EP0627656A2 - Photographic recording material - Google Patents

Abstract

A photographic silver-halide material having at least one photosensitive layer which contains, in at least one layer, a compound of the formula (I) in an amount of at least 10 mg/m<2>: <IMAGE> in which k is from 50 to 99 % by weight, preferably from 70 to 97 % by weight, l is from 0 to 49 % by weight, preferably from 0 to 27 % by weight, m is from 1 to 40 % by weight, preferably from 3 to 15 % by weight, and j is from 0 to 49 % by weight, preferably from 0 to 27 % by weight, M is a copolymerised comonomer, M1 is <IMAGE> or <IMAGE> , M2 is <IMAGE> , R1 and R2 are hydrogen or alkyl, R3 is an acidic group, and B is a chemical bond or a bridge; and which has been cured by means of an instant or rapid curing agent (hardener), is distinguished by improved wet scratch resistance and a longer shelf life.

Description

The invention relates to a photographic recording material which is improved in terms of wet scratch resistance and storage stability.

Photographic materials essentially contain gelatin as a binder. The binder-containing layers are crosslinked with a crosslinking or hardening agent in order to impart sufficient stability and strength to the materials in the dry and wet state and during processing. Formaldehyde, formaldehyde hydrates or formaldehyde releasers were previously used as curing agents (US Pat. No. 2,739,059). After it was shown that aldehydes damage the color couplers contained in color materials, new hardeners were sought. Hardeners were then developed which do not have the disadvantages mentioned and which can be used in modern multiple pouring systems, such as cascade and curtain casters. These hardeners work very quickly and are referred to as quick and instant hardeners.

The present invention preferably relates to photographic materials which are hardened with these hardeners, in particular instant hardeners.

Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting, at the latest after 24 hours, preferably after 8 hours at the latest, to the extent that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs. Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

The quick and instant hardeners have the disadvantage that due to their short hardening time the wet scratch resistance is too low and the swelling factor is too high.

Another disadvantage of using gelatin as a binder is that the stability of the photographic material, in particular the light stability, is unsatisfactory.

US 4 912 023 describes the use of water-soluble polyacrylic acid / polyvinyl alcohol block copolymers as a binder additive in photographic materials. These connections fix optical brighteners better in the photographic materials.

A disadvantage of these compounds is that the hardening of these layers with instant hardening agents is adversely affected and the wet strength and swelling factor do not meet the requirements placed on modern photographic material.

The object of the present invention was therefore to provide a binder or binder additive for gelatin which enables hardening of the photographic layers with instant hardeners and avoids the disadvantages mentioned.

It has now been found that certain vinyl alcohol copolymers, hereinafter referred to as CO-PVA, can achieve this object.

worin

• k 50 bis 99 Gew.-%, vorzugsweise 70 bis 97 Gew.-%,
• I 0 bis 49 Gew.-%, vorzugsweise 0 bis 27 Gew.-%,
• m 1 bis 40 Gew.-%, vorzugsweise 3 bis 15 Gew.-% und
• j 0 bis 49 Gew.-%, vorzugsweise 0 bis 27 Gew.-%,
• M ein einpolymerisiertes Comonomer
• Mi
  
• M₂
  
• R₁, R₂ Wasserstoff oder Alkyl,
• R₃ eine saure Gruppe, vorzugsweise -COOH, -SO₃H oder -P0₃H₂ und
• B eine chemische Bindung oder ein Brückenglied bedeuten,

und das mit einem Sofort- oder Schnellhärter gehärtet ist. B hat vorzugsweise die Bedeutung
-L₁-(L₂)_n-(L₃)_o-,
worin

• Li , L₃ ein übliches organisches Bindeglied, insbesondere einen gegebenenfalls substituierten Alkylen-, Arylen- oder Aralkylenrest mit maximal 18 C-Atomen,
• L₂ -COO-, -OC-O-, -CO-NH-, -NH-CO-, -S0₂-NH-, -NH-S0₂-, -NH-CO-O-oder -NH-CO-NH- und n und o 0 oder 1 bedeuten.

The invention therefore relates to a photographic recording material which contains at least one compound of the formula (I) in an amount of at least 10 mg / m ² in at least one layer:

wherein

• k 50 to 99% by weight, preferably 70 to 97% by weight,
• I 0 to 49% by weight, preferably 0 to 27% by weight,
• m 1 to 40 wt .-%, preferably 3 to 15 wt .-% and
• j 0 to 49% by weight, preferably 0 to 27% by weight,
• M is a polymerized comonomer
• Wed
  
• M ₂
  
• R ₁ , R _{2 are} hydrogen or alkyl,
• R _{3 is} an acidic group, preferably -COOH, -SO ₃ H or -P0 ₃ H ₂ and
• B represents a chemical bond or a bridge member,

and that is hardened with an instant or quick hardener. B preferably has the meaning
-L ₁ - (L ₂ ) _n - (L ₃ ) _o -,
wherein

• Li, L _{3 is} a conventional organic link, in particular an optionally substituted alkylene, arylene or aralkylene radical with a maximum of 18 carbon atoms,
• L ₂ -COO-, -OC-O-, -CO-NH-, -NH-CO-, -S0 ₂ -NH-, -NH-S0 ₂ -, -NH-CO-O- or -NH-CO -NH- and n and o represent 0 or 1.

Here, L ₁ is directly attached to M. ₁

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

Alkyl radicals R ₁ and R ₂ have in particular 1 to 4 carbon atoms.

The phenylene, arylene and aralkylene radicals L ₁ and L ₃ are preferably not further substituted.

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

Examples of such comonomers are esters and amides of acrylic acid and their derivatives e.g. 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 methacrylate and methylenebisacrylamide), vinyl acetate and vinyl acetate (for example vinyl propyl acetate) , Acyl nitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene, vinyl toluene, divinylbenzene, vinyl acetophenone, styrene sulfonic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), ester of maleic acid, N-vinyl-2-pyrrolidone, N-vinyl vinyl , 2-vinyl and 4-vinyl pyridine as well as acrylic acid and methacrylic acid.

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

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

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

The CO-PVA can have a statistical distribution of the comonomers or can be graft or block copolymers. In particular, they are copolymers with polyacrylic acid blocks.

Preferably 50 mg to 5 g / m ² of CO-PVA is used in the at least one layer.

Die erfindungsgemäßen CO-PVA können ohne weitere Bindemittel in fotografischen Materialien als Bindemittel eingesetzt werden. Vorzugsweise werden aber Abmischungen mit bekannten Bindemitteln wie Gelatine, Polyvinylpyrrolidon, Polyvinylalkohol verwendet. Besonders bevorzugt sind Abmischungen mit Gelatine. Bei Verwendung von CO-PVA-Gelatineabmischungen wird im allgemeinen ein Gewichtsverhälthis von CO-PVA : Gelatine von 90:10 bis 5:95, vorzugsweise von 60:40 bis 10:90, eingestellt.Examples of polymers according to the invention are:

The CO-PVA according to the invention can be used as a binder in photographic materials without further binders. However, mixtures with known binders such as gelatin, polyvinylpyrrolidone, polyvinyl alcohol are preferably used. Mixtures with gelatin are particularly preferred. When using CO-PVA gelatin mixtures, a weight ratio of CO-PVA: gelatin is generally set from 90:10 to 5:95, preferably from 60:40 to 10:90.

The PVA copolymers according to the invention can be used in all binder-containing layers of photographic materials. It is also possible to use the copolymer according to the invention in only one or a few layers. For example, it is possible to crosslink this layer more strongly than the others by adding the CO-PVA in only one layer of the layer structure.

The layers can be hardened differently by adding different amounts of CO-PVA to different gelatin-containing layers. This makes it possible to set a hardening profile.

The CO-PVA are preferably used in at least two layers of the photographic material. In order to improve the light stability of dyes, a CO-PVA layer should be provided above and a CO-PVA layer below the layer containing the dye to be protected. It is irrelevant whether the layers containing CO-PVA are emulsion, substrate, intermediate or protective layers.

This is particularly true when the photographic material contains a pyrazoloazole compound as a purple coupler. In this case, a CO-PVA-containing layer is preferably applied over and a CO-PVA-containing layer under the layer containing the pyrazoloazole coupler.

The stabilization of the purple dye obtained after processing can be improved by adding special dye stabilizers to the layer containing the purple coupler.

The dye stabilizers listed below are also suitable for stabilizing the other dyes, especially for the yellow dye.

Suitable dye stabilizers belong to the following classes St-I to St-IV:

At least one compound of classes St-V to St-VIII is preferably added to the material according to the invention in order to reduce the color and storage veil.

• Ri, R₈ und R₉ H, Alkyl, Aryl oder einen unter alkalischen Bedingungen abspaltbaren Rest,
• R₂, R₃, R₄ H, - COOH, - SO₃H, - SO₂H, Alkyl, Aryl, Acyl, Alkylsulfonyl, Arylsulfonyl, Alkenyl, Sulfamoyl, Acylamino, Alkylthio, Arylthio, Ureido, Cycloalkyl, Carbamoyl, Carbamoyloxy oder Alkoxycarbonylamino,
• Rs, R₆ OH, OR₁ oder R₂
• R₃ und R₄ können auch gemeinsam mit den beiden Atomen des Phenylrestes, an den sie gebunden sind, einen ankondensierten 5 - oder 6- gliedrigen carbocyclischen Ring bilden,
• R₇ gegebenenfalls durch OH, OR₁, R₂, Alkoxycarbonyl, Dialkylamino oder Alkoxycarbonyl substituiertes Aryl,
• R₁₀, R₁₁, R₁₂, R₁₃ OH, OR₁, R₂, Alkoxycarbonyl, Dialkylamino, Alkoxycarbonyloxy oder Halogen,
• R₁₄ Alkyl, Cycloalkyl, Aryl oder Alkenyl,
• R₁₅ H, Acyl, Carbamoyl, Alkoxycarbonyl oder R₁₄,
• R₁₆, R₁₇, R₁₈ Alkyl, Cycloalkyl, Alkenyl, Alkinyl, Aryl, Heterocyclyl, wobei Aryl und Heterocyclyl auch benzokondensiert sein können,
• R₁₉, R₂₀, R₂₁ und R₂₂ H, Alkyl, Aryl, Alkoxycarbonyl, Aryloxycarbonyl oder Carbamoyl, wobei die Summe der C-Atome von R₁₉, R₂₀, R₂₁ und R₂₂ wenigstens 8 ist und zwei Reste R₁₉, R₂₀, R₂₁ und R₂₂ einen 5-bis 7- gliedrigen Ring bilden können,
• Z₁, Z₂ gegebenenfalls durch OH, OR₁, R₂, Alkoxycarbonyl, Dialkylamino oder Alkoxycarbonyloxy substituiertes C₁-C₃-Alkylen, wobei die Summe der C-Atome in den Alkylenketten von Z₁ und Z₂ 3 bis 6 beträgt,
• A gegebenenfalls substituiertes C₁-C₆-Alkylen, -O-, S(O)p oder
  
• B H, Alkyl, Aryl, Heterocyclyl, Acyl, Alkylsulfonyl oder Arylsulfonyl,
• L₁ eine einfache Bindung, Alkylen, - O-, -S-, -NH- oder Alkylimino,
• L₂ Carbonyl, Sulfinyl, Sulfonyl, Thiocarbonyl, Hydroxyphosphoryl, Iminomethandiyl, Dialkylsilandiyl,
• X₁ Aryloxy, Alkyloxy, Heterocyclyloxy, Alkyltho, Arylthio, Heterocyclylthio, Halogen,
• X₂ -S0₂ M, - SH, Alkylamino, Azacycloalkyl,
• M Wasserstoff, Alkalimetall, gegebenenfalls substituiertes Ammonium, Methylenhydrazino, Carbonylhydrazo, Sulfonylhydrazo, Carbonylacylmethyl, Carbonylcarbonyldioxymethyl,
• Y
  
• R₂₄, R₂₅, R₆ H, Alkyl, Aryl, Heterocyclyl, Acyl, Alkylsulfonyl, Arylsulfonyl, Cyano oder R₂₅ und R₂₆ zusammen die resilichen Glieder eines Ringes,
• n 0, 1 oder 2
• m 0, wenn X₁ Halogen ist, und 1, wenn X₁ ungleich Halogen ist,
• p 0, 1 oder 2,
• R₂₃ H, Alkyl, Aryl, Acyl, Alkylsulfonyl, Alkoxycarbonyl, Aryloxycarbonyl,

In the formulas St-I to St-VIII:

• Ri, R ₈ and R ₉ H, alkyl, aryl or a radical which can be split off under alkaline conditions,
• R ₂ , R ₃ , R ₄ H, - COOH, - SO ₃ H, - SO ₂ H, alkyl, aryl, acyl, alkylsulfonyl, arylsulfonyl, alkenyl, sulfamoyl, acylamino, alkylthio, arylthio, ureido, cycloalkyl, carbamoyl, carbamoyloxy or alkoxycarbonylamino,
• Rs, R ₆ OH, OR ₁ or R ₂
• R ₃ and R ₄ can also form, together with the two atoms of the phenyl radical to which they are attached, a fused-on 5- or 6-membered carbocyclic ring,
• R ₇ aryl optionally substituted by OH, OR ₁ , R ₂ , alkoxycarbonyl, dialkylamino or alkoxycarbonyl,
• R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ OH, OR ₁ , R ₂ , alkoxycarbonyl, dialkylamino, alkoxycarbonyloxy or halogen,
• R ₁₄ alkyl, cycloalkyl, aryl or alkenyl,
• R ₁₅ H, acyl, carbamoyl, alkoxycarbonyl or R ₁₄ ,
• R ₁₆ , R ₁₇ , R ₁₈ alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heterocyclyl, where aryl and heterocyclyl can also be benzofused,
• R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ H, alkyl, aryl, alkoxycarbonyl, aryloxycarbonyl or carbamoyl, the sum of the carbon atoms of R ₁₉ , R ₂₀ , R ₂₁ and R _{22 being} at least 8 and two radicals R ₁₉ , R ₂₀ , R ₂₁ and R _{22 can form} a 5 to 7-membered ring,
• Z ₁ , Z ₂ optionally substituted by OH, OR ₁ , R ₂ , alkoxycarbonyl, dialkylamino or alkoxycarbonyloxy C ₁ -C ₃ alkylene, the sum of the C atoms in the alkylene chains of Z ₁ and Z _{2 being} 3 to 6,
• A optionally substituted C ₁ -C ₆ alkylene, -O-, S (O) p or
  
• BH, alkyl, aryl, heterocyclyl, acyl, alkylsulfonyl or arylsulfonyl,
• L _{1 is} a simple bond, alkylene, - O-, -S-, -NH- or alkylimino,
• L ₂ carbonyl, sulfinyl, sulfonyl, thiocarbonyl, hydroxyphosphoryl, iminomethanediyl, dialkylsilanediyl,
• X ₁ aryloxy, alkyloxy, heterocyclyloxy, alkyltho, arylthio, heterocyclylthio, halogen,
• X ₂ -S0 ₂ M, - SH, alkylamino, azacycloalkyl,
• M hydrogen, alkali metal, optionally substituted ammonium, methylene hydrazino, carbonyl hydrazo, sulfonyl hydrazo, carbonyl acyl methyl, carbonyl carbonyl dioxymethyl,
• Y
  
• R ₂₄ , R ₂₅ , R ₆ H, alkyl, aryl, heterocyclyl, acyl, alkylsulfonyl, arylsulfonyl, cyano or R ₂₅ and R ₂₆ together form the resilient members of a ring,
• n 0, 1 or 2
• m 0 if X _{1 is} halogen and 1 if X _{1 is} not halogen,
• p 0, 1 or 2,
• R ₂₃ H, alkyl, aryl, acyl, alkylsulfonyl, alkoxycarbonyl, aryloxycarbonyl,

Farbstoffstabilisatoren werden bevorzugt in einer Menge von 0,05 bis 1 g/m² eingesetzt. Diese Menge kann auf eine oder mehrere Schichten verteilt sein.Arylsulfonyl, carbamoyl or alkoxycarbonyl. Alkyl, aryl, cycloalkyl and heterocyclyl radicals can be further substituted. The following compounds are suitable examples of groups St-I to St-VIII:

Dye stabilizers are preferably used in an amount of 0.05 to 1 g / m ² . This amount can be distributed over one or more layers.

The CO-PVA can be synthesized by the methods known from the literature (e.g. US 2,739,059). To introduce the amino group, for example, a polymer with vinyl alcohol structural elements can be reacted with aminoalkyl aldehyde acetal. The vinyl alcohol-vinylamine copolymers can be prepared by the method described in DE-33 26 187.

• 12 g Polyvinylalkohol mit einem Molekulargewicht von 70.000 wurden in 230 g Wasser gelöst und mit 15 g konzentrierter Salzsäure versetzt. Dann wurden gleichzeitig in 20 Minuten 3,5 g 4-Carboxybenzaldehyd in 75 ml Isopropanol und 35 g konzentrierter Salzsäure zugegeben und bei 30 ° C gerührt. Anschließend wurden 3,3 g Aminoacetaldehyddimethylacetal in 25 ml Isopropanol zugetropft und 3 Stunden auf 70 ° C erwärmt. Danach wurde mit Sodalösung auf pH 6 eingestellt und die Lösung dialysiert.

The synthesis of a CO-PVA copolymer with amino and carboxyl groups is described below by way of example:

• 12 g of polyvinyl alcohol with a molecular weight of 70,000 were dissolved in 230 g of water and 15 g of concentrated hydrochloric acid were added. Then 3.5 g of 4-carboxybenzaldehyde in 75 ml of isopropanol and 35 g of concentrated hydrochloric acid were added simultaneously in 20 minutes and the mixture was stirred at 30 ° C. Then 3.3 g of aminoacetaldehyde dimethyl acetal in 25 ml of isopropanol were added dropwise and the mixture was heated at 70 ° C. for 3 hours. The pH was then adjusted to 6 using sodium carbonate solution and the solution was dialyzed.

According to the invention, the CO-PVA and CO-PVA gelatin mixtures are hardened with quick and instant hardeners.

According to the invention, rapid and instant hardeners are understood to be those compounds which, in the test described below, bring about a layer melting point of at least 95 ° C. Immediate hardeners also meet the definition given at the beginning.

Hardening test:

A coating solution containing gelatin and, based on the gelatin, 1% by weight of the hardening agent is poured onto a base, for example paper coated on both sides with polyethylene or cellulose triacetate film. The coating is dried at pH 6.2 and 35 _° C and then immersed in a water bath which is continuously heated from 20 ° C to 100 ° C over at least 5 minutes. The temperature, where the layer runs off the base, recognizable by the streaking, is referred to as the melting point.

When using compounds according to the invention, no melting can be seen at 100 ° C. If the same amount of formaldehyde is used as the hardening agent, delamination occurs at 75 ° C.

The curing agents can be those which are incorporated into the binder, for example hydroxydichlorotriazine or divinyl sulfone hardeners, or those which bring about a crosslinking of the binders without being incorporated themselves, e.g. carboxyl group activating hardener. The latter are preferably used.

worin

• R₁ Alkyl, Aryl oder Aralkyl bedeutet,
• R₂ die gleiche Bedeutung wie R₁ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel
  
  
  verknüpft ist, oder
• R₁ und R₂ zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin-oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
• R₃ für Wasserstoff, Alkyl, Aryl, Alkoxy, - NR₄-COR₅, - (CH₂)-_m-NR₈R₉,-(CH₂)_n-CONR₁₃R₁₄ oder
  
  
  oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei
• R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈ und R₁₉ Wasserstoff oder C₁-C₄-Alkyl,
• R₅ Wasserstoff, C₁-C₄-Alkyl oder NR₆ R₇,
• R₈ -COR₁₀,
• R₁₀ NR₁₁R₁₂,
• R¹¹ C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
• R₁₂ Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
• R₁₃ Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
• R₁₆ Wasserstoff, C₁-C₄-Alkyl, COR₁₈ oder CONHR₁₉,
• m eine Zahl 1 bis 3,
• n eine Zahl 0 bis 3,
• p eine Zahl 2 bis 3 und
• Y O oder NR₁₇ bedeuten oder
• R₁₃ und R₁₄ gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin-oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
• Z die zur Vervollständigung eines 5-oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und
• X⊖ ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;
  
  
  worin
• R₁, R₂, R₃ und X⊖ die für Formel (a) angegebene Bedeutung besitzen;
  
  
  worin
• R₂₀, R₂₁, R₂₂ C₁-C_2o-Alkyl, C₆-C₂₀-Aralkyl, C₅-C₂₀-Aryl, jeweils unsubstituiert oder durch Halogen, Sulfo, C₁-C₂₀-Alkoxy, N,N-Di-C₁-C₄-alkyl-substituiertes Carbamoyl und im Falle von Aralkyl und Aryl durch C₁-C₂o-Alkyl substituiert,
• R₂₄ eine durch ein nucleophiles Agens abspaltbare Gruppe bedeuten und
• X⊖ die für Formel (a) angegebene Bedeutung besitzt, wobei 2 oder 4 der Substituierten R_2o, R₂₁, R₂₂ und R₂₃ zusammen mit einem Stickstoffatom oder der Gruppe
  
  
  gegebenenfalls unter Einschluß weiterer Heteroatome wie O oder N, auch zu einem oder zwei gesättigten 5- bis 7-gliedrigen Ringen vereint sein können;
• R₂₅-N=C=N-R₂₆ (d), worin
• R₂₅ C₁-C₁₀-Alkyl, C₅-C₈ -Cycloalkyl, C₃-C₁₀-Alkoxyalkyl oder C₇-C₁₅-Aralkyl bedeutet,
• R₂₆ die Bedeutung von R₂₅ besitzt oder für einen Rest der Formel
  
  
  steht, wobei
• R₂₇ C₂-C₄-Alkylen und
• R₂₈, R₂₉ und R₃₀ C₁-C₆-Alkyl bedeuten, wobei einer der Reste R₂₈, R₂₉ und R₃₀ durch eine Carbamoylgruppe oder eine Sulfogruppe substituiert sein kann und zwei der Reste R₂₈, R₂₉ und R₃₀ zusammen mit dem Stickstoffatom zu einem gegebenenfalls substituierten heterocyclischen Ring, beispielsweise einen Pyrrolidin-, Piperazin- oder Morpholinring verknüpft sein können, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann, und
• X⊖ die für die Formel (a) angegebene Bedeutung besitzt;
  
  
  worin
• X⊖ die für Formel (a) angegebene Bedeutung hat,
• R₂₄ die für Formel (c) angegebene Bedeutung besitzt,
• R₃₁ C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl oder C₇-C₁₅-Aralkyl, jeweils unsubstituiert durch Carbamoyl, Sulfamoyl oder Sulfo substituiert,
• R₃₂ und R₃₃ Wasserstoff, Halogen, Acylamino, Nitro Carbamoyl, Alkoxy, Alkyl, Alkenyl, Aryl oder Aralkyl oder gemeinsam die restlichen Glieder eines mit dem Pyridiniumring kondensierten Ringes, insbesondere eines Benzolringes, bedeuten,
  wobei
• R₂₄ und R₃₁ miteinander verknüpft sein können, wenn
• R₂₄ eine Sulfonyloxygruppe ist;
  
  
  worin
• R_i, R₂ und X⊖ die für Formel (a) angegebene Bedeutung besitzen und
• R₃₄ C₁-C₁₀-Alkyl, C₆-C₁₄-Aryl oder C₇-C₁₅-Aralkyl bedeutet;
  
  
  worin
• R_i, R₂ und X⊖ die für Formel (a) angegebene Bedeutung besitzen,
• R₃₅ Wasserstoff, Alkyl, Aralkyl, Aryl, Alkenyl, R₃₈0-, R₃₉R_4oN-, R₄₁ R₄₂C = N-oder R₃₈ S-,
• R₃₆ und R₃₇ Alkyl, Aralkyl, Aryl, Alkenyl, R₄₃-CO-, R₄₄-S0₂-oder R₄s-N = _N-oder gemeinsam mit dem Stickstoffatom die restlichen Glieder eines heterocyclischen Ringes oder die Gruppierung
  
• R₃₈, R₃₉, R₄₀, R₄₁, R₄₂, R₄₃, R₄₄ und R₄₅ Alkyl, Aralkyl, Alkenyl, R₄₁ und R₄₂ darüber hinaus Wasserstoff, R₃₉ und R₄o bzw. R₄₁ und R₄₂ darüber hinaus die restlichen Glieder eines 5-oder 6-gliedrigen, gesättigten carbocyclischen oder heterocyclischen Ringes bedeuten;
  
  
  worin
• R₄₆ Wasserstoff, Alkyl oder Aryl,
• R₄₇ Acyl, Carbalkoxy, Carbamoyl oder Aryloxycarbonyl;
• R₄₈ Wasserstoff oder R₄₇,
• R₄₉ und R_so Alkyl, Aryl, Aralkyl oder gemeinsam mit dem Stickstoffatom die restlichen Glieder eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann, und X⊖ die für Formel (a) angegebene Bedeutung besitzt;
  
  
  worin
• R₅₁ gegebenenfalls eine ein- oder mehrfach durch -O-, -NR₅₂-, -CONH-, -NHCO-, -NHCONH-, -S0₂-, -S0₂NH-, -NHS0₂- oder Phenylen unterbrochene Alkylengruppe mit 1 bis 6 C-Atomen oder einen gegebenenfalls substituierten heteroaromatischen Ring, der mindestens q Ring-C-Atome und mindestens ein Ring-O-, Ring-S- oder Ring-N-Atom enthält,
• Rs₂ Wasserstoff oder C₁-C₄-Alkyl und
• q eine ganze Zahl ≧2 bedeuten.

Suitable examples of quick hardeners and instant hardeners are compounds of the following general formulas:

wherein

• R ₁ denotes alkyl, aryl or aralkyl,
• R _{2 has} the same meaning as R ₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond being with a group of the formula
  
  
  is linked, or
• R ₁ and R ₂ together denote the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, it being possible for the ring to be substituted, for example, by C ₁ -C ₃ alkyl or halogen,
• R ₃ for hydrogen, alkyl, aryl, alkoxy, - NR ₄ -COR ₅ , - (CH ₂ ) - _m -NR ₈ R ₉ , - (CH ₂ ) _n -CONR ₁₃ R ₁₄ or
  
  
  or a bridge link or a direct bond to a polymer chain, wherein
• R ₄ , R ₆ , R ₇ , R ₉ , R ₁₄ , R ₁₅ , R ₁₇ , R ₁₈ and R _{19 are} hydrogen or C ₁ -C ₄ alkyl,
• R _{5 is} hydrogen, C ₁ -C ₄ alkyl or NR ₆ R ₇ ,
• R ₈ -COR ₁₀ ,
• R ₁₀ NR ₁₁ R ₁₂ ,
• R ^{11 is} C ₁ -C ₄ alkyl or aryl, in particular phenyl,
• R _{12 is} hydrogen, C ₁ -C ₄ alkyl or aryl, in particular phenyl,
• R _{13 is} hydrogen, C ₁ -C ₄ alkyl or aryl, in particular phenyl,
• R _{16 is} hydrogen, C ₁ -C ₄ alkyl, COR ₁₈ or CONHR ₁₉ ,
• m is a number 1 to 3,
• n is a number 0 to 3,
• p is a number 2 to 3 and
• YO or NR ₁₇ mean or
• R ₁₃ and R ₁₄ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C ₁ -C ₃ alkyl or halogen,
• Z the C atoms and. Necessary for the completion of a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring
• X⊖ is an anion which is omitted if an anionic group is already linked to the rest of the molecule;
  
  
  wherein
• R ₁ , R ₂ , R ₃ and X⊖ have the meaning given for formula (a);
  
  
  wherein
• R ₂₀ , R ₂₁ , R ₂₂ C ₁ -C _2o alkyl, C ₆ -C ₂₀ aralkyl, C ₅ -C ₂₀ aryl, in each case unsubstituted or by halogen, sulfo, C ₁ -C ₂₀ alkoxy, N, N-di-C ₁ -C ₄ -alkyl-substituted carbamoyl and, in the case of aralkyl and aryl, substituted by C ₁ -C ₂ o-alkyl,
• R _{24 is} a group which can be split off by a nucleophilic agent and
• X⊖ has the meaning given for formula (a), where 2 or 4 of the substituents R _2o , R ₂₁ , R ₂₂ and R ₂₃ together with a nitrogen atom or the group
  
  
  optionally including other heteroatoms such as O or N, can also be combined to form one or two saturated 5- to 7-membered rings;
• R ₂₅ -N = C = NR ₂₆ (d), wherein
• R _{25 is} C ₁ -C ₁₀ alkyl, C ₅ -C ₈ cycloalkyl, C ₃ -C ₁₀ alkoxyalkyl or C ₇ -C ₁₅ aralkyl,
• R _{26 has} the meaning of R ₂₅ or for a radical of the formula
  
  
  stands, where
• R ₂₇ C ₂ -C ₄ alkylene and
• R ₂₈ , R ₂₉ and R _{30 are} C ₁ -C ₆ alkyl, it being possible for one of the radicals R ₂₈ , R ₂₉ and R _{30 to} be substituted by a carbamoyl group or a sulfo group and two of the radicals R ₂₈ , R ₂₉ and R ₃₀ may be linked together with the nitrogen atom to form an optionally substituted heterocyclic ring, for example a pyrrolidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C ₁ -C ₃ alkyl or halogen, and
• X⊖ has the meaning given for the formula (a);
  
  
  wherein
• X⊖ has the meaning given for formula (a),
• R _{24 has} the meaning given for formula (c),
• R _{31 is} C ₁ -C ₁₀ alkyl, C ₆ -C ₁₅ aryl or C ₇ -C ₁₅ aralkyl, in each case unsubstituted by carbamoyl, sulfamoyl or sulfo,
• R ₃₂ and R _{33 represent} hydrogen, halogen, acylamino, nitro carbamoyl, alkoxy, alkyl, alkenyl, aryl or aralkyl or together the remaining members of a ring condensed with the pyridinium ring, in particular a benzene ring,
  in which
• R ₂₄ and R _{31 may} be linked to each other if
• R _{24 is} a sulfonyloxy group;
  
  
  wherein
• R _i , R ₂ and X⊖ have the meaning given for formula (a) and
• R _{34 is} C ₁ -C ₁₀ alkyl, C ₆ -C ₁₄ aryl or C ₇ -C ₁₅ aralkyl;
  
  
  wherein
• R _i , R ₂ and X⊖ have the meaning given for formula (a),
• R _{35 is} hydrogen, alkyl, aralkyl, aryl, alkenyl, R ₃₈ 0-, R ₃₉ R _4o N-, R ₄₁ R ₄₂ C = N- or R ₃₈ S-,
• R ₃₆ and R ₃₇ alkyl, aralkyl, aryl, alkenyl, R ₄₃ -CO-, R ₄₄ -S0 ₂ - or R ₄ sN = _N - or together with the nitrogen atom the remaining members of a heterocyclic ring or the grouping
  
• R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ and R ₄₅ alkyl, aralkyl, alkenyl, R ₄₁ and R ₄₂ furthermore hydrogen, R ₃₉ and R ₄ o or R ₄₁ and R ₄₂ furthermore denotes the remaining members of a 5- or 6-membered, saturated carbocyclic or heterocyclic ring;
  
  
  wherein
• R _{46 is} hydrogen, alkyl or aryl,
• R ₄₇ acyl, carbalkoxy, carbamoyl or aryloxycarbonyl;
• R _{48 is} hydrogen or R ₄₇ ,
• R ₄₉ and R _are alkyl, aryl, aralkyl or, together with the nitrogen atom, the remaining members of an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being substituted, for example, by C ₁ -C ₃ alkyl or halogen can be, and X⊖ has the meaning given for formula (a);
  
  
  wherein
• R ₅₁ optionally has an alkylene group which is interrupted one or more times by -O-, -NR ₅₂ -, -CONH-, -NHCO-, -NHCONH-, -S0 ₂ -, -S0 ₂ NH-, -NHS0 ₂ - or phenylene 1 to 6 carbon atoms or an optionally substituted heteroaromatic ring which contains at least q ring C atoms and at least one ring O, ring S or ring N atom,
• Rs _{2 is} hydrogen or C ₁ -C ₄ alkyl and
• q is an integer ≧ 2.

worin

• r eine Zahl 0 bis 3 und
• R₅₃ C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Phenyl bedeutet.

The heteroaromatic ring represented by Rs ₁ is, for example, a triazole, thiadiazole, oxadiazole, pyridine, pyrrole, quinoxaline, thiophene, furan, pyrimidine or triazine ring. In addition to the at least two vinylsulfonyl groups, it can optionally contain further substituents and optionally fused-on benzene rings, which in turn can also be substituted. Examples of heteroaromatic rings (R ₅₁ ) are listed below:

wherein

• r is a number from 0 to 3 and
• R _{53 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or phenyl.

Further examples of R ₅₁ are -CH ₂ -, -CH ₂ -O-CH ₂ -, -CH ₂ -CONH-CH ₂ -, - CH ₂ -NHCONH-CH ₂ -.

Finally, the compounds described in Japanese Patent Laid-Open Nos. 38 540/75, 93 470/77, 43 353/81 and 113 929/83 and in US Pat. No. 3,321,313 are suitable as immediate hardening agents.

Alkyl, unless defined otherwise, in particular optionally substituted by halogen, hydroxy, sulfo, C ₁ -C ₂ -alkoxy-substituted C ₁ -C ₂ -alkyl.

Unless otherwise defined, aryl is in particular C ₆ -C ₁₄ aryl, aralkyl, optionally substituted by halogen, sulfo, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, unless otherwise defined, is in particular by halogen C ₁ -C ₂₀ alkoxy, sulfo or C ₁ -C ₂₀ alkyl substituted C ₇ -C ₂₀ aralkyl, alkoxy, unless otherwise defined, is in particular C ₁ -C ₂₀ alkoxy.

X⊖ is preferably a halide ion such as Cl ^e , Br ^e or BF ₄ ⊖, NO ₃ ⊖, (SO ₄ ² ⊖) _1/2 , ClO ₄ ⊖, CH ₃ OSO ₃ , PF ₆ ⊖, CF ₃ SO ₃ ⊖.

Alkenyl is especially C ₂ -C _2o alkenyl, alkylene is especially C ₂ -C _2o alkylene; Arylene, especially phenylene, aralkylene, especially benzylene and alkaralkylene, especially xylylene.

Suitable N-containing ring systems, which can stand for Z, are shown on pages 8 and 9. The pyridine ring is preferred.

R ₃₆ and R ₃₇ together with the nitrogen atom to which they are attached form in particular a pyrrolidine or piperidine ring substituted by 2 oxo groups bonded in the o- and o'-position, the benzo, cyclohexeno or [2.2.1] - can be bicyclohexenocondensed.

Acyl is especially C ₁ -C ₁₀ alkylcarbonyl or benzoyl; Carbalkoxy is especially C ₁ -C ₁₀ alkoxycarbonyl; Carbamoyl is in particular mono- or di-C ₁ -C ₄ -alkylaminocarbonyl; Carbaroxy is especially phenoxycarbonyl.

Groups R _{24 which} can be split off by nucleophilic agents are, for example, halogen atoms, C ₁ -C ₁₅ alkylsulfonyloxy groups, C ₇ -C ₁₅ aralkylsulfonyloxy groups, C ₆ -C ₁₅ arylsulfonyloxy groups and 1-pyridinyl radicals.

Suitable examples are disclosed in DE 38 36 945.

In particular 50 to 500 g / m ² , preferably 200 to 400 mg / m ² , of hardener are used. Preferred hardeners are the carbamoylpyridinium salts (1st formula of the compilation) and the hardeners of the formulas CH ₂ = CH-SO ₂ -CH ₂ -SO ₂ -CH = CH ₂ and CH ₂ = CH-S0 ₂ -CH ₂ -O-CH ₂ -S0 ₂ -CH = CH ₂ .

The casting solution for the hardening layer has in particular a viscosity of 1 to 30 mPa.s, the hardening layer in particular a wet layer thickness of 3 to 30 µm.

In addition to the polymers used according to the invention, other polymers can also be added to the layers containing binder. Examples are polyacrylamides, gelatin derivatives, polyacrylic acid or polymethacrylic acid or their salts polyvinylpyrrolidone, polyvinyl alcohol or carboxyl group-containing polyvinyl alcohol derivatives, polyvinylimidazole, polyethyl acrylate, polybutyl acrylate, polyurethane latices, polyester dispersions.

The silver halide photographic material can be a black and white material, e.g. an X-ray or graphic material, including a diffusion transfer reversal (DTR) material. It is preferably a color photographic material.

In black and white material, accelerating curing with divinyl sulfone hardeners is particularly important for layers containing gelatin and Co-PVA when the layers are applied at low pH values, as is usually the case with materials that Contain developing agents, e.g. DTR materials and materials processed by alkaline development activation solutions. In this way, complete hardening is achieved in a relatively short time, while other hardeners take several weeks to harden. With slow and incomplete curing in the case of DTR materials that contain a layer of development nuclei, the nuclei would sink from their layer into the underlying incompletely hardened layer.

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 color bleaching process.

Suitable supports for the production of color photographic materials are e.g. Films and sheets of semisynthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or a-olefin polymer layer (e.g. polyethylene). These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.

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

Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.

In addition to the compounds of the formula I, gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring 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 gelatin substitutes are usually modified natural products. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose as well as gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.

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

The gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.

The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions. It can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.

The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. 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 grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.

Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.

The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.

The silver halide is preferably precipitated in the presence of the binder, e.g. the gelatin and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include e.g. Ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are brought together either one after the other by the single-jet process or simultaneously by the doublejet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded. The pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with an excess of halide, so-called inverse precipitation with an excess of silver ions is also possible. In addition to precipitation, the silver halide crystals can also grow by physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.

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

The precipitation can also be carried out in the presence of sensitizing dyes. Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchanger.

The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached. The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).

Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (eg gold, platinum, palladi um, iridium), thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (eg imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia) der Technische Chemie, 4th edition, vol. 18, p. 431 ff. and Research Disclosure 17643 (Dec. 1978), chapter 111) are added. As an alternative or in addition, a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.

Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. by Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups are particularly suitable, e.g. Mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also being a water-solubilizing group, e.g. may contain a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.

The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Mixtures of two or more of the compounds mentioned can also be used.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics ( eg acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. Saponin are mainly used as synthetic surface-active compounds (surfactants): non-ionic surfactants. e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds, cationic surfactants, e.g. higher alkyl amines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid or phosphoric ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.

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

Research Disclosure 17643 (Dec. 1978), Chapter IV, provides an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations having a super-sensitizing effect.

• 1. als Rotsensibilisatoren 9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethylnaphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa- bzw. - benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.
• 2. als Grünsensibilisatoren 9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.
• 3. als Blausensibilisatoren symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

The following dyes, sorted by spectral range, are particularly suitable:

• 1. as red sensitizers 9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl and 9-ethylnaphthoxathia or -selencarbocyanines and 9-ethyl-naphthothiaoxa- or - benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers 9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups and benzimidazocarbocyanines, 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 asymmetrical benzimidazo-, oxa-, thia- or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromati core, and apomerocyanines with a rhodanine group.

Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.

The differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually, cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.

Color couplers for producing the blue-green partial color image are generally couplers of the phenol or a-naphthol type.

Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.

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

The color couplers can be 4-equivalent couplers, but they can also be 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

DIR couplers, the development inhibitors of the azole type, e.g. Release triazoles and benzotriazoles are described 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. Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group. Examples of these 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-A-4 146 396 and 4 438 393 as well in GB-A-2 072 363.

DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.

When using DIR couplers, in particular those which release an easily diffusible development inhibitor, suitable measures can be taken to improve the color rendering, e.g. achieve a more differentiated color rendering, as described, for example, 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 added to a wide variety of layers in a multilayer photographic material, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence the photographic properties achieved. The influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it can be advantageous to use a DIR coupler which forms a color in the coupling in the respective layer in which it is introduced, which color differs from the color to be produced in this layer.

To increase the sensitivity, the contrast and the maximum density, DAR or. FAR couplers are used that split off a development accelerator or an fogging 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 U.S.-A-4,618,572 and 4,656,123.

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

It can be advantageous to modify the effect of a photographically active group which is split off from a coupler in that an intermolecular reaction of this group occurs after its release with another group according to DE-A-35 06 805.

Since with DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).

The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).

The material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example 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-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.

High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.

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

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

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

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

The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.

Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.

Examples of suitable oil formers are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, 2-ethylphosphate, tridecoxyphosphate, tri-ethylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, tridecylphosphate, 2-ethylhexylphosphate, , Dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctylacelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N-2-t-2-n-N-2-n-N-2-t-butyl -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

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

With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be selected without the yellow filter layer, other layer arrangements in which, for example, the carrier blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

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

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

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

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

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

Ultraviolet absorbing couplers (such as a-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.

Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.

Suitable whiteners are e.g. 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.

Certain layers of binder, particularly the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of an inorganic or organic nature, e.g. 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 from 0.2 to 10 μm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

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

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

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

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

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

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

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

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

In the case of color reversal materials, development is first carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.

example 1

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

Layer structure 1.1 (comparison)

• 1st layer (substrate layer) 0.2 g gelatin
• 2nd layer (blue-sensitive layer) blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.78 μm) from 0.50 g AgN0 ₃ with 1.38 g gelatin 0.60 g Yellow coupler Y-1 0.48 g tricresyl phosphate (TKP)
• 3rd layer (intermediate layer) 1.18 g gelatin 0.08 g 2,5-dioctylhydroquinone 0.08 g dibutyl phthalate (DBP)
• 4th layer (green-sensitive layer) green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.37 μm) from 0.40 g AgN0 ₃ with 1.02 g gelatin 0.37 g Purple coupler M-1 0.40 g DBP
• 5th layer (intermediate layer) 1.20 g gelatin 0.66 g UV absorber of the formula
  
  0.052 g 2,5-dioctyl hydroquinone 0.36 g CPM
• 6th layer (red-sensitive layer) red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.35 μm) from 0.28 g AgNO ₃ with 0.84 g gelatin 0.39 g Teal coupler C-1 0.39 g TKP
• 7th layer (UV protective layer) 0.65 g gelatin 0.21 g UV absorber as in 5th layer 0.11 g CPM
• 8th layer (protective layer) 0.65 g gelatin 0.39 g hardening agent of the formula
  
  
  
  

Layer structure 1.2 (comparison)

• 1. Schicht 0,18 g Gelatine 0,02 g Polyvinylalkohol
• 2. Schicht 1,24 g Gelatine 0,14 g Polyvinylalkohol
• 3. Schicht 1,06 g Gelatine 0,12 g Polyvinylalkohol
• 4. Schicht 0,92 g Gelatine 0,1 g Polyvinylalkohol
• 5. Schicht 1,08 g Gelatine 0,12 g Polyvinylalkohol
• 6. Schicht 0,76 g Gelatine 0,08 g Polyvinylalkohol
• 7. Schicht 0,56 g Gelatine 0,09 g Polyvinylalkohol
• 8. Schicht 0,56 g Gelatine 0,09 g Polyvinylalkohol

Like layer structure 1.1, but with modified amounts of gelatin and additional polymer:

• 1st layer 0.18 g gelatin 0.02 g polyvinyl alcohol
• 2nd layer 1.24 g gelatin 0.14 g polyvinyl alcohol
• 3rd layer 1.06 g gelatin 0.12 g polyvinyl alcohol
• 4th layer 0.92 g gelatin 0.1 g polyvinyl alcohol
• 5th layer 1.08 g gelatin 0.12 g polyvinyl alcohol
• 6th layer 0.76 g gelatin 0.08 g polyvinyl alcohol
• 7th layer 0.56 g gelatin 0.09 g polyvinyl alcohol
• 8th layer 0.56 g gelatin 0.09 g polyvinyl alcohol

Layer structure 1.3 (comparison)

Like layer structure 1.2, but with the following changes: Instead of the polyvinyl alcohol, the same amount of block copolymer made of polyvinyl alcohol / polyacrylic acid according to US Pat. No. 4,912,023 (comparative polymer A1) is used in all layers.

Layer structure 1.4 (according to the invention)

• Anstelle des Polyvinylalkohols wird in allen Schichten die gleiche Menge Polymer P-3 eingesetzt. Schichtaufbau 1.5 (erfindungsgemäß)

Like layer structure 1.2 but with the following changes:

• Instead of the polyvinyl alcohol, the same amount of polymer P-3 is used in all layers. Layer structure 1.5 (according to the invention)

• Anstelle des Polyvinylalkohols wird in allen Schichten die gleiche Menge Polymer P-8 eingesetzt.

Like layer structure 1.2 but with the following changes:

• Instead of the polyvinyl alcohol, the same amount of polymer P-8 is used in all layers.

Layer structure 1.6 (according to the invention)

• 1. Schicht 0,16 g Gelatine 0,04 g Polymer P-4
• 2. Schicht 1,10 g Gelatine 0,28 g Polymer P-4
• 3. Schicht 0,94 g Gelatine 0,24 g Polymer P-4
• 4. Schicht 0,82 g Gelatine 0,20 g Poolymer P-4
• 5. Schicht 0,96 g Gelatine 0,24 g Polymer P-4
• 6. Schicht 0,67 g Gelatine 0,17g Polymer P-4
• 7. Schicht 0,52 g Gelatine 0,13 g Polymer P-4
• 8. Schicht 0,52 g Gelatine 0,13 g Polymer P-4

Like layer structure 1.1, but with modified amounts of gelatin and additional polymer:

• 1st layer 0.16 g gelatin 0.04 g polymer P-4
• 2nd layer 1.10 g gelatin 0.28 g polymer P-4
• 3rd layer 0.94 g gelatin 0.24 g polymer P-4
• 4th layer 0.82 g gelatin 0.20 g Poolymer P-4
• 5th layer 0.96 g gelatin 0.24 g polymer P-4
• 6th layer 0.67 g gelatin 0.17 g polymer P-4
• 7th layer 0.52 g gelatin 0.13 g polymer P-4
• 8th layer 0.52 g gelatin 0.13 g polymer P-4

Layer structure 1.7 (according to the invention)

• Anstelle von Polymer P-4 wird in allen Schichten in gleicher Menge Polymer P-5 eingesetzt.

Like layer structure 1.6 but with the following changes:

• Instead of polymer P-4, polymer P-5 is used in the same amount in all layers.

• a) Farbentwickler - 45 s - 35 ° C
  
• b) Bleichfixierbad - 45 s - 35 ° C
  
• c) Wässern - 2 min - 35 ° C
• d) Trocknen

The layered structures were then exposed behind a graduated gray part. The materials were then processed in the customary manner using the processing baths listed below.

• a) Color developer - 45 s - 35 ° C
  
• b) bleach-fix bath - 45 s - 35 ° C
  
• c) Soak - 2 min - 35 ° C
• d) drying

The wet scratch resistance of samples of the processed material was determined according to the following method.

The photographic recording materials are placed upside down on a horizontal sample holder in a tub filled with water at 10 DH and 38 ° C. The sample to be measured is completely covered with water. After 5 minutes of swelling, a firmly locked steel ball (0 3.2 mm) is guided over the surface of the test specimen at a speed of v = 30 mm / sec. The force (in N) with which the above-mentioned steel ball presses on the outermost protective layer of the sample is set so that it continuously increases from 0 to 10 N over a measuring distance of 20 cm in length. As a measure of the wet scratch resistance of the photographic recording material (in N), the force is given at which, after sample drying, the first layer damage on the measuring section can be recognized by the human eye.

In addition, the layer structures were viewed in the case of obliquely incident light and the layers were visually assessed for their gloss (Table 1).

The swelling factor of the samples is also measured as a measure of the crosslinking of the layer

Table 1 shows that photographic materials which have been hardened with an instant hardener and which contain the polymers according to the invention have improved mechanical properties which are expressed in the form of the wet scratch resistance and the swelling factor. In addition, the gloss of the materials is not affected by the addition of CO-PVA.

Example 2

A color photographic recording material was prepared as described in Example 1.

Layer structure 2.1 (comparison)

Like layer structure 1.1

Layer structure 2.2 (comparison)

Like layer structure 2.1, but with changed amounts of gelatin and additional polymer:

Layer structure 2.3 (comparison)

Like layer structure 2.2 but with A1 in the same amount instead of polyvinyl alcohol in layer 3 and layer 5.

Layer structure 2.4 (according to the invention)

• Schicht 3 und Schicht 5 enthalten anstelle von Polyvinylalkohol in gleicher Menge Polymer P-3.

Like layer structure 2.2 but with the following changes:

• Layer 3 and layer 5 contain polymer P-3 in the same amount instead of polyvinyl alcohol.

Layer structure 2.5 (according to the invention)

• Schicht 3 und Schicht 5 enthalten anstelle von Polyvinylalkohol in gleicher Menge Polymer P-4 Schichtaufbau 2.6 (erfindungsgemäß)

Like layer structure 2.2 but with the following changes:

• Layer 3 and layer 5 contain polymer P-4 in the same amount instead of polyvinyl alcohol Layer structure 2.6 (according to the invention)

• Schicht 3 und Schicht 5 enthalten anstelle von Polyvinylalkohol in gleicher Menge Polymer P-5.

Like layer structure 2.2 but with the following changes:

• Layer 3 and layer 5 contain polymer P-5 in the same amount instead of polyvinyl alcohol.

Layer structure 2.7 (according to the invention)

• Schicht 3 und Schicht 5 enthalten anstelle von Polyvinylalkohol in gleicher Menge Polymer P-7.

Like layer structure 2.2 but with the following changes:

• Layer 3 and layer 5 contain the same amount of polymer P-7 instead of polyvinyl alcohol.

Layer structure 2.8 (comparison)

Like layer structure 2.1, but with modified amounts of gelatin and additional polymer:

Layer structure 2.9 (according to the invention)

• Ersatz von A-1 in allen Schichten durch gleiche Mengen Polymer P-4.

Like layer structure 2.8 but with the following changes:

• Replacement of A-1 in all layers with equal amounts of polymer P-4.

Layer structure 2.10 (according to the invention)

• Ersatz von A-1 in allen Schichten durch gleiche Mengen Polymer P-5.

Like layer structure 2.8 but with the following changes:

• Replacement of A-1 in all layers with equal amounts of polymer P-5.

Layer structure 2.11 (according to the invention)

• Ersatz von A-1 in allen Schichten durch gleiche Mengen Polymer P-7.

Like layer structure 2.8 but with the following changes:

• Replacement of A-1 in all layers with equal amounts of polymer P-7.

The layer structures were processed according to Example 1.

The processed samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 4.2 x 10 ⁶ Ix.h. The percentage decrease in density was then measured at an initial density of 1.5.

In addition, as in Example 1, the wet scratch resistance, swelling factor and gloss of the samples were determined. The results are summarized in Table 2.

Example 2 shows that the combination of instant hardening agents with the amino-functional polyvinyl alcohols gives both mechanically stable layers and light-stable materials.

Example 3

A color photographic recording material was produced in accordance with Example 1.

Layer structure 3.1 (comparison)

Like layer structure 1.1.

Layer structure 3.2 (according to the invention)

• 1. Schicht 0,4 g Polymer P-7 anstelle von Gelatine
• 5. Schicht 1.2 g Polymer P-5 anstelle von Gelatine.

Like layer structure 3.1 but with the following changes:

• 1st layer 0.4 g of polymer P-7 instead of gelatin
• 5. Layer 1.2 g of polymer P-5 instead of gelatin.

Layer structure 3.3 (according to the invention)

• 3. Schicht und 5. Schicht 0,6 g Polymer P-1 und 0,6 g Polyacrylsäure (M_w = 60 000) anstelle von Gelatine

Like layer structure 3.1 but with the following changes:

• 3rd layer and 5th layer 0.6 g of polymer P-1 and 0.6 g of polyacrylic acid (M _w = 60,000) instead of gelatin

The layer structures were processed according to Example 1.

The processed samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 4.2 x 10 ⁶ Ix.h. The percentage decrease in density was then measured at an initial density of 1.5. The results are summarized in Table 3.

Example 4

A color photographic recording material was produced in accordance with Example 1.

Layer structure 4.1 to 4.3 (comparison

• Der 4. Schicht werden 0,3 g Farbstoffstabilisator gemäß Tabelle 4 zugesetzt.

Like layer structure 1.1 but with the following changes:

• 0.3 g of dye stabilizer according to Table 4 are added to the 4th layer.

Layer structure 4.4 to 4.6 (according to the invention)

• 1. Der 4. Schicht werden 0,3 g Farbstoffstabilisator (gemäß Tabelle 4) zugesetzt.
• 2. Die 3. und 5. Schicht enthält jeweils nur noch 0,6 g Gelatine und es werden jeweils 1,1 g Polymer (gemäß Tabelle 4) zugesetzt.

Like layer structure 1.1 but with the following changes:

• 1. 0.3 g of dye stabilizer (according to Table 4) are added to the 4th layer.
• 2. The 3rd and 5th layers each contain only 0.6 g gelatin and 1.1 g polymer (according to Table 4) are added.

The samples are processed as in Example 1.

The processed samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 10 x 10 ⁶ Ix.h. The percentage decrease in density was then measured (Table 4).

Table 4 shows that the light stability of dyes already provided with dye stabilizers can be further improved by adding the polymers according to the invention.

Example 5

Gelatin layers were poured, the dry substance of which consisted of 15% by weight of a polymer of 66% by weight of polyvinyl alcohol and 34% by weight of vinyl alcohol modified with aminoacetaldehyde-dimethylacetal. The curing was carried out with different amounts of methylene bis-vinyl sulfone. Control examples contained pure gelatin. All layers were applied at 5.0 g dry matter / m ² . The details are in Table 5.1.

The water absorption at 24 ° C., the degree of swelling (wet density to dry density) and the scratch resistance were determined for all samples.

The results are shown in Table 5.2.

Samples 5.4-5.6 according to the invention are distinguished by the better values for all properties.

Claims (10)

1. Silver halide photographic material with at least one light-sensitive layer which contains in at least one layer a compound of the formula (I) in an amount of at least 10 mg / m ² :

wherein k 50 to 99% by weight, I 0 to 49% by weight, m 1 to 40 wt .-%, and j 0 to 49% by weight M is a polymerized comonomer M ₁

M ₂

Ri, R _{2 is} hydrogen or alkyl and R _{3 is} an acidic group, B is a chemical bond or a bridge member.
and that is hardened with a quick hardener or an instant hardener. 2. Photographic silver halide material according to claim 1, characterized in that B is the meaning

Has, Li, L _{3 is} a conventional organic link, in particular an optionally substituted alkylene, arylene or aralkylene radical with a maximum of 18 carbon atoms, L ₂ -COO-, -OC-O-, -CO-NH-, -NH-CO-, -S0 ₂ -NH-, -NH-S0 ₂ -, -NH-CO-O- or - NH-CO -NH- and n and o represent 0 or 1 and L ₁ is bound directly to M ₁ . 3. Photographic silver halide material according to claim 3, characterized in that it with an instant hardener of the formula

is hardened, in which R _{1 is} alkyl, aryl or aralkyl. R _{2 has} the same meaning as R ₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond being with a group of the formula

is linked, or R ₁ and R ₂ together denote the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, it being possible for the ring to be substituted, for example, by C ₁ -C ₃ alkyl or halogen, R ₃ for hydrogen, alkyl, aryl, alkoxy, - NR ₄ -COR ₅ , - (CH ₂ ) _m -NR ₈ R ₉ -, - (CH ₂ ) _n -CONR ₁₃ R ₁₄ or

or a bridge link or a direct bond to a polymer chain, wherein R ₄ , R6, R ₇ , R ₉ , R ₁₄ , R ₁₅ , R ₁₇ , R ₁₈ and R _{19 are} hydrogen or C ₁ -C ₄ alkyl, R _{5 is} hydrogen, C ₁ -C ₄ alkyl or NR ₆ R ₇ , R ₈ -COR ₁₀ , R ₁₀ NR ₁₁ R ₁₂ , R ^{11 is} C ₁ -C ₄ alkyl or aryl, in particular phenyl, R _{12 is} hydrogen C ₁ -C ₄ -alkyl or aryl, in particular phenyl, R _{13 is} hydrogen, C ₁ -C ₄ alkyl or aryl, in particular phenyl, R _{16 is} hydrogen, C ₁ -C ₄ alkyl, COR ₁₈ or CONHR ₁₉ , m is a number 1 to 3 n is a number 0 to 3 p is a number 2 to 3 and YO or NR ₁₇ mean or R ₁₃ and R ₁₄ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, the ring being able to be substituted, for example, by C ₁ -C ₃ alkyl or halogen, Z the C atoms and. Necessary for the completion of a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring X⊖ is an anion which is omitted if an anionic group is already linked to the rest of the molecule. 4. Photographic silver halide material according to claim 1, characterized in that it with CH = CH-S0 ₂ -CH ₂ -S0 ₂ -CH = CH ₂ or CH = CH-SO ₂ -CH ₂ -O-CH ₂ -SO ₂ - CH = CH _{2 is} hardened. 5. Photographic silver halide material according to claim 1, characterized in that it contains the compound I in the at least one layer in an amount of 50 mg to 5 g / m ² . 6. Photographic silver halide material according to claim 1, characterized in that the compound of formula I has a molecular weight (weight average) of 10,000 to 500,000. 7. Photographic silver halide material according to claim 1, characterized in that the at least one layer contains the compound of formula I in admixture with gelatin, a weight ratio of compound I: gelatin being set from 90:10 to 5:95. 8. Photographic silver halide material according to claim 3, characterized in that the instant hardener is used in an amount of 50 to 500 mg / g ² . 9. Photographic silver halide material according to claim 1, characterized in that the compound of formula (I) contains -COOH or -SO ₃ H groups. 10. Silver halide photographic material according to claim 1, characterized in that at least one layer containing the compound of formula (I) contains no gelatin.