EP0049449A1 - Photosensitive photographic recording material based on silver halide - Google Patents

Abstract

The photographic silver halide recording material contains in at least one of its light-sensitive gelatin-containing layers a crosslinking agent which activates the carboxyl groups of the gelatin from the group of the carbamoylonium, carbamoylpyridinium and carbamoyloxypyridinium salts and a dione compound of the formula <IMAGE> which acts as an aldehyde remover in the Z for the Completion of a 5- or 6-membered carbocyclic or heterocyclic ring is required atoms, which may contain oxygen, nitrogen or sulfur as heteroatoms.

Description

The invention relates to a photographic silver halide recording material which, in addition to a crosslinking agent which activates the carboxyl groups of the gelatin used as binders, contains a compound which is capable of reacting as an aldehyde scavenger.

Photographic recording materials usually consist of a layer support and light-sensitive gelatin-containing silver halide emulsion layers and / or non-light-sensitive auxiliary layers, likewise containing gelatin, applied thereon. The light-sensitive silver halide gelatin emulsion layers of color photographic recording materials contain the color components required to form the image dyes in the three primary colors. The multilayer recording materials mentioned here in black and white and color photography and their production are generally known and are described, for example, in the "Photography" chapter in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18

Since the gelatin layers from which the photographic recording material is made up must not swell excessively during processing and must have sufficient mechanical strength in order not to be damaged, they are treated with crosslinking agents, which are also called hardeners. Both inorganic and organic, photographically inert compounds which can crosslink the gelatin via the carboxyl groups or the amino groups are suitable as hardening agents. Examples of known curing agents are aldehydes, e.g. Formaldehyde, glyoxal, glutaraldehyde, aldehyde acids, e.g. Mucochloric acid, diketones, e.g. Diacetyl, dihalides, e.g. 1,3-dichloropropanol, bis-vinyl sulfone compounds, diisocyanate bisulfite compounds, bis-epoxides, bisacyridines, peptide reagents such as carbodiimides, N-carbamoylpyridinium and isoxazolium salts or substituted 2,4-dichlorotriazines, e.g. N.N'.N "-Trisacryloyl-perhydro-s-triazine called.

It is known that the use of the above-mentioned aldehydes such as formaldehyde, glyoxal, glutaraldehyde or succinaldehyde as curing agents is associated with certain difficulties. Thus, aldehydes can not only bring about a crosslinking of the gelatin layers that is difficult to limit, they can also improve the functionality of the color components contained in the layers and they can give rise to fog. This disadvantageous effect is also to be expected if the aldehydes have not been specifically incorporated into the photographic materials, but instead have penetrated into the photographic layers during an unintended storage of the photographic material in an aldehyde-containing atmosphere. This situation can occur when photographic materials are stored in furniture that is made of plywood that has been glued with a formalin-containing adhesive, such as a melamine-formaldehyde resin or a phenol-formaldehyde resin. If a photographic material is now stored in such pieces of furniture, then the formaldehyde originating from the gluing can cause a more or less strong veiling of the photographic layers, which in any case affects the quality of the photographic images produced with this material. If the photographic material is a color photographic material, the quality loss caused by the effect of the aldehyde will be even more blatant, since in this case the δ compensation of the three emulsion layers producing the color image will also be disturbed.

In order to avoid the described disadvantages caused by aldehydes, attempts have been made to incorporate so-called aldehyde scavengers into the photographic materials, which are compounds which are able to trap the aldehyde.

For example, it is known from DE-OS 1 772 816 to add photographic layers, for example N, N'-ethylene urea, 2,3-dihydroxynaphthalene or dimedone, in order to fix formaldehyde. In DE-OS 2,332,426 a photographic recording material is described which contains in one of its colloid layers in addition to a _V inylsulfonylhärter an acyclic urea as Aldehydentferner. U.S. Patent 3,652,278 relates to a method of reducing fog in photographic materials to be stored in an atmosphere containing formaldehyde. Then a compound from the group N, N'-ethylene urea, 2,3-dihydroxynaphthalene and 1,1-dimethyl-3,5-diketocyclohexane is incorporated into the silver halide emulsion of the material.

It is also known from US Pat. No. 2,309,492 to process photographic materials which contain an aldehyde hardener in the presence of an organic compound which is capable of reacting with the aldehyde. The compounds include hydroxylamines, hydrazines, hydrazo compounds, semicarbazides, naphthalenediamines and dimethyldihydroresorcinol. US Pat. No. 3,168,400 also relates to a method for stabilizing photographic images. The method is to harden the binder of the photographic material before developing the material and after exposure to an aldehyde, and then removing the unused aldehyde by treatment with the aqueous solution of an amine compound. Suitable amines are, for example, hydroxylamine, semicarbazide, hydrazine, biuret, Aminoguanidine etc. Aldehyde-containing photographic materials are treated according to DE-OS 2 227 144 in baths which contain hydroxylamine or a water-soluble salt of hydroxylamine and an aromatic polyhydroxyl compound with 2 hydroxyl groups in the ortho position, for example an o-dihydroxy compound from the benzene series.

None of these known measures can satisfactorily prevent the impairment of a photographic material caused by the described effect of the aldehydes.

The invention has for its object to develop a photographic recording material which is protected against fogging, especially after prolonged storage under the action of aldehydes, and whose contrast and sensitivity are not adversely affected by such storage.

entspricht, worin

• Z die zur Vervollständigung eines 5- oder 6-gliedrigen gegebenenfalls substituierten carbocyclischen Ringes oder eines gegebenenfalls substituierten heterocyclischen Ringes, der als Heteroatom Sauerstoff, Stickstoff oder Schwefel enthalten kann, erforderlichen Atome bedeutet.

This object is achieved according to the invention by a light-sensitive photographic silver halide recording material which consists of a layer support and at least one light-sensitive gelatin-containing layer which thereon contains a crosslinking agent which activates the carboxyl groups of the gelatin and a compound which acts as an aldehyde remover. The material of the invention is characterized in that the crosslinking agent activating the carboxyl groups of the gelatin is a gelatin hardener from the group of carbamoylonium, carbamoyl pyridinium and carbamoyl, and the ldehydentferner as _A-acting compound of general formula

corresponds to what

• Z is the atoms required to complete a 5- or 6-membered optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring which may contain oxygen, nitrogen or sulfur as the hetero atom.

• Cyclopentan-1,3-dione,
• Cyclohexan-1,3-dione,
• Pyran-2,4-dione,
• Dihydropyran-2,4-dione,
• Thiopyran-2,4-dione,
• Dioxo-cyclohexan-2,4-dione,
• Tetrahydropyrimidin-2,4-dione und
• 2,4,6-Trioxohexahydropyrimidine,

The compounds used as aldehyde removers according to the invention are compounds from the class of

• Cyclopentane-1,3-dione,
• Cyclohexane-1,3-dione,
• Pyran-2,4-dione,
• Dihydropyran-2,4-diones,
• Thiopyran-2,4-dione,
• Dioxo-cyclohexane-2,4-diones,
• Tetrahydropyrimidine-2,4-diones and
• 2,4,6-trioxohexahydropyrimidines,

whose ring carbon atoms with 1 to 5 carbon atoms containing straight-chain or branched Be alkyl groups, carry a fused cycloaliphatic or aromatic 6-membered ring or an aliphatic 5- or 6-ring in spiro linkage. can. The total number of carbon atoms in the substituents is not greater than 6.

It has surprisingly been found that color photographic recording materials, the gelatin layers of which are hardened with a hardening agent from the group consisting of the carbamoylonium, carbamoylpyridinium and carbamoyloxypyridinium salts and which also contain one of the diketo compounds according to the invention. are largely immune to the harmful effects caused by aldehydes. This applies in particular to color photographic layers, the purple-4-equivalency couplers such as those e.g. described in DE-OS 2 015 867, DE-OS 2 408-665 and US Pat. No. 3,062,653.

The following compounds are typical examples of cyclic diketo compounds of the invention.

(A) Cycloalkane-1,3-dione compounds

(B) Pyran-2,4-dione compounds

Thiopyranedione compounds

Dihydropyran-2,4-dione compounds

(E) _D ioxa-cycloalkane-2,4-dione compounds

(F) Tetrahydropyrimidine-2,4-dione compounds

The compounds used according to the invention can be prepared by processes known from the literature. With regard to the individual classes of compounds, reference is made to the following references:

Connection class A

• Durch katalytische Hydrierung des entsprechenden Resorcin bzw. Ethylresorcin, N.L. Drake, G.F. Woods und J.W. Tucker, Org. Synth., Coll. Vol. III, 278 und D.R.P. 21915.

Connections 1 and 3:

• By catalytic hydrogenation of the corresponding resorcinol or ethylresorcinol, NL Drake, GF Woods and JW Tucker, Org. Synth., Coll. Vol.III, 278 and DRP 21915.

• Durch intramolekulare Kondensation von β,β-Dimethyl- lävulinsäure bzw. 1-Acetonyl-cyclopentan-essigsäure-(1)-methylester mit Natriumethylat, E. Rothstein und J.F. Thorpe, J. Chem. Soc. (London), 1926, 2011 und M.Qudrat-J-Kuda, J.Chem. Soc. (London) 1929, 713.

Connections 2 and 6:

• By intramolecular condensation of β, β-dimethyl-levulinic acid or 1-acetonyl-cyclopentane-acetic acid (1) -methyl ester with sodium ethylate, E. Rothstein and JF Thorpe, J. Chem. Soc. (London), 1926, 2011 and M.Qudrat-J-Kuda, J.Chem. Soc. (London) 1929, 713.

• Durch Michael-Addition von Mesityloxid bzw. 3-Ethyl-3-hexen-5-on mit Na-Malonester mit anschließender alkalischer Hydrolyse, R.L. Shriner und H.R. Todd, Org. Synth., Coll. Vol. II, 200 und G.A.R. Kon und R.P. Linstead, J. Chem. Soc. (London) 127, 815 (1925).

Connection 5:

• By Michael addition of mesityl oxide or 3-ethyl-3-hexen-5-one with Na malonic ester followed by alkaline hydrolysis, RL Shriner and HR Todd, Org. Synth., Coll. Vol. II, 200 and GAR Kon and RP Linstead, J. Chem. Soc. (London) 127, 815 (1925).

Connection classes B and C

• Durch Behandlung von Dehydracetsäure bzw. der höheren Homologen mit 90 %iger H₂SO₄ s.u. J.N. Collie, J. Chem. Soc. (London) 59,607 (1891) und F. Kögl und C.A. Salemink, Rcl. Trav. Chim. Pays-Bas 71, 779 (1952)

Verbindungen 14 und 15:

• Durch Behandlung von 3-Benzyl-4-hydroxy-5,6-trimethylen-2-pyron (aus Cyclopentanon und Benzylmalonsäure-bis-(2,4-dichlorphenol)-ester) bzw. 3_-Benzyl-4-hydroxy-5,6-tetramethylen-2-pyron mit A1C1₃ in der Hitze s.u. E. Ziegler, H. Junek und E.Nölken, Monatsh. Chem. 89, 678 (1958).

Connections 7 - 13:

• By treating dehydroacetic acid or the higher homologues with 90% H ₂ SO ₄ see JN Collie, J. Chem. Soc. (London) 59,607 (1891) and F. Kögl and CA Salemink, Rcl. Trav. Chim. Pays-Bas 71, 779 (1952)

Connections 14 and 15:

• By treating 3-benzyl-4-hydroxy-5,6-trimethylene-2-pyrone (from cyclopentanone and benzylmalonic acid bis (2,4-dichlorophenol) ester) or 3 _- benzyl-4-hydroxy-5, 6-tetramethylene-2-pyrone with A1C1 ₃ in the heat see E. Ziegler, H. Junek and E.Nölken, monthly. Chem. 89, 678 (1958).

• Durch Cyclisierung von Malonsäurediphenylester bzw. Malonsäure-di-thiophenylester mit AlCl₃ s.u. E. Ziegler und H. Junek, Monatsh. Chem. 86, 29 (1955).

Connections 16 and 17:

• By cyclization of malonic acid diphenyl ester or malonic acid di-thiophenyl ester with AlCl ₃ see E. Ziegler and H. Junek, monthly h. Chem. 86, 29 (1955).

Connection class D

• Aus 4-Hydroxy-hept-5-en-1-yne-1-carbonsäure und Piperidin in Ether s.u. H.B. Heubert, E.R.H. Jones J.Chem. Soc. (London) 1950, 3268.

Connection 18:

• From 4-hydroxy-hept-5-en-1-yne-1-carboxylic acid and piperidine in ether see HB Heubert, ERH Jones J.Chem. Soc. (London) 1950, 3268.

• Durch Etherspaltung von 5,6-Dihydro-4-methoxy-6,6-pentamethylen-2-pyron s.u. H.B. Heubert w.o.

Connection 19:

• By ether cleavage of 5,6-dihydro-4-methoxy-6,6-pentamethylene-2-pyrone see HB Heubert where

Verbindun ^g ts class E

• Durch Kondensation von Aceton bzw. des höheren Ketons (Heptanon-4, Cyclopentanon, Cyclohexanon) mit Malonsäure in Anwesenheit von Essigsäureanhydrid und Schwefelsäure s.u.
• D. Davidson u.S.A. Bernhard, J. Amer. Chem. Soc. 70, 3426 (1948), A. Kandiah, J. Chem. Soc. (London) 1932, 1212 B. Eistert und F. Geiss, Chem. Ber. 94, 929 (1961).

Connections 20, 21, 23 and 24:

• By condensation of acetone or the higher ketone (heptanone-4, cyclopentanone, cyclohexanone) with malonic acid in the presence of acetic anhydride and sulfuric acid see below
• D. Davidson uSA Bernhard, J. Amer. Chem. Soc. 70, 3426 (1948), A. Kandiah, J. Chem. Soc. (London) 1932, 1212 B. Eistert and F. Geiss, Chem. Ber. 94, 929 (1961).

• Durch Behandlung von Malonsäure mit Essigsäureanhydrid und Schwefelsäure, Entfernung der entstandenen Essigsäure und Reaktion mit Benzaldehyd s.u. A. Michael und N. Weiner, J. Amer. Chem. Soc. 58, 680 (1936).

Connection 22:

• By treating malonic acid with acetic anhydride and sulfuric acid, removing the acetic acid formed and reacting with benzaldehyde see A. Michael and N. Weiner, J. Amer. Chem. Soc. 58, 680 (1936).

Connection class F Connections 25-29

By condensing a urea with malonic acid in the presence of acetic anhydride or PoCl ₃ see AH Biltz and H. Wittek, Ber. German Chem. Ges. 54, 1036 (1929) and M. Conradt and M. Guthzeit, Ber. German chem. Ges. 14, 1643 (1881) and JB Dickey and AR Gray Org. Synth. Coll. Vol II p. 60.

• (I) Carbamoyloniumverbindungen der Formel
  
  worin bedeuten:
  • R₁ eine gegebenenfalls substituierte Alkylgruppe, vorzugsweise eine Alkylgruppe mit 1 bis 3 C-Atomen, eine gegebenenfalls mit einem Niederalkylrest oder mit Halogen substituierte Arylgruppe, z.B. Phenyl, gegebenenfalls substituiert mit Methyl, Ethyl oder Propyl, Cl oder Br, eine Aralkylgruppe, z.B. Benzyl, die in gleicher Weise wie die Arylgruppe substituiert sein kann,
  • R₂ die gleiche Bedeutung wie R₁, oder ein zweibindiger, gegebenenfalls substituierter Alkylen-, Arylen-, Aralkylen- oder Alkyl-Aryl-Alkyl-Rest, z.B. ein Ethylen-, Propylen-, Phenylen- oder Xylylen-Rest, der über seine zweite Bindung mit einer weiteren Carbamoylammoniumgruppierung der Formel
    
    verbunden ist, oder
  • R₁ und R₂ bilden zusammen die zur Vervollständigung eines gegebenenfalls substituierten Piperiden-, Piperazin- oder Morpholinringes erforderliche Atomgruppe, wobei der Ring z.B. mit einer Alkylgruppe mit 1 bis 3 C-Atomen oder mit Halogen wie Cl oder Br substituiert sein kann,
  • R₃ ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 3 C-Atomen oder die Gruppierung
    
    A
    
    _α, worin A eine Vinylgruppe einer polymerisierten Vinylverbindung oder eines Mischpolymerisates mit anderen copolymerisierbaren Monomeren und α eine solche Zahl bedeutet, daß das Molgewicht der Verbindung größer als 1000 ist,
  • R₄ ein Wasserstoffatom, Alkyl mit 1 bis 3 C-Atomen oder wenn Z für die zur Vervollständigung eines Pyridiniumringes erforderliche Atomgruppierung steht und R₃ fehlt, bedeutet R₄ eine der Gruppen:
    
    • R⁶ = H, Alkyl (1-4 C) R⁷ = H, Alkyl (1-4 C) = NR⁸R⁹ R⁸,R⁹ = H, Alkyl (C₁-C₄)
      
    • R¹⁰= -CO-R¹² R¹¹= H, Alkyl (C₁-C₄) R¹²= _H, Alkyl (C₁-C₄) R¹²= NR¹³R¹⁴ R¹³= Alkyl (C₁-C₄), Aryl R¹⁴= _H, Alkyl, Aryl m = 1 - 3
      
    • R¹⁵= H, Alkyl (C₁-C₄), Aryl R¹⁶= _H, Alkyl (C₁-C₄) oder R¹⁵ und _R ¹⁶ bilden zusammen die zur Vervollständigung eines 5- oder 6-gliedrigen aliphatischen Ringes erforderliche Atomgruppe n = 0 bis 3
      
    • R¹⁷= H, Alkyl (C₁-C₄), gegebenenfalls substituiert durch Halogen Y = -O-, -NR¹⁹-R¹⁸= H, Alkyl, -CO-R²⁰, -CO-NHR²¹ R¹⁹,R²⁰,R²¹ = H, Alkyl, (C₁-C₄) p = 2 bis 3,
  • R₅ Alkyl, Aryl oder Aralkyl, aber R₅ fehlt, wenn der Stickstoff, an den R₅ gebunden ist, in dem durch Z gebildeten heterocyclischen aromatischen Ring eine Doppelbindung trägt,
  • Z die zur Vervollständigung eines substituierten oder unsubstituierten, 5- oder 6-gliedrigen, heterocyclischen, aromatischen Ringes oder eines kondensierten Systems wie z.B. Isochinolin erforderliche Atomgruppe die neben dem Stickstoffatom noch andere Heteroatome, z.B. O und S enthalten kann und
  • X ein Anion, z.B. Halogen⊖, BF₄ ^⊖, NO₃⊖, SO₄
    
    , ClO₄⊖ oder CH₃OSO₃⊖.
• (II) Carbamoylpyridiniumverbindungen der Formel
  
  worin bedeuten:
  • R₁,R₂ gleich oder verschieden eine Alkylgruppe mit 1 bis 3 C-Atomen, eine gegebenenfalls mit einem Niederalkylrest oder mit Halogen substituierte Arylgruppe, z.B. Phenyl, gegebenenfalls substituiert mit Methyl, Ethyl, Cl oder Br, eine Aralkylgruppe, z.B. Benzyl, die in gleicher Weise wie die Arylgruppe substituiert sein kann, oder
  • R₁+R₂ bilden zusammen die zur Vervollständigung eines Piperidin- oder Morpholinringes erforderliche Atomgruppe, wobei der Ring mit Alkyl, wie z.B. Methyl oder Ethyl oder mit Halogen, wie z.B. Cl oder Br substituiert sein kann,
  • R₃ Wasserstoff, Methyl oder Ethyl,
  • R₄ Methylen, Ethylen, Propylen, oder eine einfache chemische Bindung,
  • Me⁹ ein Alkalimetallkation wie Li⊕, Na⊕, K⊕,
  • X^e ein Anion wie Cl', Br'.
• (III) Carbamoyloxy^pyridiniumverbindungen der Formel
  
  worin bedeuten:
  • R₁ Alkyl mit 1 bis 3 C-Atomen oder Aryl, wie Phenyl,
  • R₂ Alkyl mit 1 bis 3 C-Atomen oder die Gruppe
    
    worin
  • R₇ für Wasserstoff oder Alkyl wie Methyl oder Ethyl und
  • R₆ für Alkyl wie Methyl oder Ethyl steht, oder
  • R1+R2 zusammen die zur Vervollständigung eines heterocyclischen Ringsystems wie eines Pyrrolidin-, Morpholin-, Piperidin-, Perhydroazepin-, 1,2,3,4-Tetrahydrochinolin- oder Imidazolidin-2-OH-Ringes erforderlichen Atome oder
  • R1+R2 zusammen die zur Vervollständigung eines Piperazinringes, der mit seinem zweiten Stickstoffatom die Verbindung zu einem gleichartigen zweiten, der allgemeinen Formel entsprechenden Molekülrest herstellt, erforderlichen Atome,
  • R₃ Wasserstoff, Halogen wie Cl und Br, Alkyl wie Methyl und Ethyl, Oxyalkyl mit 1 bis 3 C-Atomen, Cyan, -CONH₂ oder -NH-C-O-Alkyl (wie Methyl, Ethyl),
  • R₄ Wasserstoff, Alkyl wie Methyl, Ethyl und
  • R₅ Wasserstoff oder Methyl;
  • X ein Anion wie Cl-, BF₄- oder ClO₄-.

According to the invention applied in connection with the cyclic diketo curing agents belong to the group of carbamoylonium salts, or the _C arbamoylpyridiniumsalze and Carbamoyloxypyridinium _- salts. Examples of suitable curing agents from these groups are compounds which correspond to the following general formulas:

• (I) carbamoylonium compounds of the formula
  
  in which mean:
  • R _{1 is} an optionally substituted alkyl group, preferably an alkyl group with 1 to 3 C atoms, an aryl group, for example phenyl, optionally substituted with a lower alkyl radical or with halogen, optionally substituted with methyl, ethyl or propyl, Cl or Br, an aralkyl group, for example benzyl which can be substituted in the same way as the aryl group,
  • R _{2 has} the same meaning as R ₁ , or a divalent, optionally substituted alkylene, arylene, aralkylene or alkyl-aryl-alkyl radical, for example an ethylene, propylene, phenylene or xylylene radical, which is via its second bond with another carbamoylammonium grouping of the formula
    
    is connected, or
  • R ₁ and R ₂ together form the atomic group required to complete an optionally substituted piperidene, piperazine or morpholine ring, it being possible for the ring to be substituted, for example, by an alkyl group having 1 to 3 carbon atoms or by halogen such as Cl or Br,
  • R _{3 is} a hydrogen atom, an alkyl group with 1 to 3 carbon atoms or the grouping
    
    A
    
    _α , in which A is a vinyl group of a polymerized vinyl compound or a copolymer with other copolymerizable monomers and α is a number such that the molecular weight of the compound is greater than 1000,
  • R _{4 is} a hydrogen atom, alkyl having 1 to 3 C atoms or if Z represents the atomic grouping required to complete a pyridinium ring and R ₃ is absent, R _{4 means} one of the groups:
    
    • R ⁶ = H, alkyl (1-4 C) R ⁷ = H, alkyl (1-4 C) = NR ⁸ R ⁹ R ⁸ , R ⁹ = H, alkyl (C ₁ -C ₄ )
      
    • R ¹⁰ = -CO-R ¹² R ¹¹ = H, alkyl (C ₁ -C ₄ ) R ¹² = _H , alkyl (C ₁ -C ₄ ) R ¹² = NR ¹³ R ¹⁴ R ¹³ = alkyl (C ₁ -C ₄ ), aryl R ¹⁴ = _H , alkyl, aryl m = 1-3
      
    • R ¹⁵ = H, alkyl (C ₁ -C ₄ ), aryl R ¹⁶ = _H , alkyl (C ₁ -C ₄ ) or R ¹⁵ and _R ¹⁶ together form the atomic group required to complete a 5- or 6-membered aliphatic ring n = 0 to 3
      
    • R ¹⁷ = H, alkyl (C ₁ -C ₄ ), optionally substituted by halogen Y = -O-, -NR ¹⁹ -R ¹⁸ = H, alkyl, -CO-R ²⁰ , -CO-NHR ²¹ R ¹⁹ , R ²⁰ , R ²¹ = H, alkyl, (C ₁ -C ₄ ) p = 2 to 3,
  • R _{5 is} alkyl, aryl or aralkyl, but R ₅ is absent if the nitrogen to which R _{5 is} bonded has a double bond in the heterocyclic aromatic ring formed by Z,
  • Z is the atomic group required to complete a substituted or unsubstituted, 5- or 6-membered, heterocyclic, aromatic ring or a condensed system such as isoquinoline, which may contain other heteroatoms, for example O and S, in addition to the nitrogen atom, and
  • X is an anion, for example halogen⊖, BF ₄ ^⊖ , NO ₃ ⊖, SO ₄
    
    , ClO ₄ ⊖ or CH ₃ OSO ₃ ⊖.
• (II) Carbamoylpyridinium compounds of the formula
  
  in which mean:
  • R ₁ , R _{2, the} same or different, represent an alkyl group with 1 to 3 C atoms, an aryl group, for example phenyl, optionally substituted with a lower alkyl radical or with halogen, optionally substituted with methyl, ethyl, Cl or Br, an aralkyl group, for example benzyl, which in the same way as the aryl group can be substituted, or
  • R ₁ + R ₂ together form the atomic group required to complete a piperidine or morpholine ring, which ring may be substituted with alkyl, such as methyl or ethyl, or with halogen, such as Cl or Br,
  • R _{3 is} hydrogen, methyl or ethyl,
  • R ₄ methylene, ethylene, propylene, or a simple chemical bond,
  • Me ⁹ an alkali metal cation such as Li⊕, Na⊕, K⊕,
  • X ^e an anion like Cl ', Br'.
• (III) carbamoyloxy ^p yridiniumverbindungen of formula
  
  in which mean:
  • R _{1 is} alkyl having 1 to 3 carbon atoms or aryl, such as phenyl,
  • R ₂ alkyl with 1 to 3 carbon atoms or the group
    
    wherein
  • R _{7 represents} hydrogen or alkyl such as methyl or ethyl and
  • R _{6 represents} alkyl such as methyl or ethyl, or
  • R1 + R2 together are the atoms required to complete a heterocyclic ring system such as a pyrrolidine, morpholine, piperidine, perhydroazepine, 1,2,3,4-tetrahydroquinoline or imidazolidine-2-OH ring or
  • R1 + R2 together to complete a piperazine ring with its second nitrogen atom creates the connection to a similar second molecular radical corresponding to the general formula, required atoms,
  • R _{3 is} hydrogen, halogen such as Cl and Br, alkyl such as methyl and ethyl, oxyalkyl having 1 to 3 C atoms, cyano, -CONH ₂ or -NH-CO-alkyl (such as methyl, ethyl),
  • R _{4 is} hydrogen, alkyl such as methyl, ethyl and
  • R _{5 is} hydrogen or methyl;
  • X is an anion such as Cl-, BF ₄ - or ClO ₄ -.

• Sirup stark hygroskopisch
  
• Sirup stark hygroskopisch
  
• Fp. 112°C
  
• Fp. 103°C
  
• Fp. 87-89°C
  
• F^p. 108-110°C
  
• Sirup, hygroskopisch
  
• Fp. 105-107°C
  
• Sirup
  
• Fp. 103-105°C
  
• Fp. 75-77°C
  
• Fp. 110-112°C
  
• Fp. 95-96°C
  
• Fp. 106°C
  
• Molgewicht über 1000
  
• Fp. 66-68°C
  
• Sirup, hygroskopisch
  
  
• Smp.: 103-105°C
  
  
• Smp.: 109°C
  
  
  
• Smp.: 115°C
  
• Smp.: 154°C
  
• Smp.: 140°C
  
• Smp.: 115°C
  
  
• Smp.: 140-145°C
  
• Smp.: 118-120°C
  
• Smp.: 90°C
  
• Smp.: 210°C
  
• Öl
  
• Öl
  
  
  
  
  
  

The following compounds may be mentioned as examples of hardening agents which can advantageously be used according to the invention:

• Syrup strongly hygroscopic
  
• Syrup strongly hygroscopic
  
• Mp 112 ° C
  
• Mp 103 ° C
  
• Mp 87-89 ° C
  
• F ^p . 108-110 ° C
  
• Syrup, hygroscopic
  
• Mp 105-107 ° C
  
• syrup
  
• Mp 103-105 ° C
  
• Mp 75-77 ° C
  
• Mp 110-112 ° C
  
• Mp 95-96 ° C
  
• Mp 106 ° C
  
• Molecular weight over 1000
  
• Mp 66-68 ° C
  
• Syrup, hygroscopic
  
  
• M.p .: 103-105 ° C
  
  
• M.p .: 109 ° C
  
  
  
• M.p .: 115 ° C
  
• M.p .: 154 ° C
  
• M.p .: 140 ° C
  
• M.p .: 115 ° C
  
  
• M.p .: 140-145 ° C
  
• M.p .: 118-120 ° C
  
• M.p .: 90 ° C
  
• M.p .: 210 ° C
  
• oil
  
• oil
  
  
  
  
  
  

Compounds according to formula II

Compounds according to formula III

The fast acting curing agents suitable for the process of the invention are known as such. Details regarding their manufacture and properties can be found in the following publications. _C arbamoylpyridiniumverbindungen described in British Patent Specification 1,383,630, Carbamoyloxypyridiniumverbindungen in Belgian Patent 825,726.

The cyclic diketo compounds of the invention can be used in the layers of photographic recording materials together with the curing agents mentioned, without the two additives adversely affecting one another in any way. The diketo compounds can be added to the casting solution of one or more of the sub-layers of the photographic recording material, depending on the conditions of the casting. In general, it is sufficient to coat the recording material with a top layer which contains the diketo compound. The layered structure is then adequately protected against the penetration of aldehyde vapors. The application of the diketo compounds in this form has in particular _- sondere in color photographic multilayered materials proven. Since the diketo compounds of the invention are more or less diffusible, the amount of the diketo compound applied with the top layer can be dimensioned such that they diffuse into the layer structure during the drying process The resulting compound is evenly distributed over the layers of the dressing containing the color components, thereby achieving an optimal protective effect.

Depending on their solubility and crystallization capacity, the diketo compounds can be introduced in all water-miscible solvents or in water itself. Particularly advantageous are low-boiling solvents which can be easily removed when the photographic material is poured on, e.g. Methanol, ethanol, propanol, (t) -butanol, acetone, methyl ethyl ketone, acetonitrile.

The amounts of cyclic diketo compounds to be used are understandably dependent on the extent to which protection of the recording material is required. They will therefore depend on the aldehyde concentration to be considered, the sensitivity of the components within the photographic material to be protected and finally the solubility of the cyclic diketo compounds used. In order to effectively protect color photographic recording materials against damage during storage, for which aldehydes present in the atmosphere are responsible, generally at least 0.05 mol of the cyclic diketo compound per mol of hardener is sufficient. Preferably, the use is from 0.1 to 6 moles per mole of curing agent diketo compound, said amounts of from 0.2 to 2 moles per mole of curing agent as Diketoverbindun ^g have proven particularly suitable.

As hydrophilic colloids can be used in the layers of the recording material in addition to the gelatin, colloidal albumin, agar, gum arabic, dextrans, alginic acid, cellulose derivatives, eg up to an acetyl content 19-26% hydrolyzed cellulose acetate, polyacrylamide, imidatisierte polyacrylamides, Cin, _V inylalkoholpolymere with urethane / Carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol, vinyl cyanoacetate copolymers, polyvinyl alcohols, polyvinyl pyrrolidones, hydrolyzed polyvinyl acetates, polymers such as those obtained in the polymerization of proteins and saturated acylated proteins with monomers with vinyl groups, polyvinylamines, polyaminoethyl methacrylates and polyethylenimine are used.

Color photographic recording materials in which the cyclic diketo compounds can advantageously be used according to the invention are described, for example, in German Offenlegungsschriften DE-OS 24 08 814, DE-OS 26 25 026 and DE-OS 25 17 408.

The cyclic diketo compounds used in accordance with the invention in connection with the carbamoylonium, carbamoylpyridinium and carbamoyloxypyridinium hardeners have proven to be particularly advantageous in that they in no way affect the sensitometric properties of the photographic material affect, although they would in principle be able to couple due to the presence of an active carbon atom. However, unlike the compounds known as aldehyde scavengers, they have a high reactivity towards aldehydes, which makes the use of the curing agent mentioned possible in practice.

The following examples, which describe preferred embodiments of the invention, are intended to explain the invention in more detail. Unless stated otherwise, percentages mean percentages by weight.

example 1

• Auf einem mit einer Lichthofschutzschicht und einer Haftschicht versehenen Cellulosetriacetatträger werden nacheinander die unten angegebenen Schichten aufgetragen. Die Mengenangaben beziehen sich jeweils auf 1 m². Der Silberauftrag wird durch Angabe der entsprechenden Menge Silbernitrat ausgewiesen.

The following examples are based on the following layer structure:

• The layers specified below are applied in succession to a cellulose triacetate support provided with an antihalation layer and an adhesive layer. The quantities given relate to 1 m ² . The silver order is shown by indicating the corresponding amount of silver nitrate.

The compounds identified by letters in the description of the individual layers have the following formulas:

• 1. A less sensitive layer of a red-sensitized silver bromide iodide emulsion (5 mol% AgJ) from 2.8 g of AgNO ₃ and 2.5 g of gelatin with 0.7 g of cyan coupler of the formula A), 0.3 g of the cyan coupler of the Formula B), 0.025 g of DIR coupler C) and 0.075 g of red mask D).
• 2. A highly sensitive layer of a red-sensitized silver bromide iodide emulsion (6 mol% AgJ) containing 1.9 g AgN0 ₃ , 2.0 g gelatin, 0.21 g of the cyan coupler A) and 0.09 g of the cyan coupler B).
• 3. An intermediate layer of 0.7 g gelatin.
• 4. A less sensitive layer of a green-sensitized silver bromide iodide emulsion (6 mol% AgJ) containing 2.3 g AgNO ₃ , 2.6 g gelatin, 0.3 g color coupler of the formula E) dispersed therein, 0.3 g of the color coupler Formula F), 0.06 g of DIR coupler G) and 0.09 g of yellow mask coupler H).
• 5. A highly sensitive layer of a green sensiti based silver bromide iodide emulsion (6 mol% AgJ) containing 2.6 g AgN0 ₃ , 2.2 g gelatin and 0.25 g color coupler of the formula E) dispersed therein.
• 6. An intermediate layer of 1.0 g gelatin.
• 7. A Carey Lea silver filter layer having the color density of 0.7 to 1.0 g of gelatin order p _{ro m} ^2.
• 8. A lower sensitive blue-sensitized layer (5 mol% AgJ) containing 0.95 g AgNO ₃ , 2.0 g gelatin and 1.6 g yellow coupler of the formula J) dispersed therein.
• 9. A highly sensitive blue-sensitized layer (6 mol% AgJ) containing 0.5 g AgNO ₃ , 1.0 g gelatin and 0.1 g yellow coupler J dispersed therein.
• 10. A top layer of 1.2 g gelatin.
• 11. A top layer of 0.25 g gelatin with the 3.3 mmol of the carbamoylpyridinium or carbamoyloxypyridinium salts described in more detail below have been introduced into the layer structure.

Samples of a film constructed in this way are exposed behind a gradual step wedge and after development with N-ethyl-N-β-oxyethyl-3-methyl-p-phenylenediamine (3 1/4 minutes at 38 ° C) with subsequent bleaching fixation (see the by Ernest Ch. Gehret in the British Journal of Photographie, 1974, page 597) with regard to their sensitometric properties.

To test for aldehyde stability, the samples were sized 35x250 mm for 7 days at room temperature in a vessel with a volume of 27 l containing a mixture of 650 g glycerol, 350 g water and 1 ml 30% formaldehyde, stored and then checked in comparison with a normally stored material. The purple residual color density remaining in% of the color density 1.5 via veil was evaluated in each case.

Example 2

Diketo compound no. 25 was introduced as a 2.5% aqueous solution with a pH = 6 into the casting solution of layer 10 of example 1. Compound No. III / 39. used. The results are shown in Table 1 below.

The results show that practically complete formalin protection can be achieved with just 550 mg of the diketo compound.

Analogous results are obtained if compounds I / 12, II / 10 and III / 13 are used as curing agents instead of compound III / 39.

Example 3

The effect of the present 1,3-diketo compounds is compared with that of known aldehyde removers. Of the diketo compounds and the comparison compounds, 170 mg each of layer 7 of example 1, 180 mg of layer 8 of example 1 and 100 mg of layer 9 of example 1 were added. Compound II / 15. used.

Table 2 shows that practically only the cyclic 1,3-diketo compounds of the invention have a protective effect.

Example 4

Of the diketo compound no. 26, 220 g are added to layers 1 and 2 from example 1 and 145 mg to layers 7, 8 and 9 of example 1. In all cases, compound no. II / 10. used. A purple color density of 90% was measured on all 5 samples after storage under a formalin atmosphere. As the example shows, the same protective effects are achieved it does not matter whether the diketo compound is embedded in a layer which lies above or below the purple layer to be protected or which is the purple layer itself.

Claims (5)

1. Photosensitive photographic silver halide recording material consisting of a support and at least one photosensitive gelatin-containing layer provided thereon, which contains a crosslinking agent activating the carboxyl groups of the gelatin and a compound which acts as an aldehyde remover, characterized in that the crosslinking agent activating the carboxyl groups of the gelatin is a gelatin hardener from the group the carbamoylonium, carbamoylpyridinium and carbamoyloxypyridinium salts and the compound of the general formula which acts as an aldehyde remover

corresponds to what z means the atoms required to complete a 5- or 6-membered optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring which may contain oxygen, nitrogen or sulfur as the hetero atom. 2. Material according to claim 1, characterized in that the compound acting as an aldehyde remover is a compound from the series of Cyclopentane-1,3-dione, Cyclohexane-1,3-dione, Pyran-2,4-dione, Dihydropyran-2,4-diones, Thio ^p yran-2,4-dione, Dioxa-cyclohexane-2,4-diones, Tetrahydropyrimidine-2,4-diones and 2,4,6-trioxohexahydropyrimidines,
whose ring carbon atoms can be substituted by straight-chain or branched alkyl groups containing 1 to 5 carbon atoms, can carry a fused cycloaliphatic or aromatic 6-membered ring or an aliphatic 5 or 6 ring in spiro linkage. 3. Material according to claims 1 and 2, characterized in that the number of carbon atoms of the substituents of the ring bearing the two keto groups is not greater than 6 in total. 4. Material according to claims 1 to 3, characterized in that it contains a carbamoylpyridinium sulfonic acid betaine and a tetrahydropyrimidine-2,4-dione. 5. Material according to claim 4, characterized in that it is the connections

and contains 1-methyl-2,4,6-trioxo-hexahydropyrimidine.