EP0422462B1 - Colour photographic recording material with couplers which release heat-stable dyes - Google Patents

Description

The invention relates to a color photographic, multilayer recording material with at least one silver halide emulsion layer with a sensitivity for each of the three main spectral ranges red, green, blue and associated color couplers to form the complementary colored cyan, purple or yellow partial color images, which due to the special structure of the color couplers Image dyes formed in the chromogenic development during normal and especially during MULTICOPY operation of high-performance (scan) printers do not produce a temperature-related color cast in the paper copies.

It is known that for the production of paper copies in high-performance (scan) printers, such as AGFA MSP, GRETAG 3140, both for the measuring station for determining the exposure time and for the copying station itself, advantageously high-performance quartz Halogen lamps are used, the radiant power of which is approximately 100,000 - 400,000 lux.

The absorption of the image dyes converts the light energy into thermal energy, which means that the negative used as a template can be warmed up to 45 ° C and more. Filters can be faded in during measurement and exposure, but filters also have residual permeabilities in the filtered out area due to the high radiation power.

In addition, the radiation power rises sharply from the blue to the red and infrared spectral range (FIG. 1), so that the red-light-absorbing cyan dyes in particular contribute to the heating of the original.

The IR heat radiation is expediently removed using a heat protection filter (SCHOTT, Mainz) or eliminated by passing the light beam through a water filter.

Forced cooling cannot completely prevent warming up, since the heat in the layer structure of the template is generated in situ and, due to insufficient contact (not very effective), can only be dissipated via the air.

It has been found that the warming up of the original more or less leads to a change in the absorption of the image dyes in the negative, the absorption generally decreasing with increasing temperature, and the absorption band generally decreasing Wavelength shifted. This effect is particularly noticeable when absorbing the blue-green partial color image.

Typical changes in density in the exposure station of a high-performance (scan) printer for the cyan layer are, for example, ΔD = - 0.15 based on a density D = 2.0. In the 100th copy, for example, this corresponds to an increase in the blue green density from D = 0.7 to D = 0.8 (color cast).

In multi-copy mode, high-performance (scan) printers only read (scan) the original for a large number of identical copies to determine the exposure time and filtering, and then the corresponding number of copies are printed with this fixed data. Here, the original becomes increasingly warm within a short time during the repeated exposure. This leads to a decrease in density in the original and thus to an increasing overexposure of the copy (color cast). Naturally, this error does not occur if only one copy is made of the original or in the first copy of a large number of copies which are subsequently made from the same original, but only if one in the original as a result of multiple exposure Warming has occurred.

The invention has for its object to provide a color photographic negative recording material from a negative can be produced, the image dyes of which have a better thermal stability and which is consequently more suitable as a template in the production of color copies, in particular in a high-performance (scan) printer.

A color photographic negative recording material has now been found which contains special cyan couplers which, in the chromogenic development, provide cyan dyes with better thermal stability. The recording material according to the invention is particularly adapted and suitable for processing in high-performance (scan) printers, especially also in multi-copy mode, i.e. if a large number of identical copies are made in succession from the same original.

wobei

a

für den Temperaturkoeffizienten der $${\text{Absorption A}}_{\text{(T = 23° C)}}\text{= 1g}\frac{{\text{I}}_{\text{o}}}{\text{I}}$$

und

b

für den Temperaturkoeffizienten der Absorptionswellenlänge λ _{(T = 23° C)}

stehen.The invention relates to a color photographic recording material which has at least one red-sensitive silver halide emulsion layer and a cyan coupler of the naphthol or phenol type associated therewith on a transparent layer support, at least one green-sensitive silver halide emulsion layer and one associated magenta coupler of the 5-pyrazolone or pyrazoloazole type and at least one contains a blue-sensitive silver halide emulsion layer and an associated acylacetanilide-type yellow coupler, characterized in that for the cyan coupler during chromogenic development using 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine ( CD 4) the following condition applies as a color developer in the layer of cyan dye: $$\text{a · (1 + b) ≦ 1.5}$$

in which

a

for the temperature coefficient of $${\text{Absorption A}}_{\text{(T = 23 ° C)}}\text{= 1g}\frac{{\text{I.}}_{\text{O}}}{\text{I.}}$$

and

b

for the temperature coefficient of the absorption wavelength λ _{(T = 23 ° C)}

stand.

I _o or I is the spectral radiation flow in front of or behind the sample.

The temperature coefficient a describes the temperature dependence of the absorption A of the absorption band and is the change in absorption Δ A per degree, normalized to the absorption A at 23 ° C.

The temperature coefficient b describes the temperature dependence of the position λ _{max of} the absorption band and is the spectral change Δ λ per degree, normalized to the wavelength λ _max at 23 ° C.

wobei

a

für den Temperaturkoeffizienten der $${\text{Absorption A}}_{\text{(T = 23° C)}}\text{= 1g}\frac{{\text{I}}_{\text{o}}}{\text{I}}$$

und

b

für den Temperaturkoeffizienten der Absorptionswellenlänge λ _{(T = 23° C)}

stehen.Another object of the invention is a method for producing a plurality of identical positive color images from a transparent template, preferably in a high-performance (scan) printer, the template being scanned once line by line to determine the required exposure and filter data , whereupon the exposure and filter data determined in this way successively expose a large number of different sections of a color photographic print material through the same template and then develop them chromogenically, and wherein a color photographic recording material is used to produce the transparent template which has at least one red-sensitive one on a transparent substrate Silver halide emulsion layer and a cyan coupler of the naphthol or phenol type associated therewith, at least one green-sensitive silver halide emulsion layer and a magenta coupler of 5-pyrazolone-associated therewith contains the tyrazoloazole type and at least one blue-sensitive silver halide emulsion layer and a yellow coupler of the acylacetanilide type associated therewith, and which is imagewise exposed in the usual manner and then developed chromogen, characterized in that for the cyan coupler used in chromogenic development using 1 - (N-Ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine (CD 4) as a color developer in the cyan dye formed in the layer, the following condition applies: $$\text{a · (1 + b) ≦ 1.5}$$

in which

a

for the temperature coefficient of $${\text{Absorption A}}_{\text{(T = 23 ° C)}}\text{= 1g}\frac{{\text{I.}}_{\text{O}}}{\text{I.}}$$

and

b

for the temperature coefficient of the absorption wavelength λ _{(T = 23 ° C)}

stand.

• für den Temperaturkoeffizienten der Absorption A: 0 ≦ a ≦ 1,4
• und für den Temperaturkoeffizienten der Absorptionswellenlänge λ: 0 ≦ b ≦ 0,18

The color photographic recording material according to the invention is thus a negative material which differs from conventional negative materials essentially only in that it contains special color couplers, in particular cyan couplers, which have the properties defined in the claim. The cyan couplers according to the invention preferably apply

• for the temperature coefficient of absorption A: 0 ≦ a ≦ 1.4
• and for the temperature coefficient of the absorption wavelength λ: 0 ≦ b ≦ 0.18

The importance of the invention lies in the fact that the absorption properties of the image dyes produced in the chromogenic development from the color couplers are largely independent of the ambient temperature within the temperature range of 10 - 60 ° C., so that the copying results are only slightly dependent on a temperature change within the specified range Dimensions are affected. In normal copying, only a few copies, as a rule about 1-3, are made of a negative original, the negative being warmed up only slightly by the copying light.

On the other hand, the thermal load on the negative due to the repeated copying exposure in the so-called multicopying operation is considerably greater if the same negative is exposed very often within a short time and the heat generated in this way cannot be dissipated quickly enough.

In the couplers used to date, this is noticeable by a change in the absorption properties in the negative which increases with increasing temperature, which is expressed in a clear color cast in the nth copy when compared with the first copy. However, is When using the color photographic negative material according to the invention, almost no color deviation is discernible even when producing a large number of copies. A plurality of copies in the above sense means more than 5, preferably more than 10 and most preferably more than 50.

The transparent color negative used as a template in the process of the present invention is prepared by chromogenic development of an imagewise exposed color photographic (negative) recording material which contains the aforementioned cyan, magenta and yellow couplers, at least the cyan coupler used being one for whose dye the condition mentioned applies. This condition preferably also applies to the dyes which are produced from the magenta and yellow couplers used in the chromogenic development.

worin bedeuten

R¹

H, -Z-R³ oder -NH-R⁴;

Z

-O-, -S(O)_m- oder -SO₂-NH-;

m

0, 1 oder 2;

R²

Alkyl oder Aryl mit einem Ballastrest;

R³

H, -CF₃, Alkyl, Aryl oder einen heterocyclischen Rest;

R⁴

H oder Acyl;

X

H, Halogen oder eine bei Farbkupplung abspaltbare Gruppe.

Naphtholic cyan couplers correspond to formula I.

in what mean

R¹

H, -Z-R³ or -NH-R⁴;

Z.

-O-, -S (O) _m - or -SO₂-NH-;

m

0, 1 or 2;

R²

Alkyl or aryl with a ballast residue;

R³

H, -CF₃, alkyl, aryl or a heterocyclic radical;

R⁴

H or acyl;

X

H, halogen or a group that can be split off with a color coupling.

worin bedeuten

W

H oder einen weiteren Substituenten;

n

1-4

R¹

eine Phenoxygruppe, die am Phenylring wenigstens eine unsubstituierte o-Stellung aufweist und im übrigen mit 1 - 3 Substituenten aus der Gruppe Alkyl mit 1 - 3 C-Atomen, Alkoxy oder Cycloalkyl substituiert sein kann;

R²

Alkyl mit mindestens 8 C-Atomen, vorzugsweise in gerader Kette;

X

Wasserstoff, Halogen oder eine bei Farbkupplung abspaltbare Gruppe.

The cyan couplers of the phenol type which are preferably used according to the invention are, for example, those of 2-phenylureidophenol and in particular those of the formula II

in what mean

W

H or another substituent;

n

1-4

R¹

a phenoxy group which has at least one unsubstituted o-position on the phenyl ring and can moreover be substituted by 1-3 substituents from the group alkyl having 1-3 carbon atoms, alkoxy or cycloalkyl;

R²

Alkyl with at least 8 carbon atoms, preferably in a straight chain;

X

Hydrogen, halogen or a group that can be split off with color coupling.

An alkyl group contained on the phenoxy group represented by R 1 is preferably methyl or isopropyl; an alkoxy group is preferably methoxy; a cycloalkyl group is preferably cyclohexyl.

Examples of cyan couplers according to the invention are listed in Example 1, Table 1 (couplers C-1 to C-8).

worin

R¹

einen Acylrest und

X

H, Halogen oder eine bei Farbkupplung abspaltbare Gruppe und

n

eine ganze Zahl von 1-3 bedeutet.

Magenta couplers of the 5-pyrazolone type preferably correspond to one of the formulas IIIa and IIIb

wherein

R¹

an acyl residue and

X

H, halogen or a group which can be split off in the case of a color coupling and

n

means an integer from 1-3.

worin bedeuten

R¹

Alkyl, Aralkyl oder Aryl;

X

H, Halogen oder eine bei Farbkupplung abspaltbare Gruppe und

Q

einen Rest zur Vervollständigung eines ankondensierten ungesättigten, gegebenenfalls substituierten 5-Ringes mit insgesamt 2, 3 oder 4 N-Atomen.

Pyrazoloazole type magenta couplers conform to Formula IV

in what mean

R¹

Alkyl, aralkyl or aryl;

X

H, halogen or a group which can be split off in the case of a color coupling and

Q

a radical to complete a fused-on unsaturated, optionally substituted 5-ring with a total of 2, 3 or 4 N atoms.

The coupling residue contained in the pyrazoloazole couplers of the formula IV is, for example, a residue of imidazolo [1,2-b] pyrazole, imidazolo [3,4-b] pyrazole, pyrazolo [2,3-b] pyrazole, pyrazolo [3,2 -c] -1,2,4-triazole, pyrazolo [2,3-b] -1,2,4-triazole, pyrazolo [2,3-c] -1,2,3-triazole or pyrazolo [2, 3-d] tetrazole. The corresponding structures are given below by the formulas IV-1 to IV-7.

In the general formulas IV-1 to IV-7, the substituents R, S, T and U represent hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl, Sulfamoyl, where these radicals can be further substituted and can contain, for example, a ballast radical. In formula IV-1, S and T together can also represent a radical to complete a fused-on, optionally substituted benzene ring.

• M-1:
  
  R² = H
• M-2:
  
  R² = H
• M-3: R¹ = -C₁₃H₂₇; R² = H
• M-4: R¹ = -OC₁₆H₃₃; R² = H
• M-5:
  
• M-6:
  
• M-7:
  
• M-8:
  
• M-9:
  
• M-10:
  
  
• M-11:
  
  R² = H
• M-12:
  
  R² = H
• M-13:
  
  R² = H
• M-14:
  
  
• M-15:
  
• M-16:
  
• M-17:
  
  
• M-18:
  
  R² = -CH₃
• M-19:
  
  R² = -CH₃
• M-20:
  
  R² = -C₄H₉-t
• M-21:
  
  R² = -CH₃
• M-22:
  
  R² = -CH₃
• M-23:
  
  R² = -CH₃
• M-24:
  
  R² = -CH₃
• M-25:
  

Suitable examples of magenta couplers are:

• M-1:
  
  R² = H
• M-2:
  
  R² = H
• M-3: R¹ = -C₁₃H₂₇; R² = H
• M-4: R¹ = -OC₁₆H₃₃; R² = H
• M-5:
  
• M-6:
  
• M-7:
  
• M-8:
  
• M-9:
  
• M-10:
  
  
• M-11:
  
  R² = H
• M-12:
  
  R² = H
• M-13:
  
  R² = H
• M-14:
  
  
• M-15:
  
• M-16:
  
• M-17:
  
  
• M-18:
  
  R² = -CH₃
• M-19:
  
  R² = -CH₃
• M-20:
  
  R² = -C₄H₉-t
• M-21:
  
  R² = -CH₃
• M-22:
  
  R² = -CH₃
• M-23:
  
  R² = -CH₃
• M-24:
  
  R² = -CH₃
• M-25:
  

worin bedeuten

R¹

Alkyl oder Aryl, insbesondere t-Butyl oder Phenyl, wobei der Phenylring substituiert sein kann, z.B. mit Alkoxy

R²

Wasserstoff, Halogen, Alkoxy, Aryloxy, Alkylamino;

R³

Wasserstoff, Halogen, Alkoxy, Dialkylamino, Acylamino, Sulfamoyl, Alkylcarbamoyl, Alkoxycrabonyl;

R⁴

ein Rest wie R³

Acylacetanilide type yellow couplers correspond to Formula V

in what mean

R¹

Alkyl or aryl, especially t-butyl or phenyl, where the phenyl ring can be substituted, for example with alkoxy

R²

Hydrogen, halogen, alkoxy, aryloxy, alkylamino;

R³

Hydrogen, halogen, alkoxy, dialkylamino, acylamino, sulfamoyl, alkylcarbamoyl, alkoxycrabonyl;

R⁴

a rest like R³

• Y-1: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-2: R¹ = -C₄H₉-t;
  
  R³ = -OC₁₆H₃₃; R⁴ = H; R⁵ = -SO₂NHCH₃
• Y-3: R¹ = -C₄H₉-t;
  
  R³ = Cl R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃
• Y-4: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H; R⁵ = -COOC₁₂H₂₅
• Y-5: R¹ = -C₄H₉-t; R² = H;   R³ = Cl; R⁴ = H;
  
• Y-6: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-7: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃
• Y-8: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-9: R¹ = -C₄H₉-t;
  
  R³ = -OC₁₆H₃₃; R⁴ = H; R⁵ = -SO₂NHCOC₂H₅
• Y-10: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H
  
• Y-11: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-12: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-13: R¹ = -C₄H₉-t;
  
  R³ = -OC₁₆H₃₃; R⁴ = H; R⁵ = -SO₂NHCH₃
• Y-14: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-15:
  
  R², R⁴, R⁵ = H; R³ = -OCH₃
• Y-16:
  
  R³, R⁵ = -OCH₃; R⁴ = H
• Y-17: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H; R⁵ = -COOC₁₂H₂₅
• Y-18:
  
  R³ = Cl; R⁴, R⁵ = -OCH₃
• Y-19:
  
  R³ = -OCH₃; R⁴ = H; R⁵ = -SO₂N(CH₃)₂
• Y-20:
  
  
  R³ = -OCH₃; R⁴ = H;
  
• Y-21:
  

Suitable examples of yellow couplers are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers of the formulas

• Y-1: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-2: R¹ = -C₄H₉-t;
  
  R³ = -OC₁₆H₃₃; R⁴ = H; R⁵ = -SO₂NHCH₃
• Y-3: R¹ = -C₄H₉-t;
  
  R³ = Cl R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃
• Y-4: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H; R⁵ = -COOC₁₂H₂₅
• Y-5: R¹ = -C₄H₉-t; R² = H; R³ = Cl; R⁴ = H;
  
• Y-6: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-7: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃
• Y-8: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-9: R¹ = -C₄H₉-t;
  
  R³ = -OC₁₆H₃₃; R⁴ = H; R⁵ = -SO₂NHCOC₂H₅
• Y-10: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H
  
• Y-11: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-12: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-13: R¹ = -C₄H₉-t;
  
  R³ = -OC₁₆H₃₃; R⁴ = H; R⁵ = -SO₂NHCH₃
• Y-14: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H;
  
• Y-15:
  
  R², R⁴, R⁵ = H; R³ = -OCH₃
• Y-16:
  
  R³, R⁵ = -OCH₃; R⁴ = H
• Y-17: R¹ = -C₄H₉-t;
  
  R³ = Cl; R⁴ = H; R⁵ = -COOC₁₂H₂₅
• Y-18:
  
  R³ = Cl; R⁴, R⁵ = -OCH₃
• Y-19:
  
  R³ = -OCH₃; R⁴ = H; R⁵ = -SO₂N (CH₃) ₂
• Y-20:
  
  
  R³ = -OCH₃; R⁴ = H;
  
• Y-21:
  

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as those that have an intense inherent color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler).

The color couplers used according to the invention are assigned in the usual way to silver halide emulsion layers with different spectral sensitivity, so that during the chromogenic development of the negative material, complementary-colored partial color images are generated to the color of the exposure light.

The couplers or other compounds can be incorporated into the silver halide emulsion layers in such a way that a solution, a dispersion or an emulsion is first prepared by the coupler and then the casting solution for the layer in question is added. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.

Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-26 09 741 and DE-A-26 09 742.

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.

Instead of the high-boiling solvents or additionally, oligomers or polymers, so-called polymeric oil formers, can be used.

The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

Suitable oil formers are, for example, alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.

Examples of suitable oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-octoxy-5-butyl-2-butyl , Paraffin, dodecylbenzene and diisopropylnaphthalene.

Each of the differently sensitized, light-sensitive layers of the negative material can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). In this case, red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

In addition to the couplers mentioned, the silver halide emulsion layers can contain further additives, in particular, to produce the various partial color images photographically active additives such as antioxidants, white couplers, DIR couplers, DAR couplers, FAR couplers and the like.

The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.

$$\begin{gathered} \text{R₁, R₂ = -C₈H₁₇-t} \\ \text{-C₁₂H₂₅-s} \\ \text{-C₆H₁₃-t} \end{gathered}$$

        -C₈H₁₇-s



        -C₁₅H₃₁

Examples of particularly suitable compounds are:

$$\begin{gathered} \text{R₁, R₂ = -C₈H₁₇-t} \\ \text{-C₁₂H₂₅-s} \\ \text{-C₆H₁₃-t} \end{gathered}$$

-C₈H₁₇-s



-C₁₅H₃₁

If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sublayer with higher sensitivity will be located further away from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, for example through Layers of other spectral sensitization must be separated. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.

Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).

Suitable formalin scavengers include

H₂N-CONH- (CH₂) ₂-NH-CONH₂,

Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643 (Dec. 1978), Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds that have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the deterioration of yellow color images due to the development of heat, moisture and light. In order to prevent the deterioration of magenta color images, in particular their impairment as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are substituted by hydroquinone diethers or monoethers (JP-A-89 835 / 80) particularly effective.

sowie die als EOP-Fänger aufgeführten Verbindungen.Examples of particularly suitable compounds are:

as well as the compounds listed as EOP catchers.

The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207), divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3, 5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbamoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308) , Compounds having two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

The hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.

There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry and the swelling of the layer structure occurs as a result of the crosslinking reaction . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.

• (a)
  
  worin

  R¹

  Alkyl, Aryl oder Aralkyl bedeutet,

  R²

  die gleiche Bedeutung wie R¹ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel

  
     verknüpft ist, oder

  R¹ und R²

  zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

  R³

  für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR⁴-COR⁵, -(CH₂)_m-NR⁸R⁹, -(CH₂)_n-CONR¹³R¹⁴ oder

  

  oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei

  R⁴,

  R⁶, R⁷, R⁹, R¹⁴, R¹⁵, R¹⁷, R¹⁸, und R¹⁹ Wasserstoff oder C₁-C₄-Alkyl,

  R⁵

  Wasserstoff, C₁-C₄-Alkyl oder NR⁶R⁷,

  R⁸

  -COR¹⁰

  R¹⁰

  NR¹¹R¹²

  R¹¹

  C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R¹²

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R¹³

  Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,

  R¹⁶

  Wasserstoff, C₁-C₄-Alkyl, -COR¹⁸ oder -CONHR¹⁹,

  m

  eine Zahl 1 bis 3

  n

  eine Zahl 0 bis 3

  p

  eine Zahl 2 bis 3 und

  Y

  0 oder NR¹⁷ bedeuten oder

  R¹³ und R¹⁴

  gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,

  Z

  die zur Vervollständigung eines 5- oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und

  X^⊖

  ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;

• (b)
  
  worin

  R¹, R², R³ und X^⊖

  die für Formel (a) angegebene Bedeutung besitzen.

Suitable examples of instant hardeners are, for example, compounds of the general formulas

• (a)
  
  wherein

  R¹

  Means alkyl, aryl or aralkyl,

  R²

  has the same meaning as R¹ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond being with a group of the formula

  
  is linked, or

  R1 and R2

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C₁-C₃alkyl or halogen,

  R³

  for hydrogen, alkyl, aryl, alkoxy, -NR⁴-COR⁵, - (CH₂) _m -NR⁸R⁹, - (CH₂) _n -CONR¹³R¹⁴ or

  

  or a bridge link or a direct bond to a polymer chain, wherein

  R⁴,

  R⁶, R⁷, R⁹, R¹⁴, R¹⁵, R¹⁷, R¹⁸, and R¹⁹ are hydrogen or C₁-C₄ alkyl,

  R⁵

  Hydrogen, C₁-C₄-alkyl or NR⁶R⁷,

  R⁸

  -COR¹⁰

  R¹⁰

  NR¹¹R¹²

  R¹¹

  C₁-C₄ alkyl or aryl, especially phenyl,

  R¹²

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R¹³

  Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,

  R¹⁶

  Hydrogen, C₁-C₄-alkyl, -COR¹⁸ or -CONHR¹⁹,

  m

  a number 1 to 3

  n

  a number 0 to 3

  p

  a number 2 to 3 and

  Y

  0 or NR¹⁷ mean or

  R¹³ and R¹⁴

  together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, for example, by C₁-C₃alkyl or halogen,

  Z.

  the carbon atoms required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring, and

  X ^⊖

  mean an anion which is omitted if an anionic group is already linked to the rest of the molecule;

• (b)
  
  wherein

  R¹, R², R³ and X ^⊖

  have the meaning given for formula (a).

There are diffusible curing agents that have the same curing effect on all layers within a layer structure. But there are also layer-limited, non-diffusing, low molecular weight and high molecular hardener. They can be used to link individual layers, for example the protective layer, particularly strongly. This is important if the silver halide layer is hardened little because of the increase in silver opacity and the mechanical layer has to be improved with the protective layer (EP-A-0 114 699).

Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

After the color development, an acidic stop bath or watering can follow.

Usually the material is bleached and fixed immediately after color development. As bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used. Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulfates and peroxides, e.g. Hydrogen peroxide.

The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.

Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.

However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also acts as a final bath.

example 1

In each case 8 mmol of couplers were dissolved in a ratio of 1: 3 in ethyl acetate (EA) at approx. 50 ° C. and dibutyl phalate (DBP) and manoxol were added, so that a ratio:
Coupler: DBP: EA: Manoxol = 1: 1: 3: 0.1
results. The mixture was then emulsified in 7.5% gelatin solution. The emulsate was stirred at 1000 rpm for 6 min, during which it heated up to approx. 50 ° C. and EA was suctioned off in a water jet vacuum (200-300 mbar).

The emulsions thus produced were mixed with a silver bromide iodide emulsion (0.7 mol% iodide) in a ratio of 1 mol coupler: 5.2 mol AgNO₃, applied to a layer of cellulose acetate and covered with a protective layer of a 3% gelatin solution, which as Hardening agent contained a carbamoylpyridinium betaine (CAS Reg. No. 65411-60-1). After drying and slicing, the samples thus produced were exposed behind a step wedge and processed in the negative AP 70 process (38 ° C.).

The following baths were used:

Color developer

   mit Wasser auf 10 l auffüllen; pH 10,0

make up to 10 l with water; pH 10.0

Bleach bath

   mit Wasser auf 10 l auffüllen und mit ca. 15 ml Eisessig auf pH 6,0 ± 0,1 einstellen

Make up to 10 l with water and adjust to pH 6.0 ± 0.1 with approx. 15 ml glacial acetic acid

Fixer

mit Wasser auf 10 l auffüllen; pH 7,5

make up to 10 l with water; pH 7.5

Samples of the color layers produced in this way were taken in the density range D = 1-2, and the absorption spectrum was measured between quartz plates against the layer support as a comparison sample in the λ 5 spectrophotometer from Perkin-Elmer at T = 23 ° C., 35 ° C. and 45 ° C. measured. Examples of spectra obtained in this way at T = 23 ° C. (curve 1 - solid) and 45 ° C. (curve 2 - dashed) are in FIGS. 2 to 5 for the couplers CC-1, CC-2, CC-3 and C-1 shown. The coupler structures used and the numerical values are listed in Table 1.

Table 1 also shows the measurements of the density decrease in the measuring station (scanning station) of the MSP printer when the original is stationary. The density values D are the average of 10 simultaneous measurements on the negative width of 35 mm at the time t = t _o and after 15 s (thermal equilibrium).

The greatest temperature dependence in intensity and position of the absorption band is shown by the dye of the comparative coupler CC-1 (FIG. 2), the lowest temperature dependence by the dye of the coupler C-1 according to the invention (FIG. 5).

In the temperature range T = 23 - 45 ° C, the absorption A of the dye changes reversibly with the temperature in all couplers (Fig. 6). At the absorption maximum, deviations of ± 1 - 2 nm occur within the cycle T = 23 → 45 → 35 → 23 ° C, which is attributed to the complex environment of the dye (highly saturated solution in di-n-butyl phthalate).

The extent of the temperature effect is the slopes (ΔA / ΔT) or (Δλ / ΔT), which are described by the coefficients a and b.

In accordance with the temperature dependence of the density in the MSP printer, the following series is found for the temperature effect of the absorption measurements:

A decrease in density of e.g. 0.09 at D = 1.37 of the dye CC-1-CD4 is prohibitive in multicopy and recognizable as a clear color cast.

The temperature dependency can be described more precisely by means of the absorption measurement, since the measurement is spectral, in contrast to the integral printer measurement. Therefore, the absorption measurements are preferably shown in the following examples.

Example 2

According to the information in Example 1, photographic layers were produced with the couplers (magenta and yellow) mentioned in Table 2 and processed and evaluated in the manner indicated. The results are shown in Table 2.

Claims (4)

1. A colour photographic recording material which contains on a transparent layer support at least one red-sensitive silver halide emulsion layer and a cyan coupler of the naphthol or phenol type associated therewith, at least one green-sensitive silver halide emulsion layer and a magenta coupler of the 5-pyrazolone or pyrazoloazole type associated therewith and at least one blue-sensitive silver halide emulsion layer and a yellow coupler of the acylacetanilide type associated therewith, characterized in that the following condition applies to the cyan dye formed from the cyan coupler during chromogenic development using 1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-phenylenediamine (CD 4) as colour developer in the layer: $$\text{a · (1 + b) ≦ 1.5}$$

   

   where

   a   is the temperature coefficient of the absorption $${\text{A}}_{\text{(T = 23°C)}}\text{= 1 g}\frac{{\text{I}}_{\text{o}}}{\text{I}}$$

   

   

   and

   b   is the temperature coefficient of the absorption wavelength λ_{(T = 23°C)}

   
2. A recording material as claimed in claim 1, characterized in that the following condition also applies to the image dyes formed from the magenta coupler and from the yellow coupler during chromogenic development using 1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-phenylenediamine (CD 4) as colour developer in the layer: $$\text{a · (1 + b) ≦ 1.5}$$

   

   where

   a   is the temperature coefficient of the absorption $${\text{A}}_{\text{(T = 23°C)}}\text{= 1 g}\frac{{\text{I}}_{\text{o}}}{\text{I}}$$

   

   

   and

   b   is the temperature coefficient of the absorption wavelength λ_{(T = 23°C)}

   
3. A recording material as claimed in claim 1 or 2, characterized in that the cyan coupler corresponds to formula II:

   

   in which

   W   represents H or another two substituents;

   R¹   represents a phenoxy group which has at least one unsubstituted o-position on the phenyl ring and, in addition, may be substituted by 1 to 3 substituents from the group consisting of C₁₋₃ alkyl, alkoxy or cycloalkyl;

   R²   represents alkyl containing at least 8 C atoms,

   X   represents hydrogen, halogen or a group releasable during the colour coupling reaction.
4. A process for the preparation of a plurality of identical positive dye images from a transparent original, preferably in a high-performance (scan) printer, in which the original is line-scanned once to determine the necessary exposure and filter data, after which a plurality of different sections of a colour photographic print material are successively exposed through the same original on the basis of the exposure and filter data thus determined and are then chromogenically developed and in which, to prepare a transparent original, a colour photographic recording material is used which contains on a transparent layer support at least one red-sensitive silver halide emulsion layer and a cyan coupler of the naphthol or phenol type associated therewith, at least one green-sensitive silver halide emulsion layer and a magenta coupler of the 5-pyrazolone or pyrazoloazole type associated therewith and at least one blue-sensitive silver halide emulsion layer and a yellow coupler of the acylacetanilide type associated therewith and which is exposed to form an image and then chromogenically developed in the usual way, characterized in that the following condition applies to the cyan dye formed from the cyan coupler during chromogenic development using 1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-phenylene-diamine (CD 4) as colour developer in the layer: $$\text{a · (1 + b) ≦ 1.5}$$

   

   where

   a   is the temperature coefficient of the absorption $${\text{A}}_{\text{(T = 23°C)}}\text{= 1 g}\frac{{\text{I}}_{\text{o}}}{\text{I}}$$

   

   

   and

   b   is the temperature coefficient of the absorption wavelength λ_{(T = 23°C)}

   

Images