DE19513717A1 - Colour photographic silver halide material for increased dye fastness - Google Patents

Abstract

Colour photographic Ag halide (AgX) comprises: (a) a base; (b) AgX emulsion layer(s) contg. a pyrazolo triazole magenta coupler; and (c) other layer(s); where: (i) other layer(s) contains a co-PVA of formula (I); and (ii) the layer contg. the magenta coupler contains a bisphenol of formula (IIA) or a hydroquinone ether of formula (IIB): -(CH2-CH(OH))k-(M)l-(M1(B-NHR1))m-(M2)j- (I) k = 50-99 wt.%; l, j = 0-40 wt.%; i = 1-40 wt.%; M = a comonomer; M1 = a gp. of formula -CH2-CR2- (IIIA) or (IIIB); ; M2 = a gp. of formula (IV): R1, R2 = H or alkyl; R3 = an acid gp.; B = a chemical bond or a bridging gp.; R<21> = H, prim. or sec. alkyl or acylamino; R<22> = alkyl, acyl or acylamino; R<24> = H or alkyl; m, n = 0, 1 or 2; R<31> = alkyl or -(CHR<33>)p-O-R<34>; R<32> = alkyl, acyl, Cl or acylamino; R<33> = H, 1-4C alkyl or OH; R<34> = H, alkyl or acyl; o = 0, 1, 2, 3 or 4; p = 2, 3 or 4; and adjacent -OR<31> and R<32> = a 5-6-membered ring.

Description

The invention relates to a silver halide color photographic material as Purple coupler contains at least one pyrazolotriazole and by a improved light stability, especially the purple dyes, distinguished.

From EP 627 656 is known, a layer of a color photographic Auf a vinyl alcohol copolymer, hereinafter called CO-PVA, added to the light stability of the generated from the purple couplers Stabilize purple dyes. The sunscreen is still insufficient.

The object of the invention was to color photographic materials in this capacity too improve.

It has now surprisingly been found that this object is achieved when reacting a silver halide emulsion layer containing a pyrazolotriazole Purple coupler contains, at least one compound of the formulas (II) or (III) and at least one further layer of a CO-PVA of the formula

in which
k 50 to 99% by weight, preferably 70 to 97% by weight,
from 0 to 49% by weight, preferably from 0 to 27% by weight,
m is 1 to 40% by weight, preferably 3 to 15% by weight and
j is 0 to 49% by weight, preferably 0 to 27% by weight,
M is a copolymerized comonomer,

R₁, R₂ is hydrogen or alkyl,
R₃ is an acidic group, preferably -COOH, -SO₃H or -PO₃H₂ and
B represents a chemical bond or a bridge member.

B preferably has the meaning

-L₁- (L₂) n- (L₃) o-

wherein
L₁, L₃ a conventional organic link, in particular an optionally substituted alkylene, arylene or aralkylene radical having a maximum of 18 carbon atoms,
L₂-COO-, -OC-O-, -CO-NH-, -NH-CO-, -SO₂-NH-, -NH-SO₂-, -NH-CO-O- or -NH-CO-NH- and
n and o denote 0 or 1.

In this case, L₁ is bound directly to M₁.

The molecular weight of the compound of the formula (I) is in particular 10,000 to 500,000, preferably 20,000 to 200,000 (weight average).

Alkyl radicals R₁ and R₂ in particular have 1 to 4 carbon atoms.

The phenylene, arylene and aralkylene radicals L₁ and L₃ are preferably not further substituted.

Comonomers M preferably have an acidic group, in particular a Carboxyl group on.

Examples of such comonomers are esters and amides of acrylic acid and their Derivatives z. Example of acrylic acid, α-chloroacrylic acid, methacrylic acid (for example Acrylamide, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate, lauryl meth acrylate and methylenebisacrylamide), vinyl esters (for example, vinyl acetate, vinyl propionate and vinyl laurate), acyl nitrile, methacrylonitrile, aromatic vinyl compound (for example, styrene, vinyltoluene, divinylbenzene, vinylacetophenone, Styrenesulfonic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, Vinyl alkyl ethers (for example, vinyl ethyl ether), esters of maleic acid, N-vinyl-2-pyrrolidone, N-vinyl, 2-vinyl and 4-vinylpyridine and acrylic acid and methacrylic acid.

Preferred comonomers are vinyl acetate, crotonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, styrenesulfonic acid, acrylamido 2-methylpropanesulfonic acid, sulfoethyl methacrylate and vinylsulfonic acid.  

It is further preferred that the compound of the formula I is either a copolymerized comonomer M with acidic groups and / or the group M 2 contains.

In this case, l and j together represent from 2 to 30 mol%.

The CO-PVA may have a statistical distribution of the comonomers or graft or block copolymers. In particular, they are copolymers with Polyacrylsäureblöcken.

Preferably, in the at least one layer 50 mg to 5 g / m² of CO- PVA on.

Examples of polymers according to the invention are:

k: l: m = 80: 15: 5
M _w = 130,000

k: l: m = 75: 17: 8
M _w = 84 000

k: l: m = 93: 2: 5
M _w = 48,000

k: l: m = 92: 5: 3
M _w = 200,000

k: l: m = 78: 15: 7
_Mw = 23,000

k: l: m = 79: 18: 3
M _w = 95,000

k: l: m = 65: 25: 10
M _w = 70,000

k: l: m = 78: 12: 10
M _w = 63,000

k: l: m = 74: 20: 6
M _w = 105,000.

The CO-PVA of the invention can without further binders in fotogra fish materials are used as binders. Preferably, however, will be Blends with known binders such as gelatin, polyvinylpyrrolidone,  Polyvinyl alcohol used. Particular preference is given to blends with Gelatin. When using CO-PVA gelatin blends is in general, a weight ratio of CO-PVA: gelatin of 90:10 to 5:95, preferably from 60:40 to 10:90.

The PVA copolymers according to the invention can be present in all binders the layers of photographic materials are used. It is the same possible, the copolymer of the invention only in one or a few layers use. For example, it is possible by adding the CO-PVA in only one Layer of the stratified bond to crosslink this layer stronger than the others.

By adding different amounts of CO-PVA to different gelatin containing layers, the layers can be cured differently. Thus is the setting of a curing profile possible.

The CO-PVA are preferably in at least two layers of the photo used in graphic material. To the light stability of dyes too should improve a CO-PVA layer above and a CO-PVA layer below the Be provided for the layer resulting from the development, too contains protective dye. It is irrelevant whether the CO-PVA ent holding layers are emulsion, substrate, intermediate or protective layers.

The compounds (II) and (III) correspond to the following formulas:

wherein
R 21 H, primary or secondary alkyl, acylamino,
R²² alkyl, acyl, acylamino,
R 23 is alkyl, acyl, acylamino,
R²⁴H, alkyl,
m, n is 0, 1, 2.

Adjacent radicals R 21 to R 23 may form a 5- or 6-membered ring. Several radicals R 21 to R 23 may be identical or different.

wherein

R³² alkyl, acyl, chlorine, acylamino,
R³³ H, alkyl of 1 to 4 carbon atoms, hydroxy,
R³⁴H, alkyl, acyl,
o 0, 1, 2, 3, 4 and
p is 2, 3, 4.

Neighboring radicals -OR³¹ and R³² can form a 5- or 6-membered ring. Several radicals R³¹ to R³⁴ may be the same or different.

R¹¹ to R³⁴ shown or contained therein alkyl radicals can straight chain, be branched or cyclic and - except R³³ - 1 to 18 carbon atoms  R²¹ to R²⁵ and R³² to R³⁴ can also be reacted with chlorine, fluorine, Hydroxy, -COOH, acyl, alkylsulfonyl, acylamino, acyloxy or alkoxy be substituted. From R²¹ to R³⁴ shown or contained therein acyl radicals may be of a carbon, carbon, sulfone, carbamine, phosphorus, phosphonyl, Derived from phosphorous or aminosulphuric acid.

Examples of compounds according to the invention are:

In a preferred embodiment, m and n and o are 0, 1 or 2.

In a further preferred embodiment, a through R²¹ to R³⁴ represented or contained in the acyl radical derived from a carbon, carbon, Sulfin, carbamic or aminosulfuric acid.

In a particularly preferred embodiment, R²³ is alkyl and R³² is alkyl or Acylamino.

In a further particularly preferred embodiment, the Verbindun of the formula (II) together with compounds of the formula (IV):

wherein
R⁴¹ alkyl,
R⁴² alkyl, chlorine, fluorine, alkoxy, acyl, acylamino,
Z⁴¹ alkylene having 1 to 3 carbon atoms,
Z⁴² ethylene,
X is -O-, -SO₂-, -SO-, N-SO₂-R⁴³, N = O,
R⁴³ alkyl, aryl and
q is 0, 1, 2.

In one of R⁴¹ to R⁴³ shown or contained therein alkyl or acyl radical the same applies for R²¹ to R³⁴. An alkylene radical Z⁴¹, Z⁴² can be reacted with methyl, ethyl or alkoxycarbonyl.

In a particularly preferred embodiment, q is 0, 1, Z⁴¹ ethylene, R⁴² Alkyl, alkoxy, chlorine and X is -O-, -SO₂-.

Examples are:

In addition to the polymers used according to the invention, further poly mere layers containing the binder may be added. examples are Polyacrylamides, gelatin derivatives, polyacrylic acid or polymethacrylic acid or their salts, polyvinylpyrrolidone, polyvinyl alcohol or carboxyl groups enthal  polyvinyl alcohol derivatives, polyvinyl imidazole, polyethyl acrylate, polybutyl acrylate, polyurethane latices, polyester dispersions.

Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, Color-sensitive materials for the color diffusion transfer process or the Silver dye bleach process.

Suitable carriers for the production of color photographic materials are, for. B. movies and films of semi-synthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and with a baryta or α-olefin polymer layer (eg polyethylene) laminated paper. These carriers can contain dyes and amounts of pigments, such as titanium dioxide, to be colored. You can also go to Purpose of shielding from light to be colored black. The surface of the The carrier is generally subjected to a treatment to prevent the adhesion of the photographic emulsion layer to improve, for example, a corona Ent charge with subsequent application of a substrate layer.

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

Essential constituents of the photographic emulsion layers are binders, Silver halide grains and color couplers.

As a binder, in addition to the compounds of formula (I) is preferably Gela tine used. However, this may be wholly or partly due to other synthetic, half synthetic or naturally occurring polymers are replaced. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N- vinyl-pyrrolidone, 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 gelatin substitutes are usually modified Natural products. Cellulose derivatives such as hydroxyalkylcellulose, carboxymethylcellu  and phthalyl cellulose and gelatin derivatives by reaction with Alkylating or acylating agents or by grafting polyme risierbaren monomers are examples of this.

The binders should have a sufficient amount of functional groups have sufficient so that by reaction with suitable curing agents Resistant layers can be produced. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin preferably used may be acidic or alkaline Be received digestion. Oxidized gelatin can also be used. The Preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, edited by A.G. Ward and A. Courts, Academic Press 1977, Page 295 ff. The gelatine used should be as possible low content of photographically active impurities (inert gelatin). Gelatins with high viscosity and low swelling are particularly advantageous.

The photosensitive component contained in the photographic material Silver halide may be chloride, bromide or iodide or mixtures as halide included. For example, the halide content of at least one layer from 0 to 15 mol% of iodide, to 0 to 100 mol% of chloride and 0 to 100 mol% consist of bromide. In the case of color negative and color reversal Film are usually Silberbromidiodidemulsionen, in the case of color negative and color reversal paper usually silver chloride bromide emulsions with high chloride content used to pure silver bromide emulsions. It can are predominantly compact crystals, the z. B. regular cubic or octahedral or may have transitional forms. Preferably but also platelet-shaped crystals are present, their average ratio from diameter to thickness is preferably at least 5: 1, wherein the diameter a grain of the projected area of the grain. But the layers can as well have tabular silver halide crystals in which the ratio of Diameter to thickness is much larger than 5: 1, z. From 12: 1 to 30: 1.  

The silver halide grains may also have a multi-layered grain structure have, in the simplest case with an inner and an outer grain area (core / shell), wherein the halide composition and / or other modifizie ments, such as B. doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 m and 2.0 m, the particle size distribution can be both homo- and heterodisperse. Homodisperse particle size distribution means that 95% of the grains do not exceed ± 30% deviate from the mean grain size. The emulsions can be next to the silver halide also contain organic silver salts, for. B. silver benzotriazolate or silver behenate.

Two or more types of silver halide emulsions can be separated be prepared, used as a mixture.

The photographic emulsions can be prepared by various methods (eg P.I. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) made from soluble silver salts and soluble halides become.

The precipitation of the silver halide is preferably carried out in the presence of the binder, z. As the gelatin and can in the acidic, neutral or alkaline pH range be carried out, preferably using Silberhalogenidkomplexbildner to be used in addition. The latter include, for. Ammonia, thioether, Imidazole, ammonium thiocyanate or excess halide. The together Guidance of the water-soluble silver salts and the halides is optional one after the other after the single jet or simultaneously using the double jet method or by any combination of both methods. The dosage is preferred with increasing inflow rates, the "critical" feed rate at which just no new germs arise, should not be exceeded. The pAg range can vary widely during precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg constant or a defined pAg profile during precipitation is passed through. But in addition to the preferred precipitation at halide excess is  also the so-called inverse precipitation with silver ion excess possible. Except by precipitation, the silver halide crystals can also by physical Maturation (Ostwald ripening), in the presence of excess halide and / or Silver halide complexing agents grow. The growth of the emulsions Grains can even be made predominantly by Ostwaldreifung, preferential example, a fine-grained, so-called Lippmann emulsion, with a heavier soluble emulsion is mixed and redissolved on the latter.

During the precipitation and / or physical ripening of the silver halide grains may also be salts or complexes of metals, such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe are present.

Furthermore, the precipitation may also be in the presence of sensitizing dyes respectively. Complexing agents and / or dyes can be added to each belie invalidate a given date, eg B. by changing the pH or by an oxidative treatment.

After crystallization has been completed or already at an earlier time point the soluble salts are removed from the emulsion, z. B. by pasta and washing, by flocculation and washing, by ultrafiltration or by ions exchangers.

The silver halide emulsion generally becomes a chemical sensitiser under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until reaching the Sensitive subjected to keits- and Schleieroptimums. The procedure is z. B. at H. Frieser "The Fundamentals of Photographic Processes with Silver Halides" Pages 675-734, Akademische Verlagsgesellschaft (1968).

In this case, the chemical sensitization with the addition of compounds of Sulfur, selenium, tellurium and / or compounds of the metals of VIII. Subgroup of the periodic table (eg gold, platinum, palladium, iridium), furthermore For example, thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (eg imidazoles, azaindenes) or also spectral sensitizers (described, for example, in F. Hamer "The Cyanine Dyes and  Related Compounds ", 1964, or Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec., 1978), chapter III) are added. Alternatively or additionally, a Reduktionsensibili with the addition of reducing agents (stannous salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) by hydrogen, by low pAg (eg, less than 5) and / or high pH (eg, above 8) become.

The photographic emulsions may be compounds for preventing the Fogging or to stabilize the photographic function during the Production, storage or photographic processing.

Particularly suitable are azaindenes, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. the like connections are z. B. von Birr, Z. Wiss. Phot. 42 (1952), pp. 2-58 be been written. Further, as antifogging agents, salts of metals such as Mercury or cadmium, aromatic sulfonic or sulfinic acids such as Benzolsul finsäure, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or Benzthiazoliumsalze used who the. Particularly suitable are mercapto-containing heterocycles, for. B. Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothia diazoles, mercaptopyrimidines, these mercaptoazoles also being a water-soluble making group, z. As a carboxyl group or sulfo group may contain. Other suitable compounds are described in Research Disclosure 17643 (Dec., 1978), Chapter VI, published.

The stabilizers may be added to the silver halide emulsions before, during or after their maturation are added. Of course you can do the connections also other photographic layers associated with a silver halide layer are, enforce.

It is also possible to use mixtures of two or more of the compounds mentioned be used.  

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can upper surface active agents for various purposes, such as coating aids, for Prevention of electric charge, to improve gliding to emulsify the dispersion, to prevent adhesion and to Improvement of photographic characteristics (eg development acceleration high contrast, sensitization, etc.). In addition to natural surface active Compounds, e.g. As saponin, find mainly synthetic surface-active Compounds (surfactants) Use: non-ionic surfactants, eg. B. alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic Surfactants, e.g. B. higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphines phonium compounds, anionic surfactants containing an acid group, e.g. B. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric ester or phos phorsäureestergruppe, ainpholytische Tenside, z. B. amino acid and aminosulfone acid compounds and sulfuric or phosphoric acid esters of an aminoalcohol.

The photographic emulsions can be prepared using methine dyes or other dyes spectrally sensitized. Particularly suitable color cyanine dyes, merocyanine dyes and complex merocyanine dyes substances.

An overview of the suitable as Spektralsensibilisatoren Polymethinfarb substances, their suitable combinations and supersensitizing Kom contains Research Disclosure 17643 (Dec., 1978), Chapter IV.

In particular, the following dyes - ordered by spectral regions - suitable:

• 1. as red sensitizers
  9-ethylcarbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which may be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selenacarbocyanine and 9 Ethyl naphthothia oxa- and benzimidazocarbocyanines, 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 Benzimidazo carbocyanine, which may also be further substituted and must also contain at least one sulfoalkyl group on the heterocyclic nitrogen.
• 3. as blue sensitizers
  symmetrical or asymmetric benzimidazo, oxa, thia or selenium acyanines 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.

Sensitisers can be omitted if for a specific spectral Area the intrinsic sensitivity of the silver halide is sufficient, for example show the blue sensitivity of silver bromides.

The differently sensitized emulsion layers will not diffuse associated monomeric or polymeric color couplers that are in the same Layer or in a layer adjacent thereto. Usually the red-sensitive layers become cyan couplers, the green-sensitive ones Layers of magenta coupler and the blue-sensitive layers yellow coupler assigned.

Color couplers for producing the cyan partial color image are usually Phenolic or α-naphthol type couplers and pyrrolotriazoles.

Color couplers for producing the purplish part colorant are, as stated, According to the invention pyrazolotriazoles. In addition, couplers of the type 5 Pyrazolones, the indazolone or other pyrazoloazole be used.  

Color couplers for producing the yellow partial color image are usually couplers with an open chain ketomethylene moiety, especially couplers of the type the α-acylacetamide; suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers. Also suitable are malonic acid half esters amide (US Pat. No. 5,338,634), enamines (US Pat. No. 5,310,635) and bicycloalkane radicals de coupler (U.S. 5,294,531).

The color couplers can be 4-equivalent couplers, but also to Act 2-equivalent couplers. The latter are derived from the 4-equivalent couplers characterized in that they contain a substituent in the coupling site at the clutch is split off. Among the 2-equivalent couplers are those too which are colorless, as well as those which have an intense inherent color, which disappears in the color coupling or by the color of the generated Image dye is replaced (mask coupler), and the white couplers, at Reak tion with color developer oxidation products essentially colorless products result. In addition to the 2-equivalent couplers such couplers are to be expected, the in the coupling point contain a cleavable radical which reacts with Color developer oxidation products is set free and either directly or after one or more of the primary cleavage residues 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. As a development inhibitor or accelerator. Examples for such 2-equivalent couplers, the known DIR couplers as well as DAR or FAR coupler.

DIR couplers, the azole type of development inhibitors, e.g. Triazoles and benzo triazoles are disclosed in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416 described. Further Advantages for color rendering, d. H. Color separation and color purity, and for the Detail reproduction, d. H. Sharpness and graininess are with such DIR couplers too achieve that z. B. the development inhibitor not directly as a result of Kupp split off with an oxidized color coiler, but only after a further subsequent reaction, which is achieved for example with a timing group. Examples thereof are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in  EP-A-0 157 146 and 0 204 175, in US Pat. Nos. 4,146,396 and 4,438,393 and in US Pat GB-A-2 072 363.

DIR couplers that release a development inhibitor that in the developer to is decomposed essentially photographic ineffective products are, for example in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. With This measure is a trouble-free development and processing consistency reached.

When using DIR couplers, especially those that are a good diffim split off dierbaren development inhibitor, can be by appropriate measure Improved color rendering in optical sensitization, z. B. achieve a more sophisticated color reproduction, such as in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4,707,436.

The DIR couplers can be used in a multilayer photographic material be added to various layers, for. B. also insensitive to light or intermediate layers. Preferably, however, they become the photosensitive Added silver halide emulsion layers, wherein the characteristic Eigen the silver halide emulsion, e.g. B. their iodide content, the structure of Silver halide grains or their particle size distribution of influence on he are targeted photographic properties. The influence of the released inhibitors For example, by incorporating an inhibitor scavenger layer according to DE-A-24 31 223 be limited. For reasons of reactivity or stability it may be advantageous to use a DIR coupler which is in the respective Layer in which it is introduced, one of the in this layer to be produced Color deviating color forms at the coupling.

To increase the sensitivity, the contrast and the maximum density In particular, DAR or FAR couplers can be used which have a development release accelerator or a veiling agent. Compounds of this type are 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-0 089 834, 0 110 511, 0 118 087, 0 147 765 and in US-A-4,618,572 and 4,656,123.  

As an example of the use of BAR coupler (Bleach Accelerator Releasing Coupler), reference is made to EP-A-0 193 389.

It may be advantageous to the effect of a cleaved from a coupler photo graphically effective group by modifying an intermolecular Re according to their release with another group according to DE-A-35 06 805 occurs.

Since the DIR, DAR and FAR couplers mainly the effectiveness of the in the clutch released residue is desired and less on the color-forming properties of these couplers are important, are also such DIR-, DAR or FAR coupler suitable which in the coupling substantially colorless Products result (DE-A-15 47 640).

The cleavable residue may also be a ballast residue, so that in the reaction with Color developer oxidation products are obtained coupling products that diffuse or at least weak or limited mobility (US-A-4,420,556).

The material may further contain compounds other than couplers, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent Veiling agent or an antifoggant can be set free, for example so-called DIR-hydroquinones and other compounds, such as in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-0 198 438 are described. Meet these connections the same function as the DIR, DAR or FAR couplers, except that they have no Form coupling products.

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-4 080 211. The high molecular color couplers are used in the Rule by polymerization of ethylenically unsaturated monomer Farbkupp  produced. But you can also by polyaddition or polycondensation to be obtained.

The incorporation of the couplers or other compounds in silver halide emuls layers can be carried out in such a way that first of all the Ver Made a solution, a dispersion or an emulsion and then the Casting solution for the relevant layer is added. The selection of the appropriate Solvent or dispersant depends on the particular solubility of the verbin from.

Methods for introducing substantially insoluble in water Verbin Applications by milling processes are described, for example, in DE-A-26 09 741 and US Pat DE-A-26 09 742 described.

Hydrophobic compounds can also be made using high boiling Solvents, so-called oil formers are introduced into the casting solution. Corresponding methods are described, for example, in US Pat. No. 2,322,027, US Pat. 2,801,070, US-A-2,801,071 and EP-A-0 043 037.

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

The compounds may also be in the form of loaded latices in the casting solution be introduced. Reference is made, for example, to DE-A-25 41 230, DE-A- 25 41 274, DE-A-28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, US-A-4291113.

The diffusion-resistant incorporation of anionic water-soluble compounds (eg. of dyes) can also be made with the help of cationic polymers, so-called Beizenpolymeren done.

Suitable oil formers are z. Phthalic acid alkyl ester, phosphonic acid ester, Phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, Trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.  

Examples of suitable oil formers are dibutyl phthalate, dicyclohexyl phthalate, di-2- ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethyl hexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri decyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethyl hexylphenyl phosphate, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p- hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctyl acetate, glycerol tributyrate, isostearyl lactate, tri octyl citrate, N, N-dibutyl-2-butoxy, -5-octylaniline, paraffin, dodecylbenzene and Diisopropylnaphthalene.

Each of the differently sensitized photosensitive layers may be made consist of a single layer or two or more Silberhalogenidemul partial spreading layers comprise (DE-C-11 21 470). These are red-sensitive silver halide emulsion layers often closer to the substrate than green sensitive silver halide emulsion layers and these in turn closer than blue sensitive, which is generally 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 by dispensing with the yellow filter layer other Schichtanord choose where the carrier has B. the blue-sensitive, then the red sensitive and finally the green sensitive layers follow.

The usually between layers of different spectral sensitivity arranged non-photosensitive intermediate layers may contain agents, the unwanted diffusion of developer oxidation products from a light sensitive in another photosensitive layer with different spek prevent trol sensitization.

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

If several partial layers of the same spectral sensitization are present, then these in terms of their composition, especially what kind and quantity the silver halide grains are different. In general, the Particle layer with higher sensitivity of the carrier can be arranged more remote than the sub-layer with lower sensitivity. Sublayers of the same spectral Sensitization may be adjacent to each other or through other layers, e.g. B. separated by layers of other spectral sensitization. So z. B. all highly sensitive and all low-sensitive layers in each case to one Layer pack be summarized (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).

The photographic material may further UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavenger, light stabilizers, antioxidants, D _min dyes, additives to improve the colorant, Kupp ler- and whitening stabilizer and to reduce color fog, plasticizers (latices ), Biocide and others.

UV-absorbing compounds should on the one hand the image dyes before the To prevent fading by UV-rich daylight and on the other hand as a filter color substances absorb the UV light in daylight during the exposure and thus the color improve the playback of a movie. Usually, for the two tasks Compounds of different structure used. To protect the image dyes the UV absorber polymers according to the invention are used. additionally Further UV absorbers can be used. Examples are aryl-substituted Benzotriazole compounds (US Pat. No. 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 compound (US Pat. No. 4,045,229) or benzoxazole compounds (US Pat. No. 3,700,455).

It is also possible to use ultraviolet absorbing couplers (such as cyan couplers of the α- Naphthol type) and ultraviolet absorbing polymers. These Ultraviolet absorbers can be fixed by pickling in a special layer his.  

Visible light filter dyes include oxonol dyes, hemi oxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and Azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine used particularly advantageous.

Suitable whiteners are z. In Research Disclosure 17 643 (Dec., 1978), Chapter V in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763 described.

Certain binder layers, in particular those of the carrier farthest ent distant layer, but also occasionally intermediate layers, especially if they during manufacture, represent the layer furthest away from the wearer, can photographically inert particles of inorganic or organic nature enthal th, 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 average particle diameter of the spacers is in particular in the Range of 0.2 to 10 microns. The spacers are water insoluble and can alkali-insoluble or alkali-soluble, the alkali-soluble in general in alkaline development bath are removed from the photographic material. Examples of suitable polymers are polymethyl methacrylate, copolymers of Acrylic acid and methyl methacrylate, as well as hydroxypropylmethyl cellulose hexa hydrophthalat.

Additives to improve the dye, coupler and whitening stability and to Reduction of color fog (Research Disclosure 17 643 (Dec. 1978), Chapter VII) may belong to the following chemical classes: hydroquinones, 6- Hydroxychromans, 5-hydroxycoumarans, spirochromans, spiroindanes, p-alkoxy phenols, 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 and have a sterically hindered phenol partial structure in one molecule (US Pat. 4,268,593), are particularly effective in preventing the impairment of  Yellow color images as a result of the development of heat, moisture and light. To the impairment of purple color images, in particular their Beh Impairment as a result of the action of light to prevent are spiroindanes (JP-A-159 644/81) and chromans produced by hydroquinone diethers or monoethers Substituted (JP-A-89 835/80) are particularly effective.

The layers of photographic material can be mixed with the usual Curing agents are cured. Suitable curing agents are, for. B. formaldehyde, Glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro 1,3,5-triazine and other compounds containing reactive halogen (US-A 3,288,775, US-A 2,732,303, GB-A 974,723 and GB-A 1167,207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other compounds which contain a reactive olefin bond (US Pat. No. 3,635,718, US Pat 3,232,763 and GB-A 994,869) N-hydroxymethylphthalimide and other N- Methylol compounds (US Pat. No. 2,732,316 and US Pat. No. 2,586,168); Isocyanates (US-A 3 103 437); Aziridine compounds (US-A 3,017,280 and US-A 2,983,611); Acid derivatives (US-A 2,725,294 and US-A 2,725,295); Connections from Carbodiimide type (US Pat. No. 3,100,704); Carbamoylpyridiniumsalze (DE-A 22 25 230 and DE-A 25 39 551); Carbamoyl oxypyridinium compounds (DE-A 24 08 814); Compounds having a phosphorus-halogen bond (JP-A 113 929/83); N- Carbonyloximide compounds (JP-A 43353/81); N-Sulfonyloximido compounds (US-A 4,111,926); Dihydroquinoline compounds (US-A-4 013 468); 2 Sulfonyloxypyridiniumsalze (JP-A 110 762/81), Formanidiniumsalze (EP-A No. 0 162 308), compounds having two or more N-acyloximino groups (US Pat 4 052 373), epoxy compounds (US Pat. No. 3,091,537), compounds of Isoxazole type (US-A 3,321,313 and US-A 3,543,292); halogenocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

The curing can be effected in a known manner, that the Curing agent is added to the casting solution for the layer to be cured, or in that the layer to be cured is overcoated with a layer, the one contains diffusible curing agent.  

Among the listed classes, there are slow-acting and fast-acting ones Hardening agent and so-called immediate container, which are particularly advantageous. Instant hardeners are understood to mean compounds which are suitable binders, for example network, immediately after the end of the journey, at the latest after 24 hours, preferably Hardening is completed after 8 hours at the latest so far that no further due to the crosslinking reaction change in the sensitometry and the swelling of the layer dressing occurs. Swelling is the difference of Wet layer thickness and dry layer thickness in the aqueous processing of Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These curing agents are very fast reacting with gelatin z. B. carbamoylpyridinium salts containing the free carboxyl groups of gelatin react, so that the latter with free amino groups of gelatin react to form peptide bonds and crosslink gelatin.

Color negative photographic materials are usually processed by developing, Bleaching, fixing and watering or by developing, bleaching, fixing and Stabilize without subsequent watering, bleaching and Fixing can be combined to form a processing step. When Color developer compound can be all developer compounds use that have the ability in the form of their oxidation product with Color couplers to react azomethine or indophenol dyes. suitable Color developing agents are aromatic, at least one primary Amino group-containing p-phenylenediamine type compounds, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N- methanesulfonamido-ethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxy ethyl) -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 et seq.

After color development, an acid stop bath or a watering may follow.  

Usually, the material is bleached immediately after color development and fixed. As a bleaching agent z. As Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes. Particularly preferred are iron (III) complexes of aminopolycarboxylic acids, in particular z. Ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, Diethylentriaminpentaessigsäure, Alkyliminodicarbonsäuren and of corre sp phosphonic acids. Suitable bleaching agents are further persulfates and Peroxides, e.g. B. hydrogen peroxide.

The bleach-fix bath or fixer is usually followed by a wash, which is used as a counter current drainage is executed or from several tanks with their own water supply consists.

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

The irrigation can be completely replaced by a stabilizer, the usually performed in countercurrent. This stabilizer takes over Formaldehyde addition also the function of a final bath.

For color reversal materials, a development with a black White developer whose oxidation product is not reacting with the Color couplers is capable. It closes a diffuse second exposure and then Development with a color developer, bleaching and fixing.

The compounds of the formula (I) are preferably used in a total amount of 200 to 1,500 mg / m 2, more preferably 500 to 1,000 mg / m 2, the compounds of the formula (II) and (III) in a total amount of 50 to 1,000 mg / m 2 , in particular from 50 to 500 mg / m² and the compounds of formula (IV), if used, in a total amount of 20 to 600 mg / m² _, in particular from 40 to 400 mg / m² used.

The pyrazolotriazole magenta couplers are usually in a total amount from 50 to 800 mg / m² used, in particular from 100 to 400 mg / m²  Preferred pyrazolotrial couplers are those of the formula

wherein
R₁ is hydrogen, halogen, alkyl, aryl, a heterocyclic group, cyano, alkoxy, acyloxy, carbamoyloxy, acylamino or a polymer radical,
X is hydrogen or a leaving group,
one of Z₁ and Z₂ represents a nitrogen atom and the other represents -CR 2 - and
R _{R has} the same meaning as R₁, wherein one of R₁ and R₂ is a ballast group or substituted by a ballast group, wherein the ballast group may also be a polymer radical.

Suitable magenta couplers are:

example 1

A color photographic recording suitable for a fast-processing process material was prepared by applying to a support made of both sides Polyethylene coated paper the following layers in the specified Order were applied. The quantities refer to each 1 m². For the Silberhalogenidauftrag the appropriate amounts of AgNO₃ specified.

layer structure Sample 1

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, mean grain diameter 0.8 μm)
0.63 g of AgNO₃ with
1.11 g of gelatin
0.30 g yellow coupler Y-1
0.30 g yellow coupler Y-2
0.15 g white coupler XW-1
0.10 g of dye stabilizer ST-1
0.10 g of dye stabilizer ST-2
0.24 g of oil former OF-1

Layer 3: (protective layer)
1.1 g of gelatin
0.04 g of 2,5-di-tert-octylhydroquinone
0.04 g of compound SC-1
0.04 g tricresyl phosphate (TKP)

Layer 4: (green-sensitive layer)
green sensitized silver halide emulsion (99.5 mol% chloride,
0.5 mol% bromide, mean grain diameter 0.6 μm)
0.25 g of AgNO₃ with
0.95 g gelatin
0.20 g magenta coupler M-17
0.18 g of oil former OF-2
0.12 g of oil former OF-3

Layer 5: (UV protection layer)
0.75 g of gelatin
0.2 g UV absorber UV-1
0.1 g UV absorber UV-2
0.025 g of 2,5-di-tert-octylhydroquinone
0.02 g of compound SC-1
0.1 g of oil former OF-4
0.04 g TKP

Layer 6: (red-sensitive layer)
red sensitized silver halide emulsion (99.5 mol% chloride,
0.5 mol% bromide, mean grain diameter 0.5 μm)
0.30 g of AgNO₃ with
0.75 g of gelatin
0.36 g of cyan coupler C-1
0.24 g TKP
0.12 g of dye stabilizer ST-3

Layer 7: (UV protection layer)
0.85 g of gelatin
0.36 g UV absorber UV-1
0.18 g UV absorber UV-2
0.18 g of oil former OF-4

Layer 8: (protective layer)
0.9 g of gelatin
0.3 g of hardener H-1

In the samples of Example 1 the following compounds were used:

OF-1 polyester of adipic acid, neopentyl glycol and isodecanol (viscosity 4000-5500 mPa.s; OH number <15 mg KOH / g; acid value <2 mg KOH / g)
OF-2 C₄H₉O-CO- (CH₂) ₄-CO-OC₄H₉
OF-3 C₁₄H₂₉-OH / C₁₂H₂₅-OH (1: 3)

Samples 2 to 20

Samples 2 to 20 were prepared as Sample 1 except that in the layers 3 and 5 are each 50 wt .-% of the gelatin by 0.6 g of each in Table 1 polymer was replaced and in the layer 4 if appropriate, the dye stabilizers specified in Table 1 are added were. Compounds V-1 and V-2 are comparative polymers.  

Table 1

(V: comparison, E: according to the invention)

The samples are then placed behind a graduated gray wedge and a Green filter exposed and then processed as follows:

a) Color developer - 45 s - 35 ° C Tetraethylene glycol | 20.0 g N, N-diethyl 4.0 g N-ethyl-N- (2-methanesulfonamidoethyl) -4-amino-3-methyl benzene sulphate 5.0 g potassium 0.2 g potassium carbonate 30.0 g Polymäleinsäureanhydrid 2.5 g hydroxyethane 0.2 g Whitening agent (4,4'-diaminstilbene sulfonic acid derivative) 2.0 g potassium 0.02 g

make up to 1000 ml with water; pH with KOH or H₂SO₄ to pH Set 10.2.

b) Bleach-fix bath - 45 s - 35 ° C Ammonium thiosulphate | 75.0 g sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 45.0 g

make up to 1000 ml with water; pH with ammonia (25%) or Adjust acetic acid to pH 6.0.

c) watering - 2 min - 33 ° C d) drying

For the samples, scratch resistance (NKF) and swelling factor (QF) were as follows certainly:

The photographic recording materials are located on the layer side upwards on a horizontal sample holder in a with water of 100 DH and 38 ° C filled tub. The sample to be measured is completely water covered. After 5 minutes Quelldauer a firmly locked steel ball (⌀ 3.2 mm) at a speed of v = 30 mm / s over the surface of the test object. The force (in N), with the above steel ball on presses the outermost protective layer of the sample is adjusted so that they on a Measuring section of 20 cm in length increases continuously from 0 to 10 N. As a measure of the wet scratch resistance of the photographic material (in N) becomes indicated the force at which the first layer after sample drying injury on the test section by means of the human eye is recognizable.

Furthermore, the swelling factor of the samples becomes a measure of the crosslinking of the layer measured

In addition, the samples were the light of a normalized for daylight Xenon lamp (30 klux) exposed and irradiated with 15 × 10⁶ lx · h; after that became the percent density decrease and the gb fog increase (Table 2).

Table 2

(V: comparison, E: according to the invention)

Table 2 shows that the vinyl alcohol copolymers of the invention, the mecha positively influence the niche properties of the layer structure; the comparison compounds P-1 and P-2, on the other hand, worsen it. The improvement of Light stability is only moderate in all cases. As can be seen from Table 2, the Light stability of the purple dye only by the invention verbin tion of the formulas (II) and (III) significantly increased. The comparative compound ST-4, In contrast, ST-6 and ST-7 cause virtually no or little improvement.

Furthermore, Table 2 shows the advantageous use of the combination of Compounds of the formula (II) with those of the formula (IV) in comparison to the Combination ST-5 with IV-3. In the latter case, the combination with CO-PVA a significantly lower improvement in light stability than in the case of the o.g. inventive combination.

Table 2 also shows the significant reduction in yellowing by the Use of the vinyl alcohol copolymers.  

Example 2 Samples 21 to 35

Samples 21 and 35 are prepared as samples 1 to 20 with the Difference that the magenta coupler M-1 in layer 4 by the same amount given the specified in Table l purple coupler is replaced.

Table 3

(V: comparison, E: according to the invention)

The samples were exposed and processed as described in Example 1.

Then they became the light of a normalized xenon lamp (90 klux) and irradiated with 15 × 106 1x.h; after that the process became Tual density decrease measured (Table 4).  

Table 4

(V: comparison, E: according to the invention)

As Table 4 shows, the compounds of the invention improve the formula (II) or (III) in combination with the vinyl alcohol Copolymers regardless of Magentakuppler used the light stability much better than the comparative compounds ST-4, ST-5 and ST-6. On Comparison of Samples 21 to 24 also shows that the synergistic effect of Inventive vinyl alcohol copolymers with inventive compound of the formula (II) is considerably stronger than with the comparative compound ST-6.

Claims (2)

A color photographic silver halide material comprising a support, at least one silver halide emulsion layer containing a pyrazolotriazole magenta coupler and at least one further layer, characterized in that the at least one further layer is a CO-PVA of the formula (I) contains, in which
k 50 to 99% by weight,
from 0 to 49% by weight,
m is 1 to 40% by weight, and
j is 0 to 49% by weight,
M is a copolymerized comonomer, R₁, R₂ is hydrogen or alkyl,
R₃ is an acidic group, and
B denotes a chemical bond or a bridge member,
and the at least one silver halide emulsion layer containing the pyrazolotriazole magenta coupler contains at least one compound of formula (II) or (III), wherein
R 21 H, primary or secondary alkyl, acylamino,
R²² alkyl, acyl, acylamino,
R²⁴H, alkyl,
m, n is 0, 1, 2,
wherein adjacent R²¹ to R²³ may form a 5- or 6-membered ring and a plurality of R²¹ to R²³ may be the same or different; wherein R³² alkyl, acyl, chlorine, acylamino,
R³³ H, alkyl of 1 to 4 carbon atoms, hydroxy,
R³⁴H, alkyl, acyl,
o 0, 1, 2, 3, 4 and
p is 2, 3, 4
adjacent radicals -OR³¹ and R³² form a 5- or 6-membered ring and a plurality of radicals R³¹ to R³⁴ may be the same or different. The silver halide color photographic material of claim 1, wherein
B has the meaning -L₁- (L₂) n- (L₃) _o -hat, wherein
L₁, L₃ is a common organic link,
L₂-COO-, -OC-O-, -CO-NH-, -NH-CO-, SO₂-NH-, -NH-SO₂-, -NH-CO-O- or -NH-CO-NH- and
n and o are 0 or 1 and
L₁ is bonded directly to M₁.