed is regulated in such a way that the feed rate of solutions 12 and 13 increases linearly from 4 ml / min to 36 ml / min in the first 50 minutes and the feed rate is constant at 40 ml / min in the remaining 25 minutes. An AgCl emulsion with an average particle diameter of 0.48 μm is obtained. The amount of AgCl in the emulsion is subsequently converted to AgNO ₃ . The gelatin / AgNO ₃ weight ratio is 0.14. The emulsion is ultrafiltered, washed and redispersed with so much gelatin and water that the gelatin / AgNO ₃ weight ratio is 0.56 and the emulsion contains 200 g AgNO ₃ per kg.

The emulsion is chemically ripened at pH = 5.0 with an optimal amount of gold (III) chloride and Na ₂ S ₂ O ₃ at a temperature of 75 ° C. After chemical ripening, the emulsion is spectrally sensitized at 40 ° C. with 75 μmol of the compound (RS-1) per mol of AgCl and stabilized with 2.5 mmol (ST-1) per mol of AgNO ₃ . Then 3 mmol KBr are added.

green-sensitive Emulsion EmG1

Precipitation, desalination and redispersion are carried out in the same way as for the red-sensitive emulsion EmR1. The emulsion is optimally ripened at pH 5.0 with gold (III) chloride and Na ₂ S ₂ O ₃ at a temperature of 60 ° C for 2 hours. After chemical ripening, the emulsion is spectrally sensitized at 50 ° C with 0.6 mmol of compound (GS-1) per mole of AgCl, stabilized with 1.2 mmol of compound (ST-2) and then with 1 mmol KBr added.

Blue sensitive emulsion EmB1

The following solutions are prepared with demineralized water:

Solutions 22 and 23 are added at 50 ° C. over a period of 150 minutes at a pAg of 7.7 to the solution 21 presented in the precipitation kettle with vigorous stirring. The pAg and pH are checked in the same way as for the precipitation of the EmM1 emulsion. The feed is regulated in such a way that the feed rate of solutions 22 and 23 increases linearly from 10 ml / min to 90 ml / min in the first 100 minutes, and the feed rate in the remaining 50 minutes is constant at 100 ml / min. An AgCl emulsion with an average particle diameter of 0.85 μm is obtained. The gelatin / AgNO ₃ weight ratio is 0.14. The emulsion is ultrafiltered and with so much gelatin and water redispersed that the gelatin / AgNO ₃ weight ratio is 0.56 and the emulsion contains 200 g AgNO ₃ per kg.

The emulsion is ripened at a pH of 5.0 with an optimal amount of gold (III) chloride and Na ₂ S ₂ O ₃ at a temperature of 50 ° C. for 2 hours. After chemical ripening, the emulsion is spectrally sensitized at 40 ° C. with 0.3 mmol of the compound BS-1, stabilized with 0.5 mmol of the compound (ST-3) and then mixed with 0.6 mmol KBr.

layer structure

example 1

A color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application.

Layer structure 101

Layer 1: (substrate layer)
0.10 g gelatin
Layer 2: (blue sensitive layer)
Blue-sensitive silver halide emulsion EmB1 (99.94 mol% chloride, 0.06 mol% bromide, average grain diameter 0.85 μm) from 0.4 g AgNO ₃ .
1.25 g gelatin
0.30 g yellow coupler GB-1
0.20 g yellow coupler GB-2
0.30 g tricresyl phosphate (CPM)
0.10 g stabilizer ST-4
Layer 3: (intermediate layer)
0.10 g gelatin
0.06 g EOP catcher SC-1
0.06 g EOP catcher SC-2
0.12 g CPM
Layer 4: (green sensitive layer)
green-sensitive silver halide emulsion EmGl (99.9 mol% chloride, 0.1 mol% bromide, average grain diameter 0.48 μm) from 0.2 g AgNO ₃ .
1.10 g gelatin
0.05 g purple coupler PP-1
0.10 g purple coupler PP-2
0.15 g stabilizer ST-5
0.20 g stabilizer ST-6
0.40 g CPM
Layer 5: (UV protective layer)
1.05 g gelatin
0.35 g UV absorber UV-1
0.10 g UV absorber UV-2
0.05 g UV absorber UV-3
0.06 g EOP catcher SC-1
0.06 g EOP catcher SC-2
0.25 g CPM
Layer 6: (red sensitive layer)
red-sensitive silver halide emulsion EmR1 (99.7 mol% chloride, 0.3 mol% bromide, average grain diameter 0.48 μm) from 0.28 g AgNO ₃ .
1.00 g gelatin
0.40 g of cyan coupler according to Table 1
0.40 g oil former according to table 1
Layer 7: (UV protective layer)
1.05 g gelatin
0.35 g UV absorber UV-1
0.10 g UV absorber UV-2
0.05 g UV absorber UV-3
0.15 g CPM
Layer 8: (protective layer)
0.90 g gelatin
0.05 g white toner W-1
0.07 g polyvinyl pyrrolidone
1.20 ml silicone oil
2.50 mg polymethyl methacrylate spacer, average particle size 0.8 μm
0.30 g instant hardener H-1

Differentiate the other layer structures differs from 101 by the cyan couplers shown in Table 1 and oil formers. The results of the investigations described below on these layer structures are summarized in Table 1.

Chemical processing

• a) Farbentwickler 45 s 35°C Triethanolamin 9,0 g N,N-Diethylhydroxylamin 4,0 g Diethylenglykol 0,05 g 3-Methyl-4-amino-N-ethyl-N-methansulfonamidoethyl-anilin-sulfat 5,0 g Kaliumsulfit 0,2 g Triethylenglykol 0,05 g Kaliumcarbonat 22 g Kaliumhydroxid 0,4 g Ethylendiamintetraessigsäure-di-Na-Salz 2,2 g Kaliumchlorid 2,5 g 1,2-Dihydroxybenzol-3,4,6-trisulfonsäuretrinatriumsalz 0,3 g auffüllen mit Wasser auf 1 000 ml; pH 10,0
• b) Bleichfixierbad 45 s 35°C Ammoniumthiosulfat 75 g Natriumhydrogensulfit 13,5 g Ammoniumacetat 2,0 g Ethylendiamintetraessigsäure (Eisen-Ammonium-Salz) 57 g Ammoniak 25 %ig 9,5 g auffüllen mit Essig auf 1 000 ml; pH 5,5
• c) Wässern 2 min 33°C
• d) Trocknen

All samples were processed as follows.

• a) Color developer 45 s 35 ° C triethanolamine 9.0 g N, N-diethylhydroxylamine 4.0 g diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl-aniline sulfate 5.0 g Potassium sulfite 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-trisulfonic acid trisodium salt 0.3 make up to 1,000 ml with water; pH 10.0
• b) bleach-fix bath 45 s 35 ° C ammonium thiosulfate 75 g sodium bisulfite 13.5 g ammonium acetate 2.0 g ethylenediaminetetraacetic acid (iron-ammonium salt) 57 g ammonia 25% 9.5 g fill with vinegar to 1,000 ml; pH 5.5
• c) Soak 2 min 33 ° C
• d) drying

The samples were then exposed to light from a xenon lamp normalized to daylight at 35 ° C., 85% rel. Humidity and an illuminance of 100 klx with 10 · 10 or 20 · 10 ⁶ lx · h. Then the percentage decrease in density at D = 1.0 (ΔD _1.0 ) is determined. The xenon lamp used emits a significant proportion of UV light, which is comparable to direct sun rays and is higher than that of halogen or fluorescent tubes. The test used is therefore a meaningful quick test for light resistance to UV-containing light of high intensity.

The following compounds are used in Example 1:

Table 1

From the results listed in Table 1 it can be seen that the couplers according to the invention are long-lasting intensive irradiation with UV-containing light is unsatisfactory light stability if they only use common oil formers how CPM are emulsified.

By using the polymers according to the invention as an oil former becomes the light stability however significantly improved. Completely surprising is the improvement in the couplers according to the invention and a high radiation dose particularly pronounced, so the best light stability with the couplers according to the invention and the polymers of the invention can be achieved.

Claims (12)

Copy material with a support, at least one red-sensitive, at least one cyan coupler, at least one green-sensitive, at least one magenta coupler and at least one blue-sensitive, at least one yellow coupler silver halide emulsion layer, characterized in that the red-sensitive layer contains at least one water-insoluble and organic solvent-soluble homo- contains or copolymer and the cyan coupler of the formula

in which R ^{1 is} a hydrogen atom or an alkyl group, R ^{2 is} an alkyl, aryl or hetaryl group, R ^{3 is} an alkyl or aryl group, R ^{4 is} 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 is a hydrogen atom or a group which can be split off under the conditions of chromogenic development , Copying material according to claim 1, characterized in that it is a color negative material. Copying material according to one of claims 1 or 2, characterized in that the cyan coupler of the formula

corresponds in which R ^{5 is} a hydrogen atom or an alkyl group, R ⁶ OR ⁷ or NR ⁸ R ⁹ , R ^{7 is} an unsubstituted or substituted alkyl group having 1 to 6 C atoms, R ^{8 is} an unsubstituted or substituted alkyl group having 1 to 6 C atoms , R ^{9 is} a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 6 C atoms, R ^{10 is} an unsubstituted or substituted alkyl group and Z is a hydrogen atom or a group which can be split off under the conditions of chromogenic development, the total number of C atoms being the Alkyl groups R ⁷ to R ¹⁰ in a coupler molecule are 8 to 18. Copying material according to one of claims 1 to 3, characterized in that that the polymer has no acid groups contains. Copy material according to one of claims 1 to 4, characterized in that that the weight ratio from polymer to cyan coupler 0.01 to 1 to 10 to 1. Copy material according to one of claims 1 to 5, characterized in that that the polymer is a polyalkylacrylamide or a Polyester. Copying material according to one of claims 1 to 6, characterized in that that the red sensitive layer is a high-boiling organic solvent contains. Copying material according to claim 7, characterized in that the weight ratio of high-boiling solvent for polymer is 0.02 to 1 to 100 to 1. Copying material according to one of claims 1 to 8, characterized in that that the silver halide crystals of the red sensitive layer unite Have chloride content of at least 95 mol%. Process for creating a positive supervisory picture of a color negative, the image information on a copy material exposed and then the material according to its type is processed, characterized in that a copy material according to one of the claims 1 to 9 is used. A method according to claim 10, characterized in that the Color negative is digitized and the exposure is scanned with a working copier carried out becomes. A method according to claim 10, characterized in that the Exposure is carried out with an analog copier.