EP0585546B1 - Photographic recording material - Google Patents

Description

The invention relates to a photographic recording material with at least one silver halide layer, the hydroquinone diether determined in one layer as Contains light stabilizers.

It is known to go through colored photographic images to produce chromogenic development, i.e. as a result of that exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called Color developer - developed, which is in accordance oxidation product resulting from the silver image of the developer substances with the color coupler with formation of a dye image reacts. As a color developer are usually aromatic, containing primary amino groups Compounds, especially those of the p-phenylenediamine type, used.

It is also known that through chromogenic development generated image dyes to varying degrees undergo certain changes under the influence of environmental conditions. This is particularly striking when it comes to the effects of light. As is well known especially bleach the magenta dyes produced from pyrazoloazole couplers strong, while the cyan dyes produced from phenolic couplers proven particularly vulnerable in this regard.

There has been no shortage of attempts, this lack through special measures remedy. In the case of the magenta coupler, in particular, it was possible to use light stabilizers Additions to achieve improved lightfastness. As a light stabilizer Agents are essentially phenolic compounds, in particular Derivatives of hydroquinone, either added to the couplers or are linked in the form of substituents to the coupler molecules (DE-B-1 547 803, DE-A-26 17 826, DE-A-29 52 511, JP-N-53 070 822, JP-N-54 070 830, JP-N-54 073 032). Hydroquinone dialkyl ethers are already available as Light stabilizers have been described, e.g. in US-A-4 588 679 and US-A-4 735 893. Furthermore, N-alkylated aminophenol ethers are used as light stabilizers have been proposed, for example for the stabilization of pyrazoloazole couplers generated image dyes, cf. EP-A-0 273 412. The known light stabilizers However, they do not yet meet the requirements placed on them in every respect.

The invention has for its object a color photographic recording material to provide associated silver halide emulsion layers Contains cyan, magenta and yellow couplers and by adding a light stabilizer against the fading of the chromogen formed dye under the Influence of light has been stabilized.

worin bedeuten

R¹

Alkyl, Cycloalkyl, Aryl;

R²

H, Alkyl;

R³, R⁴

H, Alkyl, Cycloalkyl, Halogen, Alkoxy, Aroxy, Acyloxy, Alkylthio, Arylthio, Acyl, Sulfonyl, Sulfamoyl, Acylamino, Sulfonylamino, Nitro;

R⁵

H, Acyl, Alkyl,

X

-O- oder -NR⁶-;

R⁶

H oder Alkyl;

n

0 oder eine ganze Zahl von 1 bis 3.

The invention relates to a color photographic recording material having at least one red-sensitive silver halide emulsion layer to which a cyan coupler is assigned, at least one green-sensitive silver halide emulsion layer to which a magenta coupler is assigned, and at least one blue-sensitive silver halide emulsion layer to which a yellow coupler is assigned which has a hydroquinone diether compound in at least one of its layers contains, characterized in that the hydroquinone diether compound is a compound of the formula I with the exception of compounds of the formula IA and that at least one of the silver halide emulsion layers present is assigned a compound of the formula I with the exception of compounds of the formula IA in combination with a color coupler:

in what mean

R ¹

Alkyl, cycloalkyl, aryl;

R ²

H, alkyl;

R ³ , R ⁴

H, alkyl, cycloalkyl, halogen, alkoxy, aroxy, acyloxy, alkylthio, arylthio, acyl, sulfonyl, sulfamoyl, acylamino, sulfonylamino, nitro;

R ⁵

H, acyl, alkyl,

X

-O- or -NR ⁶ -;

R ⁶

H or alkyl;

n

0 or an integer from 1 to 3.

An alkyl radical represented by R ¹ to R ⁶ can be straight-chain or branched, unsubstituted or substituted and can contain up to 18 carbon atoms; Examples are methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, tert-amyl, hexyl, tert-hexyl, octyl, dodecyl; Examples of substituents are halogen (eg chlorine), hydroxy, alkoxy, alkoxycarbonyl, dialkylamino.

A cycloalkyl radical represented by R ¹ , R ³ or R ⁴ is in particular cyclohexyl or cyclopentyl.

An aryl radical represented by R ¹ is, in particular, phenyl, optionally substituted, for example with alkylsulfonyl, alkyl and / or alkoxy.

An acyl radical represented by or contained in R ³ , R ⁴ or R ⁵ is derived from an aliphatic or aromatic mono- or dicarboxylic acid, from a carbonic acid monoester or from a carbamic acid, examples of such acyl radicals are acetyl, 2-ethylhexanoyl, p-hydroxybenzoyl , Nn-butylcarbamoyl, Nt-butylcarbamoyl, N-dodecylcarbamoyl, hexyloxycarbonyl, dodecyloxycarbonyl. An acyl radical represented by R ⁵ can also be derived from phosphoric acid, phosphonic acid or phosphorous acid.

In a preferred embodiment of the invention, the hydroquinone diether compound corresponds to the formula I, in which at least one of the radicals R ³ and R ^{4 is} tertiary alkyl.

In further preferred embodiments of the invention, the hydroquinone diether compound corresponds to the formula I in which -XR ^{5 is} -OH, -O-CH ₂ -CH ₂ -OH or -O-acyl, the acyl radical being derived from aliphatic or aromatic carboxylic acids, from Carbamic acid, carbonic acid monoesters or phosphoric acid, phosphonic acid or phosphorous acid.

In further preferred embodiments of the invention the hydroquinone diether compound corresponds to the formula I, where n is 0 or 1.

Examples of hydroquinone diether compounds according to the invention are given below.

Synthesis example Synthesis of the light stabilizer I-14

18.0 g (100 mmol) 3-tert-butyl-4-hydroxyanisole (compound 1) are heated to 120 ° C in 25.0 g of ethylene carbonate. 5.0 g of potassium carbonate are added in portions and it is stirred for 4 h at this temperature. The reaction mixture is added to water, taken up in ether, washed with water, dried over sodium sulfate and am Rotary evaporator concentrated. Column chromatography Purification over silica sol gives 16.4 g (73% of theory) Connection 2.

16.4 g (73.1 mmol) (compound 2, 11.0 g (76.3 mmol) of 2-ethylhexanoic acid and 0.5 g of p-toluenesulfonic acid are in 50 ml of toluene heated for 6 hours on a water separator. Subsequently the organic phase with sodium hydrogen carbanate solution and water washed neutral, dried over sodium sulfate and concentrated on a rotary evaporator. Column chromatography Cleaning over silica sol gives 22.0 g (86% of theory) I-14.

worin bedeuten

R²¹, R²²

Reste wie R⁵;

R²³, R²⁴, R²⁵

Reste wie R³;

A

eine Einfachbindung, -S(=O)_m-, Alkylen oder -NR²⁶-;

R²⁶

Alkyl oder Acyl;

m

0, 1 oder 2;

worin bedeuten

R³¹, R³²

Alkyl, Cycloalkyl;

R³³, R³⁴

Reste wie R³;

worin bedeuten

R⁴¹, R⁴²

Reste wie R⁵;

R⁴³, R⁴⁴, R⁴⁵, R⁴⁶

Reste wie R³; mit der Maßgabe, daß mindestens einer der Reste R⁴⁴ und R⁴⁵ nicht Alkyl bedeutet;

worin bedeuten

R⁵¹

Alkyl, Cycloalkyl, Aryl;

R⁵², R⁵³, R⁵⁴, R⁵⁵

Reste wie R³;

p

0, 1 oder 2.

It has been shown that the light stabilizing effect which is achieved with compounds of the formula I can be significantly increased if a compound of the formula I is used in combination with at least one compound of one of the formulas II, III, IV and V below:

in what mean

R ²¹ , R ²²

Radicals such as R ⁵ ;

R ²³ , R ²⁴ , R ²⁵

Radicals such as R ³ ;

A

a single bond, -S (= O) _m -, alkylene or -NR ²⁶ -;

R ²⁶

Alkyl or acyl;

m

0, 1 or 2;

in what mean

R ³¹ , R ³²

Alkyl, cycloalkyl;

R ³³ , R ³⁴

Radicals such as R ³ ;

in what mean

R ⁴¹ , R ⁴²

Radicals such as R ⁵ ;

R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶

Radicals such as R ³ ; with the proviso that at least one of R ⁴⁴ and R ^{45 is} not alkyl;

in what mean

R ⁵¹

Alkyl, cycloalkyl, aryl;

R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵

Radicals such as R ³ ;

p

0, 1 or 2.

An alkyl radical represented by R ²⁶ or R ⁵¹ is an alkyl radical, as can also be represented by R ¹ to R ⁶ . An alkyl radical represented by R ³¹ or R ³² can be straight-chain or branched and contain up to 18 carbon atoms.

A cycloalkyl radical represented by R ³¹ , R ³² or R ⁵¹ is a cycloalkyl radical, as can also be represented by R ¹ , R ³ or R ⁴ .

An aryl radical represented by R ⁵¹ is an aryl radical, as can also be represented by R ¹ , R ³ or R ⁴ .

An acyl radical represented by R ²⁶ is an acyl radical, as can also be represented by R ³ , R ⁴ or R ⁵ .

in Formel II:

A für Alkylen mit 1-6 C-Atomen oder für -S(=O)_m- mit m = 0, 1 oder 2; R²¹ und R²² für H;

in Formel III:

mindestens einer der Reste R³³ und R³⁴ für Alkyl;

in Formel IV:

R⁴¹ und R⁴² für H oder Alkyl;

in Formel V:

R⁵⁴ und R⁵⁵ für H.

In a preferred embodiment of the invention stands / stand

in formula II:

A for alkylene with 1-6 C atoms or for -S (= O) _m - with m = 0, 1 or 2; R ²¹ and R ²² for H;

in formula III:

at least one of R ³³ and R ³⁴ for alkyl;

in formula IV:

R ⁴¹ and R ^{42 are} H or alkyl;

in formula V:

R ⁵⁴ and R ⁵⁵ for H.

Examples of compounds of the formulas II, III, IV and V used according to the invention are given below:

The color photographic recording material according to the invention contains a sequence of several photosensitive Silver halide emulsion layers with each assigned Color couplers and possibly other auxiliary layers such as especially protective layers and between the photosensitive Layers of non-photosensitive binder layers arranged, whereby according to the present invention at least one of the existing photosensitive silver halide emulsion layers a compound of the invention Formula I in combination with a color coupler assigned. Preferably, one according to the invention Compound of formula I combined with at least a compound of one of the formulas II, III, IV and V used. Here synergistic effects occur, i.e. the azomethine dyes produced during development are through a combination of a connection of formula I and a compound of one of the formulas II, III, IV and V are even better protected against light than by a compound of formula I alone. The connections of the formula I are with compounds one of formulas II, III, IV and V in a ratio of 1:10 to 10: 1, preferably 1: 4 to 4: 1.

The compounds of the formulas used according to the invention I, II, III, IV and V act primarily as Light stabilizer, i.e. that from the color coupler Azomethine dyes formed in the chromogenic development show considerable in their presence increased stability against exposure to light on. In addition, the compounds of the invention take over the function of a whole or in part Oil generator for the color coupler, i.e. you can alone or together with other known oil formers as Coupler solvent can be used. Thereby they make compounds of the invention preferably 50 to 100 wt .-% of the total amount of oil in the respective Layer off. Accordingly, they are preferred in the 0.2 to 2 times the amount by weight, based on the color couplers used together. Of the Circumstance that other oil formers not at all or possibly only required in smaller quantities favorable to the layer load and / or the total layer thickness of the recording materials according to the invention out.

The compounds of the formulas used according to the invention I to V are used as a solution in aprotic (hydrophobic) Solvents, e.g. Ethyl acetate, during incorporation into the casting solution for the layer in question with the respective color coupler. The training takes place in the usual way, where appropriate other auxiliary solvents and / or high-boiling Coupler solvents, so-called oil formers, are used can be.

That as a photosensitive component in the invention photographic recording material Silver halide can be used as halide chloride, Contain bromide or iodide or mixtures thereof. For example the halide content can be at least one 0 to 15 mol% layer of iodide, 0 to 100 mol% consist of chloride and 0 to 100 mol% of bromide.

In the case of color negative and color reversal films usually silver bromide iodide emulsions, in the case of Color negative and color reversal paper usually silver chloride bromide emulsions with high chloride content up to pure silver chloride emulsions are used. It can are mainly compact crystals, e.g. are regular cubic or octahedral or transitional forms can have. But preferably also platelet-shaped crystals are present, their average Ratio of diameter to thickness is preferably at least 5: 1, the diameter a grain is defined as the diameter of a Circle with a circle content corresponding to the projected Area of the grain. The layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly larger than 5: 1, e.g. 12: 1 to 30: 1.

The silver halide grains can also be multi-layered Have grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as Endowments of the individual Grain areas are different. The middle The grain size of the emulsions is preferably between 0.2 µm and 2.0 µm, the grain size distribution can be both be homo- and heterodisperse. Homodisperse grain size distribution means 95% of the grains are not deviate more than ± 30% from the average grain size.

In addition to the silver halide, the emulsions can also other silver salts, e.g. contain organic silver salts, such as silver benzotriazolate or silver behenate.

Two or more types of silver halide emulsions, which are made separately, as a mixture be used.

The emulsions can be chemically and in the usual way or be spectrally sensitized; you can also by suitable additives must be stabilized. Suitable chemical Sensitizers, spectral sensitizing dyes and stabilizers are, for example, in Research Disclosure 17643 (December 1978); referred special attention is paid to chapters III, IV and VI.

The color photographic recording material according to the invention contains at least one red sensitive, at least one sensitive to green and at least one sensitive to blue Silver halide emulsion layer. For setting the sensitivity is the photosensitive Layers in a known manner using suitable sensitizing dyes spectrally sensitized; in the blue sensitive silver halide emulsion layer can yourself due to the existing sensitivity No need to add sensitizing dyes.

An overview of those suitable as spectral sensitizers Polymethine dyes, their suitable combinations and super-sensitizing combinations contains Research Disclosure 17643 (Dec. 1978), chapter IV.

Suitable green sensitizers are, for example 9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups as well as benzimidazocarbocyanines, which also may be further substituted and also at least a sulfoalkyl group on heterocyclic nitrogen must contain.

GS-1:

R¹, R³, R⁷, R⁹ = H; R² = Phenyl;

R⁵ = -C₂H₅; R⁶ = SO₃ ^⊖; R⁸ = Cl; m = 2; n = 3; X, Y = O;

GS-2:

R¹, R², R⁷, R⁸ = Cl; R³, R⁵, R⁶, R⁹ = H;

m, n = 2; X, Y = N-C₂H₅;

GS-3:

R¹, R⁷ = H; R², R³ sowie R⁸, R⁹ zusammen -CH=CH-CH=CH-; R⁴ = SO₃ ^⊖Na^⊕; R⁵ = C₂H₅; R⁶ = SO₃ ^⊖ ; m, n = 3; X, Y = O;

GS-4:

R¹, R³, R⁴, R⁷, R⁸, R⁹ = H; R² = -OCH₃; R⁵ = -C₂H₅; R⁶ = SO₃ ^⊖ ; m = 2; n = 4; X = O; Y = S;

Examples that may be mentioned are the green sensitizers GS listed below, which can be used individually or in combination with one another, for example GS-1 and GS-2.

GS-1:

R ¹ , R ³ , R ⁷ , R ⁹ = H; R ² = phenyl;

R ⁵ = -C ₂ H ₅ ; R ⁶ = SO ₃ ^⊖ ; R ⁸ = Cl; m = 2; n = 3; X, Y = O;

GS-2:

R ¹ , R ² , R ⁷ , R ⁸ = Cl; R ³ , R ⁵ , R ⁶ , R ⁹ = H;

m, n = 2; X, Y = NC ₂ H ₅ ;

GS-3:

R ¹ , R ⁷ = H; R ² , R ³ and R ⁸ , R ⁹ together -CH = CH-CH = CH-; R ⁴ = SO ₃ ^⊖ Na ^⊕ ; R ⁵ = C ₂ H ₅ ; R ⁶ = SO ₃ ^⊖ ; m, n = 3; X, Y = O;

GS-4:

R ¹ , R ³ , R ⁴ , R ⁷ , R ⁸ , R ⁹ = H; R ² = -OCH ₃ ; R ⁵ = -C ₂ H ₅ ; R ⁶ = SO ₃ ^⊖ ; m = 2; n = 4; X = O; Y = S;

Each of the light-sensitive layers mentioned can consist of consist of a single layer or in a known manner, e.g. with the so-called double layer arrangement, too two or more silver halide emulsion partial layers include (DE-C-1 121 470). With negative films usually red sensitive silver halide emulsion layers arranged closer to the substrate than those sensitive to green Silver halide emulsion layers and these again closer than blue-sensitive, which is generally between green sensitive layers and blue sensitive Layers a non-photosensitive yellow filter layer. But there are also others Arrangements conceivable, e.g. for color paper. Between Layers of different spectral sensitivity usually a non-photosensitive intermediate layer arranged, the means for preventing the Incorrect diffusion of developer oxidation products included can. If multiple layers of silver halide emulsion have the same spectral sensitivity, can these be directly adjacent to each other or be arranged so that there is a light-sensitive between them Layer with a different spectral sensitivity (DE-A-1 958 709, DE-A-2 530 645, DE-A-2 622 922).

Color photographic recording materials according to the invention usually contain in spatial and spectral Assignment to the silver halide emulsion layers different spectral sensitivity color coupler to generate the different part color images Cyan, magenta and yellow, with at least one of the color couplers together with one of the compounds according to the invention of formula I, preferably in combination with at least one compound of one of the formulas II, III, IV and V, the relevant silver halide emulsion layer assigned.

Spatial assignment is understood to mean that the color coupler is in such a spatial relationship to the silver halide emulsion layer, that an interaction between them is possible, the a pictorial correspondence between that at the Development formed silver picture and that from the color coupler color image generated. This is in the Usually achieved in that the color coupler together with the hydroquinone diether compound of formula I, preferably in combination with at least one connection one of the formulas II, III, IV and V, in the silver halide emulsion layer itself is included or in one adjacent to this, if necessary, non-light-sensitive Binder layer.

Spectral assignment means that the Spectral sensitivity of each of the photosensitive Silver halide emulsion layers and the color of the the spatially assigned color coupler Partial color image in a certain relationship to each other stand, each of the spectral sensitivities (Red, green, blue) another color of the concerned Partial color image (generally e.g. the colors cyan, Magenta or yellow in this order) is.

C-1:

R¹, R²= H;

C-2:

R¹ = -NHCOOCH₂-CH(CH₃)₂; R² = H; R³ = -(CH₂)₃-OC₁₂H₂₅

C-3:

R¹ = H; R² = -OCH₂-CH₂-SO₂CH₃; R³ =-C₁₆H₃₃

C-4:

R¹ = H; R² = -OCH₂-CONH-(CH₂)₂-OCH₃;

C-5:

R¹, R² = H;

C-6:

R¹, R² = H;

C-7:

R¹ = H; R² = Cl; R³ = -C(C₂H₅)₂-C₂₁H₄₃

C-8:

R¹ = H; R² = -O-CH₂-CH₂-S-CH(COOH)-C₁₂H₂₅ R³ = Cyclohexyl

C-9:

R¹ = -C₄H₉; R² = H; R³ = -CN; R⁴ = Cl

C-10:

R¹ = -C₄H₉; R² = H; R³ = H; R⁴ = -SO₂CHF₂

C-11:

R¹ = -C₄H₉;

R³ = H; R⁴ = -CN

C-12:

R¹ = C₂H₅; R², R³ = H; R⁴ = -SO₂CH₃

C-13:

R¹ = -C₄H₉; R², R³ = H; R⁴ = -SO₂-C₄H₉

C-14:

R¹ = -C₄H₉; R² = H; R³ = -CN; R⁴ = -CN

C-15:

R¹ = -C₄H₉; R², R³ = H; R⁴ = -SO₂-CH₂-CHF₂

C-16:

R¹ = -C₂H₅; R², R³ = H; R⁴ = -SO₂CH₂-CHF-C₃H₇

C-17:

R¹ = -C₄H₉; R², R³ = H; R⁴ = F

C-18:

R¹ = -C₄H₉; R², R³ =H; R⁴ = -SO₂CH₃

C-19:

R¹ = -C₄H₉; R², R³ = H; R⁴ = -CN

C-20:

R¹ = -CH₃; R² = -C₂H₅; R³, R⁴ = -C₅H₁₁-t

C-21:

R¹ = -CH₃; R² = H; R³, R⁴ = -C₅H₁₁-t

C-22:

R¹, R² = -C₂H₅; R³, R⁴ = -C₅H₁₁-t

C-23:

R¹ = -C₂H₅; R² = -C₄H₉; R³, R⁴ = -C₅H₁₁-t

C-24:

R¹ = -C₂H₅; R² = -C₄H₉; R³, R⁴ = -C₄H₉-t

C-25:

R¹, R² = -C₅H₁₁-t; R³ = -C₄H₉; R⁴ = H; R⁵ = -C₃F₇

C-26:

R¹ = -NHSO₂-C₄H₉; R² = H; R³ = -C₁₂H₂₅; R⁴ = Cl; R⁵ = Phenyl

C-27:

R¹, R² = -C₅H₁₁-t; R³ = -C₃H₇-i; R⁴ = Cl; R⁵ = Pentafluorphenyl

C-28:

R¹ = = -C₅H₁₁-t; R² = Cl; R³ = -C₆H₁₃; R⁴ = Cl; R⁵ = -2-Chlorphenyl

Color couplers for producing the partial color image cyan are usually couplers of the phenol or α-naphthol type; suitable examples are

C-1:

R ¹ , R ² = H;

C-2:

R ¹ = -NHCOOCH ₂ -CH (CH ₃ ) ₂ ; R ² = H; R ³ = - (CH ₂ ) ₃ -OC ₁₂ H ₂₅

C-3:

R ¹ = H; R ² = -OCH ₂ -CH ₂ -SO ₂ CH ₃ ; R ³ = -C ₁₆ H ₃₃

C-4:

R ¹ = H; R ² = -OCH ₂ -CONH- (CH ₂ ) ₂ -OCH ₃ ;

C-5:

R ¹ , R ² = H;

C-6:

R ¹ , R ² = H;

C-7:

R ¹ = H; R ² = Cl; R ³ = -C (C ₂ H ₅ ) ₂ -C ₂₁ H ₄₃

C-8:

R ¹ = H; R ² = -O-CH ₂ -CH ₂ -S-CH (COOH) -C ₁₂ H ₂₅ R ³ = cyclohexyl

C-9:

R ¹ = -C ₄ H ₉ ; R ² = H; R ³ = -CN; R ⁴ = Cl

C-10:

R ¹ = -C ₄ H ₉ ; R ² = H; R ³ = H; R ⁴ = -SO ₂ CHF ₂

C-11:

R ¹ = -C ₄ H ₉ ;

R ³ = H; R ⁴ = -CN

C-12:

R ¹ = C ₂ H ₅ ; R ² , R ³ = H; R ⁴ = -SO ₂ CH ₃

C-13:

R ¹ = -C ₄ H ₉ ; R ² , R ³ = H; R ⁴ = -SO ₂ -C ₄ H ₉

C-14:

R ¹ = -C ₄ H ₉ ; R ² = H; R ³ = -CN; R ⁴ = -CN

C-15:

R ¹ = -C ₄ H ₉ ; R ² , R ³ = H; R ⁴ = -SO ₂ -CH ₂ -CHF ₂

C-16:

R ¹ = -C ₂ H ₅ ; R ² , R ³ = H; R ⁴ = -SO ₂ CH ₂ -CHF-C ₃ H ₇

C-17:

R ¹ = -C ₄ H ₉ ; R ² , R ³ = H; R ⁴ = F

C-18:

R ¹ = -C ₄ H ₉ ; R ² , R ³ = H; R ⁴ = -SO ₂ CH ₃

C-19:

R ¹ = -C ₄ H ₉ ; R ² , R ³ = H; R ⁴ = -CN

C-20:

R ¹ = -CH ₃ ; R ² = -C ₂ H ₅ ; R ³ , R ⁴ = -C ₅ H ₁₁ -t

C-21:

R ¹ = -CH ₃ ; R ² = H; R ³ , R ⁴ = -C ₅ H ₁₁ -t

C-22:

R ¹ , R ² = -C ₂ H ₅ ; R ³ , R ⁴ = -C ₅ H ₁₁ -t

C-23:

R ¹ = -C ₂ H ₅ ; R ² = -C ₄ H ₉ ; R ³ , R ⁴ = -C ₅ H ₁₁ -t

C-24:

R ¹ = -C ₂ H ₅ ; R ² = -C ₄ H ₉ ; R ³ , R ⁴ = -C ₄ H ₉ -t

C-25:

R ¹ , R ² = -C ₅ H ₁₁ -t; R ³ = -C ₄ H ₉ ; R ⁴ = H; R ⁵ = -C ₃ F ₇

C-26:

R ¹ = -NHSO ₂ -C ₄ H ₉ ; R ² = H; R ³ = -C ₁₂ H ₂₅ ; R ⁴ = Cl; R ⁵ = phenyl

C-27:

R ¹ , R ² = -C ₅ H ₁₁ -t; R ³ = -C ₃ H ₇ -i; R ⁴ = Cl; R ⁵ = pentafluorophenyl

C-28:

R ¹ = = -C ₅ H ₁₁ -t; R ² = Cl; R ³ = -C ₆ H ₁₃ ; R ⁴ = Cl; R ⁵ = -2-chlorophenyl

M-1:

R² = H

M-2:

R² = H

M-3:

R¹ = -C₁₃H₂₇; R² = H

M-4:

R¹ = -OC₁₆H₃₃; R² = H

M-5:

R¹ = C₁₃H₂₇;

M-6:

M-7:

R¹ = -C₉H₁₉;

M-8:

M-11:

R² = H

M-12:

R² = H

M-13:

R² = H

M-14:

Color couplers for generating the magenta partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; suitable examples are

M-1:

R ² = H

M-2:

R ² = H

M-3:

R ¹ = -C ₁₃ H ₂₇ ; R ² = H

M-4:

R ¹ = -OC ₁₆ H ₃₃ ; R ² = H

M-5:

R ¹ = C ₁₃ H ₂₇ ;

M-6:

M-7:

R ¹ = -C ₉ H ₁₉ ;

M-8:

M-11:

R ² = H

M-12:

R ² = H

M-13:

R ² = H

M-14:

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;

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:

R³ = Cl; R⁴ = H; R⁵ = -COOC₁₂H₂₅

Y-18:

R³ = Cl; R⁴, R⁵ = -OCH₃

Y-19:

R³ = -OCH₃; R⁴ = -SO₂N(CH₃)₂; R⁵ = H

Y-20:

R³ = -OCH₃; R⁴ = H;

Color couplers for producing the partial color image yellow are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type; suitable examples of this are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers of the formulas

Y-1:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H;

Y-2:

R ¹ = -C ₄ H ₉ -t;

R ³ = -OC ₁₆ H ₃₃ ; R ⁴ = H; R ⁵ = -SO ₂ NHCH ₃

Y-3:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl R ⁴ = H; R ⁵ = -NHSO ₂ -C ₁₆ H ₃₃

Y-4:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H; R ⁵ = -COOC ₁₂ H ₂₅

Y-5:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H;

Y-6:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H;

Y-7:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H; R ⁵ = -NHSO ₂ -C ₁₆ H ₃₃

Y-8:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H;

Y-9:

R ¹ = -C ₄ H ₉ -t;

R ³ = -OC ₁₆ H ₃₃ ; R ⁴ = H; R ⁵ = -SO ₂ NHCOC ₂ H ₅

Y-10:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H

Y-11:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H;

Y-12:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H;

Y-13:

R ¹ = -C ₄ H ₉ -t;

R ³ = -OC ₁₆ H ₃₃ ; R ⁴ = H; R ⁵ = -SO ₂ NHCH ₃

Y-14:

R ¹ = -C ₄ H ₉ -t;

R ³ = Cl; R ⁴ = H;

Y-15:

R ² , R ⁴ , R ⁵ = H; R ³ = -OCH ₃

Y-16:

R ³ , R ⁵ = -OCH ₃ ; R ⁴ = H

Y-17:

R ³ = Cl; R ⁴ = H; R ⁵ = -COOC ₁₂ H ₂₅

Y-18:

R ³ = Cl; R ⁴ , R ⁵ = -OCH ₃

Y-19:

R ³ = -OCH ₃ ; R ⁴ = -SO ₂ N (CH ₃ ) ₂ ; R ⁵ = H

Y-20:

R ³ = -OCH ₃ ; R ⁴ = H;

worin bedeuten

R⁶¹

H, Alkyl, Aralkyl oder Aryl;

Y

H oder eine durch Kupplung freisetzbare Gruppe;

Z_a, Z_b, Zc

eine gegebenenfalls substituierte Methingruppe, =N- oder -NH-, wobei entweder die Bindung Z_a - Z_b oder die Bindung Z_b - Z_c eine Doppelbindung und die jeweils andere Bindung eine Einfachbindung ist;

Kuppler der Formel VI werden zusammenfassend als Pyrazoloazolkuppler bezeichnet. Darunter versteht man insbesondere Kuppler, die sich ableiten von Imidazolo[1,,2-b]pyrazol, Imidazolo[3,4-b]pyrazol, Pyrazolo[2,3-b]pyrazol, Pyrazolo[3,2-c]-1,2,4-triazol, Pyrazolo[2,3-b]-1,2,4-triazol, Pyrazolo[2,3-c]-1,2,3-triazol oder Pyrazolo[2,3-d]tetrazol. Die entsprechenden Strukturen sind nachstehend durch die Formeln VIa bis VIg angegeben.

In a preferred embodiment, the recording material of the present invention contains in at least one of its silver halide emulsion layers a combination of a hydroquinone diether compound of the formula I and a magenta coupler of the formula VI

in what mean

R ⁶¹

H, alkyl, aralkyl or aryl;

Y

H or a clutch releasable group;

Z _a , Z _b , Zc

an optionally substituted methine group, = N- or -NH-, where either the bond Z _a - Z _b or the bond Z _b - Z _{c is} a double bond and the other bond is a single bond;

Couplers of the formula VI are referred to collectively as pyrazoloazole couplers. These are understood to mean, in particular, couplers which are derived from 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 VIa to VIg.

In the general formulas (VIa) to (VIg), the radicals R ⁶¹ , 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.

Furthermore, Y stands for hydrogen or one for color coupling removable residue such as a halogen atom or a via an oxygen atom, a sulfur atom or a Nitrogen atom preferably attached to the coupling point cyclic group.

If the split group is one cyclic group, the link to the Coupling point of the coupler molecule either directly above an atom that is part of a ring, e.g. B. a Nitrogen atom, or indirectly via an intermediate Link has been made. Such Cleavable groups are known in large numbers, e.g. B. as escape groups of 2 equivalent magnetic couplers.

Examples of cleavable groups attached via oxygen correspond to the formula - O - R ⁶² in which R ^{62 represents} an acyclic or cyclic organic radical, for example alkyl, aryl, a heterocyclic group or acyl which is derived, for example, from an organic carbon or sulfonic acid. In the case of particularly preferred cleavable groups of this type, R ⁶² denotes an optionally substituted phenyl group.

Examples of cleavable groups linked via nitrogen are described in the following German patent applications (DE-A-):
25 36 191, 27 03 589, 28 13 522, 33 39 201.

These are often 5-membered heterocyclic Rings that have a ring nitrogen atom with the Coupling point of the purple coupler are connected. The heterocyclic rings often contain adjacent to which mediates the bond to the coupler molecule Nitrogen atom activating groups, e.g. B. carbonyl or Sulfonyl groups or double bonds.

If the cleavable group is attached to the Coupling point of the coupler is bound, it can for the rest of a diffusible carbocyclic or heterocyclic mercapto compound, which inhibit the development of silver halide can Such inhibitor residues are numerous than at the coupling point of couplers, also purple couplers bonded cleavable group described e.g. in US-A-3,227,554.

worin R⁶³ und R⁶⁴ für Alkyl und R⁶⁵ für H oder einen Substituenten stehen. Of the pyrazoloazole couplers of the formulas VIa to VIg, those of the formulas VId and VIe are preferably used according to the invention together with a hydroquinone diether compound of the formula I. In the formulas VId and VIe, at least one of the radicals R ⁶¹ and S or at least one of the radicals R ⁶¹ and T preferably represents a secondary alkyl or tertiary alkyl radical, ie a radical of the formula

wherein R ⁶³ and R ^{64 are} alkyl and R ^{65 is} H or a substituent.

Possible substituents are alkyl, aryl, cycloalkyl, hydroxy, halogen, -COOH, -SO ₃ H, -SO ₂ H, alkoxy, aryloxy, alkylthio, arylthio, nitro, sulfonyl, sulfamoyl, sulfonylamino, acylamino, carbamoyl, acyloxy, alkoxycarbonyl, Aryloxycarbamoyl, ureido, carbamoyloxy, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyloxy and aryloxycarbonyloxy.

Preferred substituents are alkyl, sulfonyl, sulfonylamino, Sulfamoyl, ureido, acylamino, carbamoyl, alkoxy, Aryloxy and alkoxycarbonylamino.

VI-24

R⁶¹ = CH₃

VI-25

R⁶¹ = CH₃

VI-26

R⁶¹ = CH₂-CH(CH₃)₂

VI-27

R⁶¹ = -CH₃

VI-28

R⁶¹ = -CH₃

VI-29

R⁶¹ = -CH₃

VI-30

R⁶¹ = -CH₃

VI-31

R⁶¹ = -CH₃

VI-32

R⁶¹ = -CH₃

VI-33

R⁶¹ = -C₃H₇-n

VI-34

R⁶¹ = -CH₃

VI-35

T = -CH₂-CH₂-OCH₃

Examples of pyrazoloazole couplers of the formula VI are:

VI-24

R ⁶¹ = CH ₃

VI-25

R ⁶¹ = CH ₃

VI-26

R ⁶¹ = CH ₂ -CH (CH ₃ ) ₂

VI-27

R ⁶¹ = -CH ₃

VI-28

R ⁶¹ = -CH ₃

VI-29

R ⁶¹ = -CH ₃

VI-30

R ⁶¹ = -CH ₃

VI-31

R ⁶¹ = -CH ₃

VI-32

R ⁶¹ = -CH ₃

VI-33

R ⁶¹ = -C ₃ H ₇ -n

VI-34

R ⁶¹ = -CH ₃

VI-35

T = -CH ₂ -CH ₂ -OCH ₃

The color couplers can be 4-equivalent couplers, but also act as 2-equivalent couplers. The latter are derived from the 4 equivalent couplers in that they have a in the coupling point Contain substituents in the coupling is split off. To the 2 equivalent couplers are count those that are colorless, as well as those which have an intense intrinsic color, which at Color coupling disappears or by the color of the generated Image dye is replaced (mask coupler), but also the white couplers, which react with color developer oxidation products essentially colorless Products result. To the 2 equivalent couplers are furthermore to count such couplers in the coupling point contain a cleavable residue, the reaction with color developer oxidation products in freedom is set, either directly or after the primary split off one or more other groups have been split off (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolded, e.g. as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

The couplers used, especially those according to the invention preferably used magenta couplers of the type Pyrazoloazoles, for example of the formulas (VId) and (VIe) can also be in polymeric form, e.g. as polymer latex apply.

High molecular weight color couplers are described, for example in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular color couplers are usually by polymerizing ethylenically unsaturated monomers Color couplers manufactured.

The color couplers used can also be those that Dyes with poor or limited mobility deliver.

Under poor or restricted mobility is to be understood a mobility that is measured in this way is that the contours of chromogenic development formed discrete dye stains run and are smeared into each other. This degree of mobility is to be distinguished on the one hand from the usual Case of complete immobility in photographic Layers used in conventional photographic materials for the color couplers or from them Dyes produced is aimed at a possible to achieve high sharpness, and on the other hand by the case of complete mobility of the dyes, the for example in color diffusion processes becomes. The latter dyes usually have about at least one group they are in alkaline Make medium soluble. The extent of the invention aimed weak mobility can be controlled are made by varying substituents, for example the solubility in the organic medium of the oil former or the affinity for the binder matrix in a more targeted manner Way to influence.

In addition to the components mentioned, the color photographic Recording material of the present Invention contain other additives, such as Antioxidants, dye stabilizers and Means for influencing the mechanical and electrostatic Properties as well as UV absorbers. Advantageous such additional connections are combined with the compounds of the invention, i.e. in the same Binding agent layer or in adjacent to each other Binder layers used.

These other additives to improve the dye, Coupler and whiteness stability and to reduce the Color veils (Research Disclosure 17 643 (Dec. 1978), Chapter VII) can include the following chemical classes include: hydroquinones, 5-, 6-, 7- and 8-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, Spiroindanes, p-alkoxyphenols, sterically hindered Phenols, gallic acid derivatives, methylenedioxybenzenes, Aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, Derivatives with acylated amino groups, metal complexes.

Compounds that have both a sterically hindered amine partial structure as well as a sterically hindered Have phenol partial structure in one molecule (US-A-4 268 593), are particularly effective in preventing the Impairment of yellow color images as a result of Development of heat, moisture and light. To the Impairment of purple color images, in particular their impairment as a result of exposure to prevent light are spiroindanes (JP-A-159 644/81) and Chromane by alkoxy and / or Hydroxy groups are substituted (JP-A-89 835/80) particularly effective, also alkylureidophenols (German patent application P 42 09 346.5).

Examples of particularly suitable compounds are:

Compounds that absorb UV light are said to be on the one hand the image dyes before fading by UV-rich Protect daylight and on the other hand as filter dyes the UV light in daylight during exposure absorb and thus improve the color rendering of a film. Usually for the two tasks Connections of different structures are used. 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).

R, R¹ = H;    R² = -C₄H₉-t

R = H;    R¹, R² = -C₄H₉-t

R = H;    R¹, R² = -C₅H₁₁-t

R = H;    R¹ = -C₄H₉-s;    R² = -C₄H₉-t

R = Cl;    R¹ = -C₄H₉-t;    R² = -C₄H₉-s

R = Cl;    R¹, R² = -C₄H₉-t

R = Cl;    R¹ = -C₄H₉-t;    R² = -CH₂-CH₂-COOC₈H₁₇

R = H;    R = -C₁₂H₂₅-i;    R² = -CH₃

R, R¹, R² = -C₄H₉-t

R¹, R² = -C₆H₁₃ ;    R³, R⁴ = -CN

R¹, R² = -C₂H₅;

R⁴ = -CO-OC₈H₁₇

R¹, R² = -C₂H₅;

R₄ = -COO-C₁₂H₂₅

R¹, R² = -CH₂=CH-CH₂; R³, R⁴ = -CN

R¹, R² = H; R³ = -CN; R⁴ = -CO-NHC₁₂H₂₅

R¹, R² = -CH₃; R³ = -CN; R⁴ = -CO-NHC₁₂H₂₅

Examples of particularly suitable compounds are

R, R ¹ = H; R ² = -C ₄ H ₉ -t

R = H; R ¹ , R ² = -C ₄ H ₉ -t

R = H; R ¹ , R ² = -C ₅ H ₁₁ -t

R = H; R ¹ = -C ₄ H ₉ -s; R ² = -C ₄ H ₉ -t

R = Cl; R ¹ = -C ₄ H ₉ -t; R ² = -C ₄ H ₉ -s

R = Cl; R ¹ , R ² = -C ₄ H ₉ -t

R = Cl; R ¹ = -C ₄ H ₉ -t; R ² = -CH ₂ -CH ₂ -COOC ₈ H ₁₇

R = H; R = -C ₁₂ H ₂₅ -i; R ² = -CH ₃

R, R ¹ , R ² = -C ₄ H ₉ -t

R ¹ , R ² = -C ₆ H ₁₃ ; R ³ , R ⁴ = -CN

R ¹ , R ² = -C ₂ H ₅ ;

R ⁴ = -CO-OC ₈ H ₁₇

R ¹ , R ² = -C ₂ H ₅ ;

R ₄ = -COO-C ₁₂ H ₂₅

R ¹ , R ² = -CH ₂ = CH-CH ₂ ; R ³ , R ⁴ = -CN

R ¹ , R ² = H; R ³ = -CN; R ⁴ = -CO-NHC ₁₂ H ₂₅

R ¹ , R ² = -CH ₃ ; R ³ = -CN; R ⁴ = -CO-NHC ₁₂ H ₂₅

Ultraviolet absorbing couplers (such as Cyan couplers of the α-naphthol type) and ultraviolet absorbing Polymers are used. These ultraviolet absorbents can be done by pickling in a special Layer fixed.

The invention is used to produce color photographic images color photographic recording material, assigned to at least one silver halide emulsion layer a color coupler and a connection of the Formula I contains, with a color developer compound developed. Can be used as a color developer compound use all developer connections that the Have ability in the form of their oxidation product Color couplers react to azomethine dyes. Suitable Color developer compounds are aromatic at least compounds containing a primary amino group of the p-phenylenediamine type, for example N, N-dialkyl-p-phenylenediamine, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine, 1- (N-ethyl-N-3-hydroxypropyl) -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: 3100 (1951); in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff; and in German patent application P 42 41 532.2.

After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, for example Fe ³⁺ salts and Fe ³⁺ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids of corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.

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 sample 1

Layer 1:

(Substrate layer)
0.2 g gelatin

Layer 2:

(blue sensitive layer)
blue sensitive silver halide emulsion
(99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgNO ₃ with

1.38 g gelatin

0.95 g yellow coupler Y-9

0.2 g white coupler W-1

0.29 g tricresyl phosphate (CPM)

Layer 3:

(Protective layer)

1.1 g gelatin

0.06 g 2,5-dioctyl hydroquinone

0.06 g dibutyl phthalate (DBP)

Layer 4:

(green sensitive layer)
green-sensitized silver halide emulsion
(99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm)

0.45 g AgNO ₃ with

1.08 gelatin

0.38 g magenta coupler VI-1

0.08 g 2.5 dioctyl hydroquinone

0.34 g DBP

0.04 g CPM

Layer 5:

(UV layer)

1.15 g gelatin

0.6 g UV absorber UV-1

0.045 g 2.5 diocytl hydroquinone

0.04 g CPM

Layer 6:

(red sensitive layer)
red-sensitized silver halide emulsion
(99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm)

0.3 g of AgNO ₃ with

0.75 g gelatin

0.36 g C-24 cyan coupler

0.36 g CPM

Layer 7:

(UV protective layer)

0.35 g gelatin

0.15 g UV absorber UV-1

0.2 g CPM

Layer 8:

(Protective layer)

0.9 g gelatin

0.3 g hardening agent carbamoylpyridinium salt CAS Reg. 65411-60-1.

The following connection (white coupler W-1) was used in layer 2:

The following compound (UV absorber UV-1) was used in layers 5 and 7.

Samples 2 to 20

Samples 2 to 9 were made in the same manner as sample 1 produced with the difference that the layer 4 additionally 0.31 g of light stabilizer of the structural formulas VP-1 to VP-3 or light stabilizers according to the invention the structural formula I was added. Both Samples 10 to 13, 14 to 17 and 18 to 20 were the Coupler VI-1 shown in the table below Quantity replaced by other couplers of formula VI. In coupler VI-23 there was an additional 4th layer 0.34 g DBP and 0.04 g CPM through 0.38 g 2,4-di-tert-pentylphenol replaced (samples 18 to 20).

According to the invention, 0.31 g of light stabilizer of the formula I was added to the samples 11 to 12, 15 to 16 and 19 with a coupler of the formula VI. Samples 2-4, 13, 17 and 20 contained a comparison compound of one of the formulas VP-1, VP-2, VP-3.

a) Farbentwickler - 45 s - 35°C Triethanolamin 9,0 g NN-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-trisulfonsäure-trinatriumsalz 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 Die Proben wurden dem Licht einer für Tageslicht norminierten Xenonlampe ausgesetzt und mit 5,0 x 10⁶ lx'h belichtet; danach wurde die prozentuale Dichteabnahme gemessen (Tabelle 1).

The samples were then exposed behind a graduated gray wedge. The materials were then processed in the following manner using the processing baths listed below.

a) Color developer - 45 s - 35 ° C Triethanolamine 9.0 g NN-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 g 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 25% ammonia 9.5 g fill up to 1,000 ml with vinegar; pH 5.5

c) Watering - 2 min - 33 ° C. The samples were exposed to the light of a xenon lamp normalized for daylight and exposed to 5.0 x 10 ⁶ lx'h; the percentage decrease in density was then measured (Table 1).

The example shows that the compounds of formula I the light stability of the image dyes is significantly improved. As a comparison used connections VP-1 to VP-3 according to GB-A 2 135 788 cause a significantly less improvement in light stability.

Example 2

Sample 14 serves as a comparison as described under Example 1.

Samples 21 to 23 according to the invention differ from sample 14 in that in the green-sensitive layer DBP and TKP were replaced by 0.38 g of light stabilizer of the formula I. Processing and testing were carried out as described in Example 1 (Table 2).

Example 2 shows that the light stabilizers according to the invention of formula I as an oil generator in combination with Pyrazoloazole couplers can be used. Sensitivity, Gradation and maximum density are comparable with DBP / TKP, the light stability is significantly increased.

Example 3

In this example, the advantages of the invention Measures shown in a color reversal film.

Color photographic recording materials for the Reverse processing was made by clicking on a with an adhesive layer Cellulose triacetate sequentially listed below Layers are applied.

The quantities given relate to 1 m ² .

Sample 24 (comparison)

Layer 1

(Antihalation layer)
black colloidal silver sol with

0.25 g Ag

1.60 g gelatin

0.24 g UV absorber UV-2

Layer 2

(Intermediate layer)
0.64 g gelatin

Layer 3

(1st red-sensitized layer)
red-sensitized silver bromoiodide emulsion
(25 mol% iodide; average grain diameter 0.25 µm)

from 0.60 g AgNO ₃ , with

0.59 g gelatin

0.24 g cyan coupler C-25

0.12 g CPM

Layer 4

(2nd red-sensitized layer)
red-sensitized silver bromoiodide emulsion
(3.0 mol% iodide; average grain diameter 0.43 µm)

from 0.95 g AgNO ₃ , with

1.96 g gelatin

0.95 g cyan coupler C-25

0.48 g CPM

Layer 5

(Intermediate layer)

1.78 g gelatin

0.24 g of compound A

0.12 g CPM

Layer 6

(1st green-sensitized layer)
Mixture 3: 1 from a silver bromide iodide emulsion
(1.0 mol% iodide; average grain diameter 0.26 µm)
and a silver bromoiodide emulsion
(4.0 mol% iodide; average grain diameter 0.21 µm) both green-sensitized,

from 0.67 g AgNO ₃ , with

1.13 g gelatin

0.22 g magenta coupler VI-7

0.10 g CPM

Layer 7

(2nd green sensitive layer)
green-sensitized silver bromoiodide emulsion
(1.5 mol% iodide;
average grain diameter 0.42 µm)

from 1.05 g AgNO ₃ , with

2.72 g gelatin

1.00 g magenta coupler VI-7

0.45 g CPM

Layer 8

(Intermediate layer)

0.55 g gelatin

0.10 g of compound A

Layer 9

(Yellow filter layer)
yellow colloidal silver sol with

0 11 g Ag,

0.45 g gelatin

Layer 10

(Intermediate layer)
0.71 g gelatin

Layer 11

(1st blue sensitive layer)
blue-sensitized silver bromoiodide emulsion
(4.0 mol% iodide; average grain diameter 0.28 µm)

from 0.58 g AgNO ₃ , with

1.31 g gelatin

0.24 g yellow coupler Y-19

0.12 g CPM

Layer 12

(2nd blue sensitive layer)
blue-sensitized silver bromide iodide emulsion (3.0 mol% iodide;
average grain diameter 0.66 µm)

from 0.66 g AgNO ₃ , with

2.04 g gelatin

0.83 g yellow coupler Y-19

0.41 g CPM

Layer 13

(Intermediate layer)

0.76 g gelatin

0.54 g of compound A

0.50 g UV absorber UV-1

0.02 g CPM

Layer 14

(Protective layer)
Mikrat-silver bromide iodide emulsion
(4.0 mol% iodide;
average grain diameter 0.15 µm)

from 0.20 g AgNO ₃ with

0.57 g gelatin

Layer 15

Hardening layer

0.25 g gelatin

0.87 g hardening agent carbamoylpyridinium salt CAS Reg.No. 65411-60-1

In Example 3, the following compounds are used in addition to the compounds already mentioned:

Samples 25 to 30

Samples 25 and 26 according to the invention were in the manufactured in the same way as the sample 24 with the Difference that the oil generator TKP in layers 6 and 7 replaced by compounds I-14 and I-17 has been. In sample 27, coupler VI-7 was replaced by the Coupler VI-14 replaced, TKP (comparison) served as oil generator.

The samples 28 to 30 according to the invention differ differs from sample 27 in that CPM in the layers 6 and 7 replaced by compounds I-4, I-14 and I-17 has been.

The samples prepared in this way were behind exposed a step wedge and a color reversal development subjected as described in "Manual for PROCESSING Kodak Ektrachrome Film using Process E7 ", Eastman Kodak Company, 1977 (see Kodak publication Z-119).

The light stability test was carried out as described in Example 1, but exposure was carried out at 7.5 · 10 ⁶ lux.h. The results are summarized in Table 3.

The example shows that the inventive Compounds of the formulas I the light stability of the Image dyes in color reversal films increased significantly could be. Sensitivity, gradation and maximum density were not adversely affected.

Example 4

A suitable one for a rapid processing process color photographic material was prepared as in example 1, sample 1, with the difference that in layer 4 instead of magenta coupler VI-1 the Magenta coupler VI-6 in an amount of 0.41 g and instead of the oil-forming mixture only 0.38 g CPM were used (sample 31).

Verarbeitung, Bestrahlung und Auswertung der Proben erfolgte wie in Beispiel 1, mit dem Unterschied, daß mit 10.10⁶ luxh bestrahlt wurde. Die Ergebnisse sind aus Tabelle 4 ersichtlich.

Sample 32-52 was produced in the same way as sample 31, with the difference that the light stabilizers VP-1, VP-3, VP-4 or light stabilizers according to the invention, which are given in table 1, were additionally added to layer 4.

Processing, irradiation and evaluation of the samples were carried out as in Example 1, with the difference that 6.10 ⁶ was irradiated with 10.10. The results are shown in Table 4.

Example 4 shows that by using light stabilizers Formula I improves light stability can be (samples 33, 34, 35, 38) and that by Compounds of formula I achieved light stability can be further improved if the connections of the formula I in combination with compounds of the formulas II, III, IV and V can be used (samples 39-52).

Example 5

Sample 31 from Example 4 serves as a comparison.

Samples 53-59

Samples 53-59 are made in the same way like sample 31 from example 4, with the difference that the oil former in layer 4 by the invention Compounds of formula I is replaced and other compounds one of the formulas II, III, IV and V or the Comparative compound VP-3 can be added.

Processing and testing were carried out as described in Example 1. In addition, the sensitivity, gradation and maximum density were determined for the processed samples before irradiation. The results are summarized in Table 5.

Example 5 shows that the light stabilizers according to the invention Formula I also the function of a Oil can take over without being disadvantageous Effects on sensitivity, gradation and Maximum density can be observed. The light stability is due to the combination according to the invention with compounds of the formula II, III, IV or V again clearly elevated. For comparison link VP-3 is here significantly less effective.

Example 6 Sample 60

Schicht 1:

Eine Substratschicht aus 200 mg Gelatine mit KNO₃- und Chromalaunzusatz.

Schicht 2:

Eine Haftschicht aus 320 mg Gelatine.

Schicht 3:

Eine grünempfindliche Silberbromidchloridemulsionsschicht (20 mol-% Chlorid) aus

530 mg AgNO₃ mit 750 mg Gelatine,

0,57 g Magentakuppler VI-1, emulgiert mit

0,51 g TKP

Schicht 4:

Eine Schutzschicht aus 1 g Gelatine und 16 mg eines Netzmittels der Formel C₈F₁₇ SO₃ ^⊖ N(C₂H₅)₄)₄ ^⊖ Auf diese Schicht trägt man eine Härtungsschicht auf, die als Härtungsmittel 120 mg Carbamoylpyridiniumsalz CAS Reg. No. 65411-60-1 enthält.

A layer support made of paper coated on both sides with polyethylene was provided with the following layers. The quantities given relate to 1 m ² .

Layer 1:

A substrate layer made of 200 mg gelatin with addition of KNO ₃ and chrome alum.

Layer 2:

An adhesive layer made of 320 mg gelatin.

Layer 3:

A green sensitive silver bromide chloride emulsion layer (20 mol% chloride)

530 mg AgNO ₃ with 750 mg gelatin,

0.57 g magenta coupler VI-1, emulsified with

0.51 g CPM

Layer 4:

A protective layer of 1 g of gelatin and 16 mg of a wetting agent of the formula C ₈ F ₁₇ SO ₃ ^⊖ N (C ₂ H ₅ ) ₄ ) ₄ ^⊖ A hardening layer is applied to this layer which contains 120 mg carbamoylpyridinium salt CAS Reg. 65411-60-1 contains.

Samples 61-72

Samples 61-72 were made in the same manner like sample 60 with the difference that the layer 3 the added light stabilizers listed in Table 6 were. Samples 65-72 also became the magenta coupler VI-1 by those given in Table 6 (VI-5, VI-23) replaced.

The samples obtained were then exposed behind a graduated gray wedge. The materials were then processed in the following manner using the processing baths listed below: development 210 s, 33 ° C bleaching 50 s, 20 ° C Fix 60 s, 20 ° C Water 120 s, 20 ° C Dry. Composition of the bathrooms developer Benzyl alcohol 13 ml Hydroxylammonium sulfate 3 g Sodium sulfite 2 g 4-amino-N-ethyl-N (β-methanesulfonamidoethyl) -m-toloidin-sesquisulfate (monohydrate) 4.5 g Potassium carbonate 36 g Potassium bromide 1.4 g Diethylene triamino pentaacetic acid, pentasodium salt 2 g Diethylene glycol 12 ml Fill up with water to 1 liter pH = 10.4 Bleach bath water 700 ml NH ₄ -Fe-EDTA 65 g EDTA 10 g MMH ₄ Br 100 g adjust to pH 6.0 with acetic acid, make up to 1 1 with water Fixer Ammonium thiosulfate 100 g Na sulfite, sicc. 10 g Na disulfite 3 g fill up to 1 liter with water.

In addition, the samples were exposed to the light of a xenon lamp normalized for daylight and exposed to 7.2 x 10 ⁶ lx.h; the percentage decrease in density was then measured (Table 6).

Example 6 shows the improvement in light stability by using compounds of formula I. (Samples 61, 66, 70) and the increased effectiveness again when combined with connections one of the Formulas II, III, IV and V as light stabilizers. As Comparison of compounds used VP-1, VP-3 and VP-4 are significantly less effective.

Claims (12)

1. Colour photographic recording material having at least one red-sensitive silver halide emulsion layer, which is associated with a cyan coupler, at least one green-sensitive silver halide emulsion layer, which is associated with a magenta coupler, and at least one blue-sensitive silver halide emulsion layer, which is associated with a yellow coupler, which contains a hydroquinone diether compound in at least one of the layers thereof, characterised in that the hydroquinone diether compound is a compound of the formula I with the exception of compounds of the formula IA and that at least one of the silver halide emulsion layers present is associated with a compound of the formula I with the exception of compounds of the formula IA in combination with a colour coupler:

   

   

   in which

   R¹

   means alkyl, cycloalkyl, aryl;

   R²

   means H, alkyl;

   R³, R⁴

   mean H, alkyl, cycloalkyl, halogen, alkoxy, aroxy, acyloxy, alkylthio, arylthio, acyl, sulphonyl, sulphamoyl, acylamino, sulphonylamino, nitro;

   R⁵

   means H, acyl, alkyl,

   X

   means -O- or -NR⁶-;

   R⁶

   means H or alkyl;

   n

   means 0 or an integer from 1 to 3.

2. Recording material according to claim 1, characterised in that at least one of the residues R³ and R⁴ in the formula I demotes tertiary alkyl.
3. Recording material according to one of claims 1 and 2, characterised in that the residue -X-R⁵ in the formula I denotes -OH, -O-CH₂-CH₂-OH or -O-acyl, wherein the acyl residue is derived from an aliphatic or aromatic carboxylic acid, a carbamic acid, a carbonic acid monoester or from phosphorous acid.
4. Recording material according to one of claims 1 to 3, characterised in that the index n in the formula I denotes 0 or 1.
5. Recording materieal according to one of claims 1 to 4, characzerised in that in contains in combination with a hydroquinone diether compound of the formula I at least one compound of one of the formulae II, III, IV and V

   

   in which

   R²¹ , R²²

   mean residues as R⁵;

   R²³, R²⁴ R²⁵

   mean residues as R³;

   A

   means a single bond, -S(=O)_m-, alkylene or -NR²⁶-;

   R²⁶

   means alkyl or acyl;

   m

   means 0, 1 or 2;

   

   in which

   R³¹, R³²

   mean alkyl, cycloalkyl;

   R³³, R³⁴

   mean residues as R³;

   

   in which

   R⁴¹, R⁴²

   mean residues as R⁵;

   R⁴³, R⁴⁴, R⁴⁵, R⁴⁶

   mean residues as R³; providing that at least one of the residues R⁴⁴ and R⁴⁵ does not mean alkyl;

   

   in which

   R⁵¹

   means alkyl, cycloalkyl, aryl;

   R⁵², R⁵³, R⁵⁴, R⁵⁵

   mean residues as R³;

   p

   means 0, 1 or 2.

6. Recording material according to claim 5, characterised in that in the formula II A denotes alkylene and R²¹ and R²² denote H.
7. Recording material according to claim 5, characterised in that in the formula III at least one of the residues R³³ and R³⁴ denotes alkyl.
8. Recording material according to claim 5, characterised in that in the formula IV at least one of the residues R⁴³ and R⁴⁶ and/or at least one of the residues R⁴⁴ and R⁴⁵ denote H.
9. Recording material according to claim 5, characterised in that in the formula V R⁵⁴ and R⁵⁵ denote H.
10. Recording material acccrding to one of claims 1 to 9, characterised in that at least one green-sensitive silver halide emulsion layer is associated with a compound of the formula I in combination with a magenta coupler of the formula VI,

    

    wherein in the formula VI

    R⁶¹

    means H, alkyl, aralkyl or aryl;

    Y

    means H or a group releasable by coupling;

    Z_a, Z_b, Z_c

    mean an optionally substituted methine group, =N- or -NH-, wherein either the bond Z_a-Z_b or the bond Z_b-Z_c is a double bond and the other bond is a single bond.

11. Recording material according to claim 10, characterised in that the magenta coupler is of one of the formulae VId and VIe

    

    in which R⁶¹ denotes H, alkyl, aralkyl or aryl, and S and T denote hydrogen, alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl carbamoyl or sulphamoyl,
    wherein at least one of the residues R⁶¹ and S (in the formula VId) or at least one of the residues R⁶¹ and T (in the formula VIe) means a secondary alkyl or tertiary alkyl residue, and in which Y denotes hydrogen or a residue eliminable on colour coupling.
12. Recording material according to claim 10, characterised in that the compound of the formula I or the combination of a compound of the formula I with at least one compound of one of the formulae II, III, IV and V is present in the green-sensitive silver halide emulsion layer in 0.2 to 2 times the quantity by weight, relative to the magenta coupler of the formula VI.