EP0049449B1 - Photosensitive photographic recording material based on silver halide - Google Patents

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 multi-layered 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 hardening agents. 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. B. formaldehyde, glyoxal, glutaraldehyde, aldehyde acids, e.g. B. mucochloric acid, diketones, e.g. B. diacetyl, dihalides, e.g. B.1,3-dichloropropanol, bis-vinyl sulfone compounds, diisocyanate-bisulfite compounds, bis-epoxides, bis-acyridines, peptide reagents such as carbodiimides, N-carbamoylpyridinium and isoxazolium salts or substituted 2,4-dichlorotriazines, e.g. B. N, N ', N "-Trisacryloylperhy- dro-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 cause crosslinking of the gelatin layers that is difficult to limit, they can also impair the functionality of the color components contained in the layers, and they can give rise to the formation of fog. This disadvantageous effect is also to be expected if the aldehydes have not been specifically incorporated into the photographic materials, but, e.g. B. during an unintended storage of the photographic material in an aldehyde-containing atmosphere in the photographic layers. This situation can occur if photographic materials are stored in furniture, for the manufacture of which plywood was used, which with a formal adhesive, e.g. B. a melamine-formaldehyde resin or a phenol-formaldehyde resin has been glued. 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 y-compensation of the three emulsion layers producing the color image will also be disturbed.

In order to avoid the disadvantages caused by aldehydes described, 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, known from DE-A-1772816 to add photographic layers, for example N, N'-ethylene urea, 2,3-dihydroxynaphthalene or dimedone, in order to fix formaldehyde. DE-A-2332426 describes a photographic recording material which, in addition to a vinylsulfonyl hardener, contains an acyclic urea as aldehyde remover in one of its colloid layers. US-A-3 652 278 relates to a method for reducing fog in photographic materials to be stored in an atmosphere containing formaldehyde. A compound from the group N, N'-ethylene urea, 2,3-dihydroxynaphthalene and 1,1-dimethyl-3,5-diketocyclohexane is then incorporated into the silver halide emulsion of the material.

It is further known from US-A-2309492 to process photographic materials which contain an aldehyde hardener in the presence of an organic compound which is able to react with the aldehyde. The compounds include hydroxylamines, hydrazines, hydrazo compounds, semicarbazides, naphthalenediamines and dimethyldihydroresorcinol. US-A-3 168400 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 e.g. B. hydroxylamine, semicarbazide, hydrazine, biuret, aminoguanidine etc. Aldehyde-containing photographic materials are treated according to DE-A-2227 144 in baths containing hydroxylamine or a water-soluble salt of Hydroxylamine and an aromatic polyhydroxyl compound with 2 hydroxyl groups in the ortho position, e.g. B. contains an o-dihydroxy compound from the benzene series.

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

The invention has for its object to develop a photographic recording material which is protected against fogging, especially in the case of 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 6gliedrigen gegebenenfalls substituierten carbocyciischen 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 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 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.

• 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,

deren Ringkohlenstoffatome mit 1 bis 5 Kohlenstoffatome enthaltenden geradkettigen oder verzweigten Alkylgruppen substituiert sein, einen annelierten cycloaliphatischen oder aromatischen 6gliedrigen Ring oder einen aliphatischen 5- oder 6-Ring in Spiroverknüpfung tragen können. Hierbei ist die Zahl der Kohlenstoffatome der Substituenten insgesamt nicht größer als 6.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 are substituted with 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. 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 a diketo compound of the formula given, are largely immune to the harmful effects caused by aldehydes . This is especially true for color photographic layers, the purple-4 equivalent couplers such as z. As described in DE-A-2 015 867, DE-A-2 408 665 and US-A-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

(C) thiopyranedione compounds

(D) Dihydropyran-2,4-dione compounds

(E) Dioxa-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 Connections 1 and 3

By catalytic hydrogenation of the corresponding resorcinol or ethylresorcinol, N.L. Drake, G.F. Woods and J.W. Tucker, Org. Synth., Coll. Vol.III, 278 and D.R. P. 21 915.

Connections 2 and 6

By intramolecular condensation of β, β-dimethyl levulinic acid or 1-acetonyl-cyclopentane-acetic acid (1) methyl ester with sodium methylate, E. Rothstein and J. F. Thorpe, J. Chem. Soc. (London), 1926,2011 and M. Qudrat-J-Kuda, J. Chem. Soc. (London) 1929.713.

Connection 5

By Michael addition of mesityl oxide or 3-ethyl-3-hexen-5-one with Na malonic ester followed by alkaline hydrolysis, R. L. Shriner and H. R. Todd, Org. Synth., Coll. Vol. II, 200 and G.A.R. Kon and R.P. Linsted, J. Chem. Soc. (London) 127, 815 (1925).

Connection classes B and C Connections 7-13

By treating dehydroacetic acid or the higher homologues with 90% H ₂ S0 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 benzylamonic acid bis (2,4-dichlorophenol) ester) or 3-benzyl-4-hydroxy-5, 6-tetramethylene-2-pyrone with AlCl ₃ in the heat, see below

E. Ziegler, H. Junek and E. Nölken, monthly. Chem. 89,678 (1958).

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 Connection 18

From 4-hydroxy-hept-5-en-1-yne-1-carboxylic acid and piperidine in ether. u.

H. B. Heubert, E. R. H. Jones J. Chem. Soc. (London) 1950.3268.

Connection 19

By ether cleavage of 5,6-dihydro-4-methoxy-6,6-pentamethylene-2-pyrone s. u. H. B. Heubertw. O.

Connection class E 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 s. u.

D. Davidson et al. S. A. 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).

Connection 22

By treating malonic acid with acetic anhydride and sulfuric acid, removing the acetic acid formed and reacting with benzaldehyde. u.

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 below

A. H. 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 J. B. Dickey and A. R. 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, CI oder Br, eine Aralkylgruppe, z. B. Benzyl, die in gleicher Weise wie die Arylgruppe substituiert sein kann,
  • R₂ die gleiche Bedeutung wie R_i, 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 CI oder Br substituiert sein kann,
  • R₃ ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 3 C-Atomen oder die Gruppierung
    
    worin A eine Vinylgruppe einer polymerisierten Vinylverbindung oder eines Mischpolymerisates mit anderen copolymerisierbaren Monomeren und x 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, Alkyk (1-4 C) = NR⁸R⁹
    • R⁸, R⁹ = H, Alkyl (C₁-C₄)
      
    • R¹⁰ = -CO-R¹²
    • R¹¹ = H, Alkyl (C₁-C₄)
    • R¹² = H, Alkyl (C_I-C₄)
    • R¹² = NR¹³R¹⁴
    • R¹³ = Alkyl (C_I-C₄), Aryl
    • R¹⁴ = H, Alkyl, Aryl
    • m = 1-3
      
    • R¹⁵ = H, Alkyl (C_I-C₄), Aryl
    • R¹⁶ = H, Alkyl (C₁-C₄) oder
    • R¹⁵ und R^I6 bilden zusammen die zur Vervollständigung eines 5- oder 6gliedrigen aliphatischen Ringes erforderliche Atomgruppe
    • n = 0 bis 3
      
      • R¹⁷ = H, Alkyl (C₁-C₄), gegebenenfalls substituiert durch Halogen
      • Y = -O-,
      • 
        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 6gliedrigen, heterocyclischen, aromatischen Ringes oder eines kondensierten Systems wie z. B. Isochinolin erforderliche Atomgruppe die neben dem Stickstoffatom noch andere Heteroatome, z. B. 0 und S enthalten kann und
  • X ein Anion, z. B. Halogene, BF₄Θ NO₃Θ, SO₄Θ, ClO₄Θ oder CH₃OSO₃Θ.
• (II) Carbamoylpyridiniumverbindungen der Formel
  
  worin bedeuten:
  • R_i, 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, CI 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^Θ ein Anion wie CI', Br'.
• (III) Carbamoyloxypyridiniumverbindungen 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 Imidazo- lidin-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 CI 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-.

The curing agents used according to the invention in connection with the cyclic diketo compounds belong to the group of the carbamoylonium salts or the carbamoylpyridinium salts and the 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 having 1 to 3 carbon atoms, an aryl group optionally substituted by a lower alkyl radical or by halogen, e.g. B. phenyl, optionally substituted with methyl, ethyl or propyl, CI or Br, an aralkyl group, e.g. B. benzyl, which can be substituted in the same way as the aryl group,
  • R _{2 has} the same meaning as R _i , or a divalent, optionally substituted alkylene, arylene, aralkylene or alkyl-aryl-alkyl radical, for. B. an ethylene, propylene, phenylene or xylylene radical, the 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, the ring being e.g. B. can be substituted with an alkyl group having 1 to 3 carbon atoms or with halogen such as CI or Br,
  • R _{3 is} a hydrogen atom, an alkyl group with 1 to 3 carbon atoms or the grouping
    
    wherein A is a vinyl group of a polymerized vinyl compound or a copolymer with other copolymerizable monomers and x 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, alkyk (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 _I -C ₄ )
    • R ¹² = NR ¹³ R ¹⁴
    • R ¹³ = alkyl (C _I -C ₄ ), aryl
    • R ¹⁴ = H, alkyl, aryl
    • m = 1-3
      
    • R ¹⁵ = H, alkyl (C _I -C ₄ ), aryl
    • R ¹⁶ = H, alkyl (C ₁ -C ₄ ) or
    • R ¹⁵ and R ^I6 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-,
      • 
        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 to complete a substituted or unsubstituted, 5- or 6-membered, heterocyclic, aromatic ring or a condensed system such. B. isoquinoline required atomic group in addition to the nitrogen atom other heteroatoms, z. B. can contain 0 and S and
  • X is an anion, e.g. B. halogens, BF ₄ Θ NO ₃ Θ, SO ₄ Θ, ClO ₄ Θ or CH ₃ OSO ₃ Θ.
• (II) Carbamoylpyridinium compounds of the formula
  
  in which mean:
  • R _i , R _{2, the} same or different, are an alkyl group having 1 to 3 carbon atoms, an aryl group optionally substituted with a lower alkyl radical or with halogen, e.g. B. phenyl, optionally substituted with methyl, ethyl, CI or Br, an aralkyl group, e.g. B. benzyl, which can be substituted in the same way as the aryl group, or
  • R ₁ + R ₂ together form the atomic group required to complete a piperidine or morpholine ring, the ring with alkyl, such as. B. methyl or ethyl or with halogen, such as. B. Cl or Br can be substituted,
  • 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 ^Θ an anion like CI ', Br'.
• (III) carbamoyloxypyridinium compounds of the 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
  • R ₁ + R ₂ 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-ring
  • R ₁ + R ₂ together are the atoms required to complete a piperazine ring which, with its second nitrogen atom, forms the connection to a similar second molecular radical corresponding to the general formula,
  • R _{3 is} hydrogen, halogen such as CI 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

Fp. 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

Smp.: 60-65°C

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

Syrup, very hygroscopic

Syrup, very hygroscopic

Mp 112 ° C

Mp 103 ° C

Mp 87-89 ° C

Mp 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

M.p .: 60-65 ° C

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. Carbamoylpyridinium compounds are described in British Patent 1,383,630, carbamoyloxypyridinium compounds 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 use of the diketo compounds in this form has proven particularly useful for color photographic multilayer materials. 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 the compound diffusing into the layer structure during the drying process is evenly distributed over the layers of the structure containing color components, thereby providing an optimal protective effect is achieved.

Depending on the 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. B. 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. The use of 0.1 to 6 moles of diketo compound per mole of curing agent is preferred, with amounts of 0.2 to 2 moles of diketo compound per mole of curing agent having proven particularly suitable.

As hydrophilic colloids in the layers of the recording material, in addition to the gelatin, colloidal albumin, agar, gum arabic, dextrans, alginic acid, cellulose derivatives, e.g. B. up to an acetyl content of 19 to 26% hydrolyzed cellulose acetate, polyacrylamides, imidated polyacrylamides, cein, vinyl alcohol polymers with urethane / carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol, vinyl cyanoacetate mixed polymers, polyvinyl alcohols, polyvinylpyrrolidones, such as hydrolyzed polymers, vinyl hydrolyzed polymers the polymerization of proteins and saturated acylated proteins with monomers obtained with vinyl groups, polyvinylamines, polyaminoethyl methacrylates and polyethyleneimines can be 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-A-2 408 814, DE-A-2 625 026 and DE-A-2 517 408.

The in accordance with the invention in connection with the carbamoylonium, carbamoylpyridinium Cyclic diketo compounds used with carbamoyloxypyridinium hardeners have proven to be particularly advantageous in that they do not in any way impair the sensitometric properties of the photographic material, although in principle they would be capable of coupling 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 specifying the corresponding amount of silver nitrate.

• 1. Eine weniger empfindliche Schicht aus einer rotsensibilisierten Silberbromidjodidemulsion (5 Mol-% AgJ) aus 2,8 g AgNO₃ und 2,5 g Gelatine mit 0,7 g darin dispergiertem Blaugrünkuppler der Formel A), 0,3 g des Blaugrünkupplers der Formel B), 0,025 g des DIR-Kupplers C) und 0,075 g der Rotmaske D).
• 2. Eine hochempfindliche Schicht aus einer rotsensibilisierten Silberbromidjodidemulsion (6 Mol-% AgJ) enthaltend 1,9 g AgN0₃, 2,0 g Gelatine, 0,21 g des Blaugrünkupplers A) und 0,09 g des Blaugrünkupplers B).
• 3. Eine Zwischenschicht aus 0,7 g Gelatine.
• 4. Eine weniger empfindliche Schicht aus einer grünsensibilisierten Silberbromidjodidemulsion (6 Mol-% AgJ) enthaltend 2,3 g AgN0₃, 2,6 g Gelatine, 0,3 g darin dispergiertem Farbkuppler der Formel E), 0,3 g des Farbkupplers der Formel F), 0,06 g des DIR-Kupplers G) und 0,09 g des Gelbmaskenkupplers H).
• 5. Eine hochempfindliche Schicht aus einer grünsensibilisierten Silberbromidjodidemulsion (6 Mol-% AgJ) enthaltend 2,6 g AgN0₃, 2,2 g Gelatine und 0,25 g darin dispergiertem Farbkuppler der Formel E).
• 6. Eine Zwischenschicht aus 1,0 g Gelatine.
• 7. Eine Carey Lea-Silberfilterschicht mit der Farbdichte 0,7 bei 1,0 g Gelatineauftrag pro m^2.
• 8. Eine niedriger empfindliche blausensibilisierte Schicht (5 Mol-% AgJ) enthaltend 0,95 g AgN0₃, 2,0 g Gelatine und 1,6 g darin dispergiertem Gelbkuppler der Formel J).
• 9. Eine hochempfindliche blausensibilisierte Schicht (6 Mol-% AgJ) enthaltend 0,5 g AgNO₃. 1,0 g Gelatine und 0,1 g darin dispergiertem GelbkupplerJ).
• 10. Eine Deckschicht aus 1,2 g Gelatine.
• 11. Eine Deckschicht aus 0,25 g Gelatine mit der 3,3 mMol der im folgenden näher beschriebenen Carbamoylpyridinium- oder Carbamoyloxypyridinium-Salze in den Schichtverband eingebracht worden sind.

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 AgN0 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-sensitized 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 with a color density of 0.7 and 1.0 g of gelatin applied per m ^2.
• 8. A lower sensitive blue-sensitized layer (5 mol% AgJ) containing 0.95 g AgN0 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 of gelatin with 3.3 mmol of the carbamoylpyridinium or carbamoyloxypyridinium salts described in more detail below has 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 (3¼ minutes at 38 ° C.) with subsequent bleaching fixation (see the one by Ernest Ch Gehret in the British Journal of Photographie, 1974, pages 597), with regard to their sensitometric properties.

To test for aldehyde stability, the samples were in a size of 35 x 250 mm for 7 days at room temperature in a vessel with a volume of 27 l in which there was a mixture of 650 g glycerol, 350 g water and 1 ml 30% formaldehyde found, 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 dicot compound.

Analogous results are obtained if compounds 1/12, II / 10 and III / 13 are used as curing agents instead of compound No. 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 11/15 was used as the curing agent.

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. Compound No. 11/10 is used as the hardening agent in all cases. 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, regardless of 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. Light-sensitive photographic silver halide recording material consisting of a layer support and applied to this layer at least one light-sensitive gelatine-containing layer containing a cross-linking agent which activates the carboxyl groups of the gelatine and a compound acting as aldehyde-scavenger, characterised in that the cross-linking agent which activates the carboxyl groups of gelatine is a gelatine hardener from the group comprising carbamoylonium salts, carbamoylpyridinium salts and carbamoyloxypyridinium salts, and the compound acting as aldehyde-scavenger corresponds to the general formula

wherein

Z represents the atoms required for completing a 5- or 6-membered optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring which may contain oxygen, nitrogen or sulphur as heteroatom.

2. Material according to Claim 1, characterised in that the compound acting as aldehyde-scavenger is a compound from the series comprising

cyclopentane-1,3-diones,

cyclohexane-1,3-diones,

pyran-2,4-diones,

dihydropyran-2,4-diones,

thiopyran-2,4-diones,

dioxa-cyclohexane-2,4-diones,

tetrahydropyrimidine-2,4-diones and

2,4,6-trioxohexahydropyrimidines,

in which compounds the ring carbon atoms may be substituted with straight- or branched-chain alkyl groups having 1 to 5 carbon atoms or carry a condensed cycloaliphatic or aromatic 6-membered ring or an aliphatic 5- or 6-membered ring in spiro-linkage.

3. Material according to Claims 1 and 2, characterised in that the total number of carbon atoms of the substituents in the ring carrying the two keto groups is not greater than 6.

4. Material according to Claims 1 to 3, characterised in that it contains a carbamoylpyridinium sulphonic acid betaine and a tetrahydropyrimidine-2,4-dione.

5. Material according to Claim 4, characterised in that it contains the compounds

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