DE4038965A1 - Colour photographic recording materials giving enhanced light stability and colour purity - having at least one non-diffused pyrazolo-azole type colour coupler - Google Patents

Abstract

In colour photographic recording materials with at least one Ag halide emulsion layer on a layer carrier and at least one non-diffused pyrazolo-azole colour coupler, the coupler is of formula (I). In (I), PAZ is the colour coupling gp. of the pyrazolo-azole-type colour coupling range; L is a bonding gp. bound to the non-coupled part of PAZ; R1 is alkyl, cycloalkyl or aryl, R2 is alkyl or aryl and t is 1 or 2. - Pref. the gp. PAZ is a pyrazolo(3,2-c) -1,2,4-triazole-, pyrazole(2,3-b)- 1,2,4-triazole, or pyrazolo(2,3-d)-tetrazole gp.. Pref. the recording material contains a colour coupler of formula (II)-(IV), where X is H or a gp. cleavable by colour coupling; R3, S, T and H is alkyl, aralky, aryl, alkoxycarbonyl, carbamoyl or sulphamoyl where at least one of R3, S and T is a gp. of formula (V); L is a bonding gp. of formula -L1-(L2)l-(L3)m-(L4)n -(L5)o-(L6)p-(L7)q-; L1, L3, L5 and L7 is alkylene, aralkylene or arylene; L2, L4 and L6 = -O-, -NH-, -NHCO-, -CONH, -NHSO2-, -SO2NH- or -SO2-; l, m, n, o, p and q = 0 or 1, and l-m+n-o+p-q = 0.

Description

The invention relates to a color photographic recording material with at least one silver halide emulsion layer and a color coupler of the pyrazoloazole type, due to the presence of a special group the production of magenta dye formers with improved Light stability allows.

It is known to go through colored photographic images to produce chromogenic development, d. H. in that one imagewise exposed silver halide emulsion layers in Presence of suitable color couplers by means of suitable color-forming Developer substances - so-called color developer - developed in accordance with the Silver image resulting oxidation product of the developer substances with the color coupler to form a dye image responding. As color developers become ordinary aromatic compounds containing primary amino groups, especially those of the p-phenylenediamine type, used.  

For the preparation of magenta dye images are üb It is also possible to use pyrazolone couplers. The from these Have pyrazolone couplers obtained image dyes often not ideal absorption. Especially disturbing is the yellow secondary color density, which is to achieve of brilliant colors in the photographic image the Use of mask couplers or the use of others Masking techniques required. A certain improvement in this regard could by the use be achieved by 3-Anilinopyrazolonkupplern. The color reproduction but still leaves much to be desired.

As particularly advantageous in this regard have become Magenta couplers of pyrazoloazole type proved. they deliver usually color cleaner magenta dye images. Mangetakuppler of this type are described for example in DE-A-18 10 462, DE-A-35 16 996, EP-A-01 43 570, EP-A-01 76 804. A disadvantage of the magenta couplers of Pyrazoloazole type is that the manganese dyes produced from them often not sufficiently stable are the action of light.

The invention is based on the object of a color photographic Recording material with at least one Silver halide emulsion layer and at least one Indicate magenta coupler from which by chromogenic development Magenta dyes with desired color purity and improved light stability can be generated.

The invention is a color photographic Auf Drawing material with at least one silver halide  emulsion layer and at least one non-diffusing Color couplers of the pyrazoloazole type, characterized in that the coupler is the following corresponds to general formula I.

in which mean
PAZ the group capable of color coupling of a color coupler of the pyrazoloazole series;
L is a link attached to a noncoupling position of PAZ;
R¹ is alkyl, cycloalkyl or aryl;
R² is alkyl or aryl;
t 1 or 2.

The alkyl and aryl radicals represented by R¹ or R² may be unsubstituted or substituted. A through R¹ represented alkyl radical can be straight-chain or branched be and contain, for example, up to 18 carbon atoms. Suitable substituents are, for example, OH, alkoxy, Aryl. A cycloalkyl group represented by R¹  is, for example, cyclopentyl or cyclohexyl. On For example, aryl represented by R¹ or R² is Phenyl. An alkyl radical represented by R² for example, 1 to 6 C atoms, a preferred one Example is tertiary butyl.

Couplers of the formula I which contain only one radical R² (t = 1) are preferred. R 2 is preferably a ter tiärbutylgruppe in the 2- or 3-position.

The coupling residual PAZ can stand for a remainder 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 represented below by the formulas I-1 to I-7 indicated.

In the general formulas I-1 to I-7, the substituents R³, S, T and U are hydrogen, alkyl, Aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, Amino, anilino, acylamino, cyano, alkoxycarbonyl, Carbamoyl, sulfamoyl, where these radicals are further substituted and wherein, however, in each of the formulas I-1 to I-7 at least one of the radicals R³, S, T and U for a group of the formula

stands, as defined in formula I. Furthermore, X is hydrogen or a cleavable with color coupling remainder such as a halogen atom or an oxygen atom Sulfur atom or a nitrogen atom to the coupling Site attached preferably cyclic group.

If the cleavable group is a cyclic group, the link to the Clutch point of Kupplermoleküls either directly over  an atom that is part of a ring, eg. B. a Nitrogen atom, or indirectly via an intermediate Link has been made. Such detachable Groups are known in large numbers, eg. B. as escape groups of 2-equivalent magenta couplers.

Examples of oxygen cleavable cleavable Groups correspond to the formula

-O-R⁴,

wherein R⁴ is an acyclic or cyclic organic Rest stands, z. As for alkyl, aryl, a heterocyclic Group or acyl, which derives, for example, from an organic carboxylic or sulfonic acid. Especially preferred cleavable groups of this type means R⁴ an optionally substituted phenyl group.

Examples of oxygen cleavable cleavable Groups are in the following German Offenlegungsschriften (DE-A-) described:

25 36 191, 27 03 589, 28 13 522, 33 39 201.

These are often 5-membered heterocyclic Rings containing a ring nitrogen atom with the Clutch point of the purple coupler are connected. The heterocyclic rings often contain adjacent to the nitrogen atom linking the coupler molecule activating groups, e.g. B. carbonyl or sulfonyl groups or double bonds.  

When the leaving group is attached via a sulfur atom to the Coupling point of the coupler is bound, it may be in it around the remainder of a diffusible carbocyclic or heterocyclic mercapto compound, which inhibit the development of silver halide can. Such inhibitor residues are more common than to the Coupling point of couplers, also bound to magenta couplers cleavable group has been described, for. In US-A-32 27 554.

The non-cleavable bound to a non-coupling position Link -L- can be a compound Structure and, for example, as shown below become:

-L¹- (L²) ₁- (L³) _m - (L⁴) _n - (L⁵) _o - (L⁶) _p - (L⁷) _q -

in which L¹ denotes the part of the linking group which is first of the group PAZ and L⁷ that of the hydroquinone ether group, and in which (identical or different) mean:
L¹, L³, L⁵, L⁷ alkylene, aralkylene, arylene;
L², L⁴, L⁶ -O-, -NH-, NHCO-, -CONH-, -NHSO₂-, -SO₂NH-, -SO₂-;
l, m, n, o, p, q are each 0 or 1, where 1 - m + n - o + p - q = 0.

An alkylene group represented by L¹, L³, L⁵, L⁷ may be straight-chain or branched and up to 20 ° C atoms respectively.

An aralkylene group represented by L¹, L³, L⁵, L⁷ is one of the following groups, for example:

An arylene group represented by L¹, L³, L⁵, L⁷ preferably a phenylene group which may be substituted can, for. B. with alkyl, hydroxy, alkoxy, halogen, acylamino.

The non-cleavable link -L- preferably contains a ballast rest, extending through the whole the partial binder L¹ to L⁷ results or for example in that one of the subbonding members L¹, L³, L⁵ and L⁷ a ballast in the form of a branch or in the form of a substituent. For example an alkylene radical may be a 1,2-alkylene radical or an alkylidene radical with up to 20 carbon atoms, or an arylene radical may be substituted, for. B. with an alkoxy group or an acylamino group, wherein the alkoxy group of the  the acylamino group up to 20 carbon atoms and / or optionally contains further substituents.

As Ballastreste are to be considered such remnants, which make it possible the magenta couplers according to the invention in the usually in photographic recording materials used hydrophilic colloids resistant to diffusion store. These are preferably organic radicals suitable, which are generally straight-chain or branched aliphatic groups with generally 8 to 20 C atoms and optionally also carbocyclic or heterocyclic optionally contain aromatic groups. With the remaining part of the molecule are the radicals either directly or indirectly, e.g. B. via one of the following Groups connected: -NHCO-, -NHSO₂-, -NR-, where R is hydrogen or alkyl, -O- or -S-. Possibly can such a ballast also in addition contain water-solubilizing groups, such as. Hy droxygruppen or carboxyl groups, which are also in anionic Form can be present. Because the diffusion resistance of the molecule size or total compound used depends in certain cases, even if the total molecule used several short-chain residues Contains as Ballastrest. The inventively used Ballast residues preferably have a molecular weight of less than 1000.

The magenta couplers according to the invention can have a Ballastrest not having the group  

is identical. Such a ballast can damage the structure Have -L'-H, wherein L 'is defined in the same way like L.

For example, for pyrozoloazole couplers according to the invention, the following are indicated:

The synthesis of the different pyrazolotriazoles can be up done in a variety of ways; reference is made to this on:

z. BJ Bailey: Journ. Chem. Soc. Perk. I, 2047 EP-A-02 84 240;
Research Disclosure 12,443, August 1974
HGO Becker u. H. Böttcher: Journ. f. Prakt. Chemistry, 314, (1) 55 to 65 (1972)
EP-A-02 00 354, EP-A-01 78 788, EP-A-02 84 240;
J. Het. Chem. 16, 195 (1979) EP-A-01 19 860.

The pyrazoloazole ring system can be synthesized, for example, as follows:

Synthesis of coupler M-4

0.1 mol of 7-chloro-6-methyl-3- (p-amino-phenyl-propyl) -1-H-pyrazolo [3,2-c] -s-triazole (according to EP-A 00 73 636 Preparative Example 9, (S 31 and 32) are in
Dissolved 200 ml of dioxane and treated with a solution of 4 g of NaOH in 20 ml of water.

Then be
0.1 mol of α - [(3-t-butyl-4-acetoxyethoxy) phenoxy] - myristic acid chloride in
50 ml dioxane slowly added dropwise.

It is stirred for 30 min at room temperature, in
2 l ice / water stirred in and with
Shaken out 200 ml of ethyl acetate.

After washing with water, drying over Na₂SO₄ and Distilling off the solvent gives a residue which melts after recrystallization at 85 ° C.

This residue is mixed with
200 ml of methanol
30 ml of water and
30 ml conc. Sodium hydroxide solution and heated for a short time at 50 ° C. After complete reaction (control by thin layer chromatography) is stirred in ice / HCl and taken up with a little ethyl acetate. After addition of the same amount of petroleum ether crystallize overnight in the refrigerator 67 g M-4, mp. 155 ° C.

Synthesis of coupler M-21

0.1 mol of coupler 59 according to EP-A-01 19 860 are in
Presented dissolved 200 ml of dioxane and treated with a solution of 4 g of NaOH in 200 ml of water.

Then be
0.1 mol of α - [(3-t-butyl-4-acetoxyethoxy) phenoxy] - myristic acid chloride in
50 ml dioxane slowly added dropwise.

It is stirred for 30 min at room temperature, in
2 l ice / water stirred in and with
Shaken out 200 ml of ethyl acetate.

After washing with water, drying over Na₂SO₄ and Distilling off the solvent remains a tough Oil.

This residue was in
200 ml of methanol dissolved with
40 ml of 2N sodium hydroxide added and stirred at 40 ° C for 15 min.

It is then stirred in ice / HCl and washed with 200 ml of ethyl acetate.

After evaporation of the solvent, the residue from ether / petroleum ether (1: 1) recrystallized.

Yield: 56.8 g
Mp 96-98 ° C

Examples of color photographic materials are in particular Color negative films, color reversal films and color photographic Papers.

Suitable carriers for the production of color photographic materials are z. B. films and films of semi-synthetic and synthetic polymers, such as cellulose nitrate,  Cellulose acetate, cellulose butyrate, polystyrene, poly vinyl chloride, polyethylene terephthalate and polycarbonate and with a barite layer or α-olefin polymer layer (eg polyethylene) laminated paper. These carriers can with dyes and pigments, for example titanium dioxide, be colored. The surface of the carrier becomes generally subjected to a treatment to the adhesion to improve the photographic emulsion layer, for example, a corona discharge followed by Application of a substrate layer.

The color photographic materials usually contain at least one red-sensitive, green-sensitive one and blue-sensitive silver halide emulsion layer and optionally intermediate layers and Protective layers.

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

The binder used is preferably gelatin. However, this can be done in whole or in part by others synthetic, semi-synthetic or naturally occurring Be replaced polymers. Synthetic gelatin Substitutes are, for example, polyvinyl alcohol, poly- N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are for example other proteins such as albumin or casein,  Cellulose, sugar, starch or alginates. semi-synthetic Gelatine substitutes are usually modified Natural products, cellulose derivatives such as hydroxy alkylcellulose, carboxymethylcellulose and phthalylcellulose and gelatin derivatives obtained by reaction with alkylating or acylating agents or by Grafting of polymerizable monomers obtained are examples of this.

The binders should be over a sufficient amount functional groups, so that by implementation sufficiently resistant with suitable curing agents Layers can be generated. Such functional Groups are especially amino groups, but also Carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin preferably used can be acidic or alkaline digestion. It can also oxidized gelatin can be used. The production Such gelatins are described, for example, in The Science and Technology of Gelatine, edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 et seq. The gelatine used should be as possible low content of photographically active impurities contained (inert gelatin). Gelatins with high viscosity and low swelling are special advantageous.

As the photosensitive component in the photographic Material located silver halide can as  Halide chloride, bromide or iodide or mixtures included. For example, the halide content at least one layer to 0 to 15 mol% of iodide, to 0 to 100 mol% of chloride and to 0 to 100 ml-% consist of bromide. In the case of color negative and color reversal films are usually silver bromide iodide emulsions, in the case of color negative and color reversal paper usually high chloride silver chloride bromide emulsions Chloride content used to pure silver chloride emulsions. It can be mostly compact crystals act, the z. B. are regular cubic or octahedral or transitional forms. Preferably but it is also possible for platelet-shaped crystals to be present, their average ratio of diameter to Thickness is preferably at least 5: 1, wherein the diameter a grain is defined as the diameter of a grain Circle with a circle content corresponding to the projected Area of the grain. But the layers can also have tabular silver halide crystals, where the ratio of diameter to thickness is significantly greater than 5: 1, z. From 12: 1 to 30: 1.

The silver halide grains may 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. B. doping of the individual Grain areas are different. The middle Grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the particle size distribution can be both  homo- as well as heterodisperse. Homodisperse grain Size distribution means that 95% of the grains do not more than ± 30% deviate from the mean grain size. The emulsions may be in addition to the silver halide contain organic silver salts, for. B. silver benzotriazolate or silver behenate.

There can be two or more types of silver halide emulsions, which are prepared separately, as a mixture be used.

The emulsions can be chemically mixed in the usual way or spectrally sensitized and the emulsion layers as well as other non-photosensitive Layers can be known in the usual way Curing agents, in particular with carboxyl groups activating hardeners such as carbamoylpyridinium salts (eg according to DE-A-22 25 230, DE-A-23 17 677, DE-A-24 39 551), be cured.

Usually contain color photographic silver halo at least one silver halide emulsion layer for the recording of light each of the three spectral ranges red, green and blue. To this Purpose, the photographic emulsions using of methine dyes or other dyes spectrally sensitized. Particularly suitable Dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.  

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

In particular, the following dyes - are ordered according to spectral regions - suitable:

• 1. as red sensitizers
  9-ethylcarbocyanines with benthiaziol, benzselenazole or naphtholtiazole as basic end groups, which may be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethyl-naphtoxathia or -selenacarbocyanine and 9- Ethyl-napthothiaoxa and -benz imidazocarbocyanines, respectively, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers
  9-Ethylcarbocyanine with benzoxazole, naphthoxazole or a benzoxazole and a benzothiazole as basic end groups and benzimidazocarbocyanines, which may also be further substituted and must also contain at least one sulfoalkyl group on heterocyclic nitrogen.
• 3. as blue sensitizers
  symmetrical or asymmetric benzimidazo, oxa, thia or selenacyanines having at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and also apomerocyanines having a rhodanine group.

From sensitisers can be waived, if for a certain spectral range the intrinsic sensitivity of the silver halide is sufficient, for example the blue sensitivity of silver bromides.

The differently sensitized emulsion layers become non-diffusing monomeric or polymeric color couplers assigned, which are in the same layer or in a layer adjacent thereto. Usually the red-sensitive layers become cyan couplers, the green-sensitive layers magenta coupler and associated with the blue-sensitive layers yellow couplers.

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

For generating the purple partial color image contains the Recording material of the present invention at least a magenta coupler of formula (I), e.g. B. a Magenta coupler of formula M-1 to M-63.

Color coupler for producing the yellow partial color image are usually couplers with an open-chain keto methylene moiety, especially couplers of the type α-Acylactamids; suitable examples of this are α- Benzoylacetanilide couplers and α-pivaloylacetanilide couplers the formulas  

The color couplers may be 4-equivalent couplers, but also act around 2-equivalent couplers. Latter derive from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off at the clutch. To the 2 Equivalent couplers are those that are colorless are, as well as those that have an intense intrinsic color have, which disappears in the color coupling or replaced by the color of the generated image dye is (mask coupler), and the white couplers, the reaction with color developer oxidation products substantially give colorless products. To the 2-equivalent couplers Furthermore, such couplers are to be expected, which in the Clutch point contain a cleavable residue, the upon reaction with color developer oxidation products in Freedom is set and thereby either directly or after the primary split-off remainder one or several further groups have been split off (eg DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A- 33 19 428), a particular desired photographic Effectiveness unfolded, z. B. as a development inhibitor or -accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR- or FAR couplers.  

Examples of white couplers are:

Examples of mask couplers are:

DIR couplers, the azole-type development inhibitors, z. B. release triazoles and benzotriazoles are in DE A-24 14 006, 236 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416 described. Other advantages for color rendering, d. H. color separation and color purity, and for detail reproduction, d. H. Sharpness and graininess, are associated with such DIR To achieve couplers z. B. the development inhibitor not directly as a result of the coupling with a split off oxidized color developer, but only after a further follow-up action, for example, with a timing group is reached. Examples of this are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-01 57 146 and 02 04 175, in US-A- 41 46 396 and 44 38 393 and in GB-A-20 72 363.  

DIR couplers which release a development inhibitor, in the developer bath to essentially photographic ineffective Product is decomposed, for example in DE-A-32 09 486 and in EP-A-01 67 168 and 02 19 713 described. With this measure, a trouble-free Development and processing consistency achieved.

When using DIR couplers, in particular those, the a well diffusible development inhibitor split off, can be by appropriate measures the optical sensitization color rendering improvement, z. B. a more differentiated color rendering, achieve, for example, in EP-A-01 15 304, 01 67 173, GB-A-21 65 058, DE-A-37 00 419 and US Pat. 47 07 436 described.

The DIR couplers can be used in a multilayer photographic Material added to various layers be, for. B. light-insensitive or intermediate layers. Preferably, however, they are the photosensitive silver halide emulsion layers added, with the characteristic properties the silver halide emulsion, e.g. B. their iodide content, the Structure of silver halide grains or their grains Size distribution of influence on the obtained photographic Properties are. The influence of the released Inhibitors, for example, by incorporation an inhibitor scavenger layer according to DE-A-24 31 223 limited become. For reasons of reactivity or stability it may be advantageous to use a DIR coupler,  the one in each layer in which he is placed is one of those to be generated in this layer Color deviating color forms at the coupling.

To increase the sensitivity, the contrast and DAR or FAR Couplers are used which are a development accelerator or split off a haze. links of this kind are described for example in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-00 89 834, 01 10 511, 01 18 87, 01 47 765 and in US-A-46 18 572 and 46 56 123.

As an example of the use of BAR couplers (Bleach Accelerator Releasing Coupler) is assigned to EP-A-1 93 389 directed.

It can be beneficial to the effect of one out of a Coupler cleaved photographic effective group by modifying that an intermolecular reaction this group after its release with a another group according to DE-A-35 06 805 occurs.  

Examples of DIR couplers are:

Examples of DAR couplers:

Since the DIR, DAR and FAR couplers mainly the effectiveness of the released in the coupling Restes is desired and it is less on the color-forming Properties of these couplers arrives, are also such DIR, DAR or FAR coupler suitable in the Coupling substantially colorless products (DE- A-15 47 640).

The cleavable residue may also be a ballast residue, so that in the reaction with color developer oxidation products Coupling products are obtained which are diffusible are or at least weak or restricted Have mobility (US-A-44 20 556).  

The material can also be different from couplers Contain connections, for example, a Ent development inhibitor, a development accelerator, a bleach accelerator, a developer, a sil halide solvent, a fog or a Antifoggants can be set free, for example so-called DIR-hydroquinones and other compounds, as described, for example, in US-A-46 36 546, 43 45 024, 46 84 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-1 98 438 are described. These Connections perform the same function as the DIR, DAR or FAR couplers, except that they are not coupling products form.

High molecular color couplers are described, for example, in DE-C- 12 97 417, 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-40 80 211 described. The high molecular color couplers are in usually by polymerization of ethylenically unsaturated produced monomeric color couplers. You can but also obtained by polyaddition or polycondensation become.

The incorporation of the couplers or other compounds in silver halide emulsion layers can in the way be done first by the relevant connection prepared a solution, a dispersion or an emulsion and then the casting solution for that particular Layer is added. The selection of the appropriate  Solvent or dispersant depends on the particular Solubility of the compound.

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

Hydrophobic compounds can be made using high-boiling solvents, so-called oil formers, be introduced into the casting solution. Appropriate methods are described, for example, in US Pat. No. 2,322,027, US Pat. 28 01 170, US-A-28 01 171 and EP-A-00 43 037. Suitable oil formers for the magenta couplers according to the invention are described for example in DE-A-39 18 547.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers use Find.

The compounds may also be in the form of loaded latices be introduced into the casting solution. Is referred For example, DE-A-25 41 230, DE-A-25 41 274, DE-A- 28 35 856, EP-A-00 14 921, EP-A-00 69 671, EP-A- 01 30 115, US-A-42 91 113.

The diffusion-resistant inclusion of anionic water-soluble Compounds (eg of dyes) can also be used with Help of cationic polymers, so-called pickling made of polymers.  

Suitable oil formers are z. Phthalic acid alkyl ester, Phosphoric acid ester, phosphoric acid ester, citric acid ester, Benzoic acid esters, amides, fatty acid esters, trimes säureester, alcohols, phenols, aniline derivatives and Hydrocarbons.

Examples of suitable oil formers are dibutyl phthalate, Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Triphenyl phosphate, tricresyl phosphate, 2-ethyl hexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2- ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphe nylphosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2- Ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N- Tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t- amylphenol, dioctylacelate, glycerol tributyrate, iso stearyl lactate, trioctyl citrate, N, N-dibutyl-2-butoxy-5- t-octylaniline, paraffin, dodecylbenzene and diiso propylnaphthalene.

Each of the differently sensitized, photosensitive Layers can consist of a single layer or two or more silver halide emulsions partial layers include (DE-C-11 21 470). There are red-sensitive silver halide emulsion layers Layer support often arranged closer than green sensitive Silver halide emulsion layers and these in turn closer than blue sensitive, being in the general between green-sensitive layers and blue-sensitive layers a non-photosensitive yellow filter layer is located.  

With suitably low intrinsic sensitivity of the green or red-sensitive layers can be waived on the yellow filter layer other layer arrangements choose in which the carrier z. B. the blue-sensitive, then the red-sensitive and finally the günempfindlichen layers follow.

The usually between layers of different Spectral sensitivity arranged non-photosensitive Interlayers may contain agents the unwanted diffusion of developer Oxidation products from a photosensitive to a other photosensitive layer with different prevent spectral sensitization.

Suitable agents that include scavengers or EOP scavengers are referred to in Research Disclosure 17 643 (Dec., 1978), Chapter VII, 17,842 (Feb. 1979) and 18,716 (Nov. 1979), page 650 as well as in EP-A-00 69 070, 00 98 072, 01 24 877, 01 25 522 described.

Examples of particularly suitable compounds are:

If several sublayers have the same spectral sensitization before, so they can with regard to their Composition, especially what kind and amount of Sil differ from berhalogenidkörnchen. In general becomes the sub-layer with higher sensitivity be located more distant from the carrier than the sub-layer with lower sensitivity. sublayer same spectral sensitization can each other adjacent or through other layers, e.g. B. by  Layers of other spectral sensitization separated his. So z. B. All the most sensitive and all low-sensitive layers in each case to a layer package be summarized (DE-A-19 58 709, DE-A- 25 30 645, DE-A-26 22 922).

The photographic material may further comprise UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, dye, coupler and whitener stabilizer additives, color fog reducing agents, plasticizers (latices), Biocide and other included.

UV-absorbing compounds on the one hand the image dyes from 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 Compounds of different structure used. Examples are aryl-substituted benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. A-33 14 794 and 33 52 681), benzophenone compounds (JP A-27 84/71), cinnamic acid ester compounds (US-A-37 05 805 and 37 07 375), butadiene compounds (US Pat. No. 4,045,229) or benzoxazole compounds (US Pat. No. 3,700,455).  

Examples of particular suitable compounds are:

It is also possible to use ultraviolet absorbing couplers (such as Cyan coupler of the α-naphthol type) and ultraviolet sorbing polymers are used. These ultraviolet absorbers can by pickling in a special Layer to be fixed.

For visible light suitable filter dyes include Oxonol dyes, heminoxonol dyes, styryl dyes, Merocyanine dyes, cyanine dyes and azo  dyes. Of these dyes, oxonol dyes, Hemioxonol dyes and merocyanine dyes used particularly advantageous.

Suitable whiteners are z. In Research Disclosure 17,643 (Dec., 1978), Chapter V, in US-A-26 32 701, 32 69 840 and in GB-A-8 52 075 and 13 19 763 described.

Certain binder layers, in particular those of Wearer furthest away, but also occasionally Interlayers, especially if they are during production the furthest from the wearer represent distant layer, can photographically inert Contain particles of inorganic or organic nature, z. B. as a matting agent or as a spacer [DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI].

The mean particle diameter of the spacers is in particular in the range of 0.2 to 10 microns. The spacers are insoluble in water and can be alkali-insoluble or alkali-soluble, the alkali-soluble generally in the alkaline development bath removed from the photographic material. Examples suitable polymers include polymethylmethacrylate, copolymers from acrylic acid and methyl methacrylate as well Hydroxypropylmethyl cellulose.  

Additives to improve the dye, coupler and White stability and to reduce color fog (Research Disclosure 17 643 (Dec., 1978), Chapter VII) may belong to the following chemical classes: Hydroquinones, 6-hydroxychromates, 5-hydroxycoumarans, Spirochromans, spiroindans, p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, Methylenedioxybenzenes, aminophenols, sterically hindered Amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds containing both a sterically hindered amine Partial structure as well as a sterically hindered one Phenol partial structure in one molecule (US Pat. A-42 68 593), are particularly effective for prevention the impairment of yellow color images as a result the development of heat, moisture and light. Around the impairment as a result of the action of light, are spiroindanes (JP-A 1 59 644/81) and chromans produced by hydroquinone diethers or monoethers are substituted (JP-A-89 835/80) especially effective.  

Examples of particularly suitable compounds are:

and the compounds listed as EOP scavengers.  

Color photographic recording materials usually become through development, bleaching, fixing and Watering or developing, bleaching, fixing and Stabilizing processed without subsequent washing, wherein bleaching and fixing become a processing step can be summarized. As a color developer compound All developer compounds can be used use that have the ability to get in shape their oxidation product with color couplers to azomethine or indophenol dyes. Suitable color Developer compounds are aromatic, at least one primary amino-containing compounds of p-phenylenediamine type, for example, N, N-dialkyl-p-phe nylenediamines 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 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 can be an acid stop bath or follow a watering.

Usually, the material is immediately after the Color development bleached and fixed. As a bleach can z. B. (Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes be used. Particularly preferred  Iron (III) complexes of aminopolycarboxylic acids, in particular z. For example, ethylenediaminetetraacetic acid, propylene diamintetraacetic acid, diethylenetriaminepentaacetic acid, Nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethyl ethylenediaminetriacetic acid, alkyliminodicarboxylic acids and of corresponding phosphonic acids. suitable as bleaching agents persulfates and peroxides, z. B. hydrogen peroxide.

The bleach-fix or fixer is usually followed by one Irrigation, which is designed as countercurrent irrigation or consists of several tanks with their own water supply.

Cheap results can be obtained by using one The following conclusion, the little or no Formaldehyde.

However, the watering can be complete by a stabilizer be replaced, usually in countercurrent to be led. This stabilizer takes on form aldehyde addition also the function of a final bath.

In the case of color reversal materials, development first takes place with a black and white developer whose oxidation product not capable of reacting with the color couplers is. It closes a diffuse second exposure and then development with a color developer, Bleaching and fixing.  

Examples Example 1

10 g of coupler are mixed with 10 g of dibutyl phthalate and 20 g Dissolved ethyl acetate and then in 100 g of a 10% Gelatin solution containing 0.5% dodecyl benzene sulfonate, emulsified in the usual way. After that it will be Ethyl acetate evaporated.

The resulting emulsifier becomes a blue-sensitized Silver chloride emulsion added so that the mixture then per 1 g of AgNO₃ contains 1.3 g of coupler.

The casting solution is then added after addition of a wetting agent onto a 0.55 g polyethylene coated paper AgNO₃ / m² applied. Over it is a gelatin protection layer with 0.8 g gelatin / m² potted.

On the potted layer is a hardening layer 400 mg gelatin and 400 mg instant hardener (CAS Reg.-No. 65 411-50-1). The layering becomes dried at 50 to 60 ° C. After drying on the Paper one step wedge behind a blue filter exposed and processed as follows:

• a) Color developer - 45 s - 35 ° C Triethanolamine | 9.0 g N, N-diethyl 6.0 g diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl-aniline sulfate 6.0 g potassium 0.2 g triethylene 0.05 g potassium carbonate 22.0 g potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid disodium salt 2.2 g Make up to 1000 ml with water; pH 9.2.
• b) Bleach-fix bath - 45 s - 35 ° C Ammonium thiosulphate | 75 g Sodium bisulfate 13.5 g ammonium acetate 2.0 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 57.0 g Ammonia 25% 9.5 g acetic acid 9.0 g Make up to 1000 ml with water; pH 5.5.
• c) watering - 2 min - 33 ° C.

Subsequently, the wedges thus obtained become different long periods irradiated with a xenon tester.

Subsequently, the residual densities remaining at different initial densities (0.5, 1.0, 1.5 D _max ) are measured and reported in% reduction, based on the initial densities (Table 1).

From Table 1 shows that the inventive Coupler suffer a lower color density loss and have significantly higher residual densities after irradiation.

In addition, the comparison coupler CC-1 is the essential poorer color rendering due to higher Yellow side densities on.

The following comparison couplers were used:

Table 1

example 2

A color photographic recording material which for a fast-processing process was prepared by placing on a substrate on both sides polyethylene coated paper the following Layers applied in the order given were. The quantities refer to each 1 m². For the silver halide order, the corresponding Amounts indicated AgNO₃.

layer structure

Layer 1 (substrate layer):
0.2 g of gelatin

Layer 2 (blue-sensitive layer):
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 microns) from 0.5 g AgNO₃, with
1.38 g of gelatin
0.7 g yellow coupler Y-12
0.2 g white coupler W-6
0.7 g tricresyl phosphate (TKP)

Layer 3 (protective layer):
1.1 g of gelatin
0.06 g of 2,5-dioctylhydroquinone
0.06 g dibutyl phthalate (DBP)

Layer 4 (green-sensitive layer):
green sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.6 μm) from 0.45 g AgNO₃, with
1.08 g of gelatin
0.50 g magenta coupler CC-5
0.08 g of 2,5-dioctylhydroquinone
0.50 g DBP

Layer 5 (red-sensitive layer):
red sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 microns) from 0.3 g AgNO₃ with
0.75 g of gelatin
0.36 g of cyan coupler C-22
0.36 g TKP

Layer 6 (protective layer):
0.9 g of gelatin
0.3 g of curing agent of the following formulas

The material thus prepared is called sample 1 (comparative) designated. In an analogous manner, a sample 2  prepared by using in layer 4 instead of the contained therein Vergleichskupplers CC-5 of the invention Magenta coupler M-10 was used. Samples 1 and 2 were processed as in Example 1 and the obtained Color wedges of different lengths in a Xenotestgerät irradiated. The results (percentage color density decrease) are shown in Table 2.

Apart from those already mentioned, the following connections were made used in Samples 1 and 2:

Table 2

Is between the layers 4 and 5 an additional Layer 4a with

1.03 g of gelatin
0.50 g UV absorber UV-4
0.09 g UV absorber UV-7
0.045 g of 2,5-dioctylhydroquinone
0.040 g tricresyl phosphate

and between layers 5 and 6 an additional Layer 5a with

0.35 g of gelatin
0.16 g UV absorber UV-4
0.03 g UV absorber UV-7
0.008 g of 2,5-dioctylhydroquinone
0.20 g of tricresyl phosphate

applied, the results in Table 3 Values (percentage color density decrease).  

Table 3

Claims (5)

1. Color photographic recording material having at least one arranged on a support silver halide emulsion layer and at least one non-diffusing color coupler of Pyra zoloazol type, characterized in that the coupler of the following general formula I corresponds in which mean
PAZ the group capable of color coupling of a color coupler of the pyrazoloazole series;
L is a link attached to a noncoupling position of PAZ;
R¹ is alkyl, cycloalkyl or aryl;
R² is alkyl or aryl;
t 1 or 2. 2. Recording material according to claim 1, characterized that in formula I PAZ for a Py razolo [3,2-c] -1,2,4-triazole, pyrazolo [2,3-b] - 1,2,4-triazole or pyrazolo [2,3-d] tetrazole residue stands.   3. A recording material according to claim 1, characterized by a content of a color coupler of the formulas I-4, I-5 and I-7 in which mean
XH or a colorless cleavable radical other than H;
R³, S, T, H, alkyl, aralkyl, aryl, alkoxycarbonyl, carbamoyl or sulfamoyl
with the proviso that at least one of R³, S and T is a group of formula stands, in which mean
R¹ is alkyl, cycloalkyl or aryl
R² is alkyl or aryl
t 1 or 2
L is a linker of the formula -L¹- (L²) ₁- (L³) _m - (L⁴) _n - (L⁵) _o - (L⁶) _p - (L⁷) _q -worin L¹ of the group PAZ and L⁷ that of the hydroquinone ether group denote initially located part of the link and in which mean (the same or different):
L¹, L³, L⁵, L⁷ alkylene, aralkylene, arylene;
L², L⁴, L⁶ -O-, -NH-, NHCO-, -CONH-, -NHSO₂-, -SO₂NH-, -SO₂-;
l, m, n, o, p, q are each 0 or 1, where 1 - m + n - o + p - q = 0. 4. Recording material according to one of claims 1 and 3, characterized in that R² is for ter is tiärbutyl and t = 1. 5. Recording material according to one of claims 1 to 4, characterized in that the color coupler of the formula I of a green-sensitive silver halo is assigned to genidemulsionsschicht and that the Layer support is opaque.