US3880665A - Hardening with a heterocyclic carbamoyl ammonium compound of a photographic material containing a silver halide layer - Google Patents

Hardening with a heterocyclic carbamoyl ammonium compound of a photographic material containing a silver halide layer Download PDF

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US3880665A
US3880665A US362484A US36248473A US3880665A US 3880665 A US3880665 A US 3880665A US 362484 A US362484 A US 362484A US 36248473 A US36248473 A US 36248473A US 3880665 A US3880665 A US 3880665A
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hardener
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Wolfgang Himmelmann
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
    • C07D217/10—Quaternary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/205—Radicals derived from carbonic acid
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • ABSTRACT As rapidly acting hardeners for protein-containing photographic layers carbamoyl ammonium compounds are used the quaternised nitrogen atom of which being present in a 5- or 6-membered heterocyclic aromatic group.
  • metal salts such as chromium, aluminium or zirconium salts, aldehydes and halogenated aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and 1,4-diketones such as cyclohexane-l,2-dione and quinones as well as chlorides of dibasic organic acids, the anhydrides of tetracarboxylic acids, compounds which contain several reactive vinyl groups such as vinyl sulfones, acrylamides, compounds containing at least two heterocyclic threemembered rings which can easily be split off, such as ethylene oxide and ethylene imine, polyfunctional methane sulfonic acid esters and bis-oz-chloracylamido compounds.
  • metal salts such as chromium, aluminium or zirconium salts, aldehydes and halogenated aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric
  • High molecular weight hardeners which are used particularly as hardeners of which the effect is to be confined to the layer having recently become known, for example polyacrolein and its derivatives or copolymers and alginic acid derivatives.
  • Some cross-linking agents for gelatin for example the ethylene imine compounds, also have a harmful effect on the skin and are therefore in any case unsuitable on physiological grounds.
  • Hardening of the compounds is quite satisfactory after a certain time but the compounds are only sparingly soluble in water so that hardening is liable to be irregular within the layer.
  • a process for hardening photographic layers which contain proteins and preferably gelatin has now been found which is characterised by the use of a hardener which contains in the molecule at least one carbamoyl radical with a heterocyclic, aromatic S-membered or 6-membered ring which in addition to a quaternary nitrogen atom may also contain other hetero atoms.
  • the hardeners of this invention correspond to the following general formula R R X N-CO-N Z X R/ l inwhich R represents a substituted or unsubstituted alkyl group preferably containing 1 to 3 carbon atoms, an aryl group optionally substituted with a lower alkyl radical or with halogen, e.g., phenyl, if desired substituted with methyl, ethyl or propyl, C1 or Br, or an aralkyl group, e.g., benzyl, which may be substituted in the same manner as the aryl group;
  • R has the same meaning as R or it may represent a divalent optionally substituted alkylene, arylene, aralkylene or alkyl-aryl-alkyl radical, e.g., an ethylene, propylene, phenylene or xylylene radical which is attached by its second bond to a further carbamoyl ammonium group of the formula R 4 1 --1?
  • iZ X 01" R R, and R may together represent a group required to complete a substituted or unsubstituted heterocyclic ring, such as piperidine, piperazine, or morpholine ring which may be substituted e.g., with an alkyl group containing 1 to 3 carbon atoms or with halogen such as C1 or Br;
  • R represents hydrogen or an alkyl group containing 1 to 3 carbon atoms or the group R represents an alkyl, aryl or aralkyl group but R is absent if the nitrogen to which R is attached is involved in a double bond in the heterocyclic aromatic ring formed by Z,
  • Z represents the atomic grouping required to complete a S-membered or 6-membered aromatic ring optionally substituted on the nitrogen atom, e.g., with an alkyl group containing 1 to 3 carbon atoms or it may represent the atomic grouping required to complete a condensed system such as isoquinoline, which atomic grouping may contain other hetero atoms in addition to the nitrogen atom, e.g., O or S, and
  • X represents an acid anion such as halogen Bfl
  • the preparation of the other compounds is carried out in a corresponding manner.
  • the salts can be easily prepared by addition of the suitable acids.
  • the compounds used according to the invention are preferably added to the protein layers which are to be hardened immediately before they are cast, preferably in the form of aqueous or alcoholic solutions. It is necessary to add them only shortly before the layers are cast because they react very rapidly with gelatin or other proteins normally used in photography. Once the compounds have been added, the casting solutions should be cast within a few minutes. The rate at which the hardening reaction takes place depends primarily on the concentration of proteins in the casting solution.
  • Another possiblity consists in casting solutions which have not been hardened and then coating the resulting layers with a solution of the hardening compounds.
  • photographic layers which have not been hardened or only slightly hardened may be bathed in aqueous solutions of the compounds containing sodium sulfate at some stage of processing the photographic material, for example before development.
  • photographic layers is used in this context as a general term to denote any layers used in photographic materials, for example light sensitive silver halide emulsion layers, protective layers, filter layers, antihalation layers, back coating layers or, in general, any photographic auxiliary layers.
  • the light sensitive emulsion layers for which the hardening process according to the invention is particularly suitable are, for example, those layers which are based on non-sensitized emulsions, orthochromatic, panchromatic or infra-red emulsions, X-ray emulsions and other emulsions which are spectrally sensitized.
  • the hardening process according to the invention has also proved suitable for hardening gelatin layers used for various black-and-white photographic processes and colour photographic processes.
  • the process according to the invention has proved particularly advantageous for hardening composite photographic layers used for colour photographic processes, e.g., those which contain emulsion layers with colour couplers or emulsion layers which are designed to be treated with solutions which contain colour couplers.
  • the effect of the compounds used according to the invention is not impaired by the usual photographic additives and the hardeners are also uneffected by photographically active substances such as water-soluble or emulsified water insoluble dry components, stabilizers, sensitizers and the like. Moreover, they have no influence on the light sensitive silver halide emulsions. They may be combined with any compounds from the known classes of hardeners, for example formalin, mucochloric acid, triacrylic formal, bis-vinylsulfones, bisvinylsuflonamides, dialdehydes or bischloroacetamides.
  • hardeners for example formalin, mucochloric acid, triacrylic formal, bis-vinylsulfones, bisvinylsuflonamides, dialdehydes or bischloroacetamides.
  • the layers may also contain water-soluble high polymer compounds, in particular polyvinyl alcohol, polyacrylic acid sodium and other copolymers which contain carboxyl groups, polyvinyl pyrrolidone, polyacrylamide or high molecular weight natural substances such as dextrans, dextrins, starch ether,alginic acid or alginic acid derivatives.
  • water-soluble high polymer compounds in particular polyvinyl alcohol, polyacrylic acid sodium and other copolymers which contain carboxyl groups, polyvinyl pyrrolidone, polyacrylamide or high molecular weight natural substances such as dextrans, dextrins, starch ether,alginic acid or alginic acid derivatives.
  • concentrations at which the hardeners according to the invention are used may vary within wide limits and depend mainly on the hardening compound used.
  • the hardening reaction between the compounds according to the invention and gelatin or proteins sets in immediately so that the optimum degree of hardening is reached more or less simultaneously with drying of the layers after they are cast or processed.
  • the activity of the hardening compounds is determined by means of the melting point of the layers, which can be found as follows: Half of a layer cast on a support is dipped in water which is continuously heated up to C. The temperature at which the layer runs from the support (formation of streaks) is taken as the melting point or melting off point. When measured by this method, no increase in melting point is found in any pure protein layers or gelatin layers which contain no hardener, on the contrary the layers run off at 3035C.
  • the compounds according to the invention react surprisingly quickly with proteins and therefore enable materials which contain proteins to be hardened to their optimum degree of hardness within a very short time.
  • This unexpected effect of the compounds is particularly important for the hardening of photographic materials which contain proteins as binders. Hardening can be adjusted to the required degree in a readily controlled nammer at the stage of preparation of the materials and does not require prolonged storage times with the concomitant unreliability of uncontrollable after hardening.
  • EXAMPLE 1 l by weight and 2 by weight, respectively, of compounds 2. l9 and 20 based on the dry weight of gelatin, are added in the form of an aqueous solution at pH 6.2 to 100 ml portions of a photographic silver bromide gelatin emulsion containing 10 by weight of gelatin which is ready for casting. The mixture is vigorously stirred and immediately cast on a prepared cellulose triacetate support by means of a conventional casting apparatus and dried. The usual additives are not altered. After a storage time of 24 hours at room temperature, the melting points of the layers are measured.
  • EXAMPLE 2 14 EXAMPLE 3 A 10 casein solution in water is prepared by the addition of sodium hydroxide solution. The solution is divided in 9 parts of 100 ml and 0.1 g of tartrazine is added as filter dye to each solution. 3 by weight of compounds 2, 19, 20, 21, 24, 25, 30, 31 and 37 dissolved in water are added at pH 7 before casting. The mixtures are cast on glass plates and hardened filter foils which are no longer soluble in aqueous alkali are obtained after drying.
  • EXAMPLE 4 A 20 by weight of solution of zein is prepared in a mixture of ethanol and water (8:2) and cast on the back of a cellulose acetate film. After drying, a layer which is readily soluble in a mixture of ethanol and water is obtained.
  • EXAMPLE 5 An unhardened silver halide emulsion containing 10 by weight of gelatin as binder is cast on a triacetyl cellulose support without the addition of a hardener. The layer contains all the other usual additives. Samples of the dried layer are coated with 0.5, l, 2 and 3 aqueous solutions of compounds 1. 2. 5, 24, 29 and 33 and then dried. The melting points, degree of swelling and resistance to scratching when wet are then determined on the layers. The results are summarized in the following Table.
  • the degrees of swelling are determined gravimetrically after 10 minutes treatment of the layers in distilled water at 22C and are indicated in percent.
  • a metal point of a specified size is passed over the wet layer and loaded with an increasingly heavy weight.
  • the wet scratch resistance is indicated by the weight at which the point leaves a visible scratch trace on the layer. The larger the weight the higher the scratch resisimmersion time layer melting points remarks in minutes in "C 50 tance.
  • compound comgound compound layer swelling wet scratch melting point in 7 resistance 0.5 50C 60C in p l 100C 100C soft layer 5 5 2 l00C l00C increased strength campound of layer 0.5 it 355 750 3 100C l00C very high strength 1 7, 3K) 850 of layer 2 l0 H10 280 950 untreated layer 34C 3 250 950 60 gompound 2: .5 "l 325 950 At a bath temperature of 40C, the required tmmerl o, 295 950 sion times are much shorter and layer melting points 2 3 H 52? 8 above 100C are obtained after only 45 seconds.
  • the layer is not dissolved off after l0 minutes in boiling water.
  • EXAMPLE 7 The usual additives with the exception of a hardener EXAMPLE 6 are added tp 100 ml o fa phpoqgrzgphic siLverfbrolmide e atln emu sion contalnm wei t 0 e atin. 25 by weight, based on the weight of the gelatin, g g 0 y g g f b] l f th f n f l The mixture is cast 0 a ue green coup er 0 e o owing ormu a a on baryta paper and b. on paper backed with polyethylene on both sides.
  • a 4p. green sensitive middle layer which contains 35 g of silver bromide, 80 g of gelatin and 16 g of top coating melting swelling wet scratch 'p y' p y fpy point in 7r resistance in p 5 per k f CmUISiOn, compound I: 4. a 2p. yellow filter layer of colloidal silver in gelatin, 0.5 1o'
  • a 4 blue sensitive top layer which contains 35 Z: 32 8 328 g of silver bromide, g of gelatin and 20 g 3- 3 250 950 stearylammobenzoyl acetyl-S, 3-d1carboxyanilide per kg of emulsion and compound 2: I 0 0 6 2 I f l 0.5 10 C 325 950 a u protective ayer o ge atm 22 2 is cast in known manner on a layer support of cellulose 3 235 1150 triacetate p. in thickness and dried. The film is coated with a l aqueous solution and a 2 aqueous gg a l c 350 850 65 solution of compounds 2 5, l9 and 30. l 3 8 2 The layer melting points and the temperatures at g 250 50 which the layers dissolve off are determined after drying and 12 hours storage at room temperature.
  • temperature 1 A process for providing a protein-containing with n Coalmg M layer mcltlng P f binder selected from the group consisting of gelatin, ca-
  • a photographic silver halide emulsion compound 2 1% 752C 10'100C layer coated on a support wherein the improvement comprises incorporating in a binder for the layer a compound 5 l 7? 100 C l0 100 C 2 100C g'mo c hardening amount of a hardener of the formula compound 19 l 70 l00C l0'l0OC 2 7! 100C l0'l0OC compound 30 l 71. l00C l0'l00C 2 7!
  • R is selected from the group consisting of alkyl, aryl, aralkyl groups and the methylene group substituted with a group of the formula 40 ml of a 5 70 aqueous solution of polyacrylic acid sodium salt and 10 ml of a 40 SiO suspension are added to 100 ml of a 10 gelatin solution. The solution is vigorously mixed. 0.2 g of compounds 6 and 20 are added to each 100 ml of the solution. Then the pH is adjusted to 6.2 and the mixtures are cast on cellulose triacetate supports. Layers with a melting point above N co N 100C and exellent wet strength are obtained after drying and 12 hours storage. A layer without the addition CH ONH2 of the compounds according to the invention melts in water at 40C.
  • 0.2 g of compounds 6 and 23 are added to l00 ml of R5 is Selacted f the group of one alkyl 10 aqueous solutions of acetyl gelatin which have gro ups ar ld not f when the mtmgFn to been obtained by reacting gelatin with 20 acetic anwhch attached car nes double bond f the hydride and the mixtures are cast on cellulose acetate hetemcychc aromatc rmg formed by Substltuted films. A layer containing 0.2 g of formalin instead of compounds 6 and 23 is cast for comparison.
  • the layers containing compounds 6 and 23 are re- 6'membered heterocycllc 8 whlch y sistant to boiling whereas the layer which has been Include one or more Condensed mugs and one or hardened with formalin melts at temperatures below more heleroa'loms,
  • R stands for -NR -c0-R R H, alkyl (llc) R H, alkyl (1-4 G) 9 o R", R H, alkyl (c -c 2)m lO ll R10 l2 R H, alkyl (c -c R12: H, alkyl (c -c R alkyl (c -c aryl R1 H, alkyl, aryl ..(CH -CONR R R H, alkyl (c -c aryl R H, alkyl (c -ci or R and R together represent the atomic grouping required to complete a S
  • R H alkyl, -c0-R -CO-NHR
  • R R20, R21 H alkyl
  • c -c X is the anion radical of the formula, or poly-4-vinyl- N,N-dimethyl-carbamoyl-pyridinium chloride having molecular weight of about 10,000.
  • Page 1 of 2 Column 4 lines 17 & 18 should read as follows X represents an acid anion such as halogen BF N0 S0 010;, cn oso Column 6, formula 12, the left-hand ring should read as follows Column 18, the right-hand side of the first formula should read as follows GB N Column 18, the right-hand side of the second formula should CONH UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATEN N 3,880,665 Page 2 of 2 DATED :April 29, 1975 INVENTOR(S) t Wolfgang Himmelmann It is certified that error appears in the ab0ve-identified patentand that said Letters Patent are hereby corrected as shown below:
  • the hardener is polyr-vinyl-N,N-dimethyl-carbamoylpyridinium chloride having molecular weight of about 10,000.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
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US362484A 1972-05-24 1973-05-21 Hardening with a heterocyclic carbamoyl ammonium compound of a photographic material containing a silver halide layer Expired - Lifetime US3880665A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19722225230 DE2225230C2 (de) 1972-05-24 1972-05-24 Verfahren zur Härtung photographischer Schichten
DE19732317677 DE2317677C2 (de) 1973-04-07 1973-04-07 Verfahren zur Härtung photographischer Schichten

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JP (1) JPS5612853B2 (cs)
CA (1) CA1019615A (cs)
CH (1) CH582897A5 (cs)
FR (1) FR2185807B1 (cs)
GB (1) GB1383630A (cs)
IT (1) IT988201B (cs)

Cited By (19)

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Publication number Priority date Publication date Assignee Title
US3951940A (en) * 1974-09-30 1976-04-20 Ciba-Geigy Ag Method of producing a hardened gelatin layer using aqueous solution of a 2-halogeno pyridinium compound
US3977881A (en) * 1974-01-31 1976-08-31 Ciba-Geigy Ag Acylurea compounds
US4014862A (en) * 1972-07-12 1977-03-29 Ilford Limited Production of hardened gelatin layers by the addition of quaternary carbamoyl pyridinium compounds
US4047957A (en) * 1975-02-10 1977-09-13 Agfa-Gevaert N.V. Process of hardening protein-containing photographic layers with a mixture of a carboxyl group-activating, low molecular weight compound and a carboxyl group-activating polymer
US4055427A (en) * 1974-02-23 1977-10-25 Agfa-Gevaert Aktiengesellschaft Process of hardening a silver halide photographic material with a 1-carbamoyloxypyridinium salt
US4061499A (en) * 1975-10-11 1977-12-06 Agfa-Gevaert Aktiengesellschaft Process for hardening silver halide photographic layers with organic asymmetric monocarbodiimides
US4063952A (en) * 1974-08-17 1977-12-20 Agfa-Gevaert Aktiengesellschaft Process for hardening silver halide containing photographic layers with sulpho- or sulphoalkyl-substituted carbamoyl pyridinium compounds
US4067741A (en) * 1975-10-24 1978-01-10 Agfa-Gevaert, A.G. Hardening photographic layers containing silver halide with a 1-sulphonyl-4-amino-pyridinium salt
US4119464A (en) * 1976-06-03 1978-10-10 Agfa-Gevaert Aktiengesellschaft Process for hardening photographic layers containing gelatine
US4123281A (en) * 1975-09-06 1978-10-31 Agfa-Gevaert N.V. Photographic silver halide color material containing fast-acting hardener and 2-pyrazolin-5-one coupler precursors
US4233398A (en) * 1974-04-11 1980-11-11 Agfa-Gevaert, A.G. Process for the hardening of photographic layers utilizing fast acting hardener and polysaccharide
US4810625A (en) * 1986-04-25 1989-03-07 Agfa-Gevaert Aktiengesellschaft Photographic material with pyrazolone coupler and oil former
US5034249A (en) * 1986-08-29 1991-07-23 Agfa Gevaert Aktiengesellschaft Process for hardening layers containing proteinaceous binders
WO1993012667A1 (en) * 1991-12-26 1993-07-08 Opta Food Ingredients, Inc. Purification of zein from corn gluten meal
US5378842A (en) * 1993-12-21 1995-01-03 E. I. Du Pont De Nemours And Company Imidazolium hardeners for proteinaceous materials
US5576155A (en) * 1994-10-07 1996-11-19 Sterling Diagnostic Imaging, Inc. Fast-processing photographic recording material for medical radiography
US5601971A (en) * 1991-06-18 1997-02-11 Sterling Diagnsotic Imaging, Inc. Hardening of hydrophilic colloids with imidazolium and triazine combinations
US6028199A (en) * 1995-07-20 2000-02-22 Agfa-Gevaert Nv Hardeners for photographic materials
US6468339B1 (en) 2001-08-23 2002-10-22 Eastman Kodak Company Alumina filled gelatin

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JPS53113856A (en) * 1977-03-16 1978-10-04 Mitsubishi Paper Mills Ltd Gelatine curing process
JPS62291565A (ja) * 1986-05-28 1987-12-18 マイルス・ラボラトリ−ズ・インコ−ポレ−テッド 硬化試薬マトリックス被膜及びその製造方法
DE3626221A1 (de) * 1986-08-02 1988-02-04 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial zur herstellung farbiger aufsichtsbilder

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US2950197A (en) * 1955-04-18 1960-08-23 Eastman Kodak Co Hardening of gelatin
US3676143A (en) * 1969-08-21 1972-07-11 Agfa Gevaert Ag Treatment of exposed silver halide emulsion with acidic hardening bath following by alkaline activating bath

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GB1393959A (en) * 1972-07-12 1975-05-14 Ilford Ltd Hardened gelatin layers

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Publication number Priority date Publication date Assignee Title
US2950197A (en) * 1955-04-18 1960-08-23 Eastman Kodak Co Hardening of gelatin
US3676143A (en) * 1969-08-21 1972-07-11 Agfa Gevaert Ag Treatment of exposed silver halide emulsion with acidic hardening bath following by alkaline activating bath

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014862A (en) * 1972-07-12 1977-03-29 Ilford Limited Production of hardened gelatin layers by the addition of quaternary carbamoyl pyridinium compounds
US3977881A (en) * 1974-01-31 1976-08-31 Ciba-Geigy Ag Acylurea compounds
US4055427A (en) * 1974-02-23 1977-10-25 Agfa-Gevaert Aktiengesellschaft Process of hardening a silver halide photographic material with a 1-carbamoyloxypyridinium salt
US4233398A (en) * 1974-04-11 1980-11-11 Agfa-Gevaert, A.G. Process for the hardening of photographic layers utilizing fast acting hardener and polysaccharide
US4063952A (en) * 1974-08-17 1977-12-20 Agfa-Gevaert Aktiengesellschaft Process for hardening silver halide containing photographic layers with sulpho- or sulphoalkyl-substituted carbamoyl pyridinium compounds
US3951940A (en) * 1974-09-30 1976-04-20 Ciba-Geigy Ag Method of producing a hardened gelatin layer using aqueous solution of a 2-halogeno pyridinium compound
US4047957A (en) * 1975-02-10 1977-09-13 Agfa-Gevaert N.V. Process of hardening protein-containing photographic layers with a mixture of a carboxyl group-activating, low molecular weight compound and a carboxyl group-activating polymer
US4123281A (en) * 1975-09-06 1978-10-31 Agfa-Gevaert N.V. Photographic silver halide color material containing fast-acting hardener and 2-pyrazolin-5-one coupler precursors
US4061499A (en) * 1975-10-11 1977-12-06 Agfa-Gevaert Aktiengesellschaft Process for hardening silver halide photographic layers with organic asymmetric monocarbodiimides
US4067741A (en) * 1975-10-24 1978-01-10 Agfa-Gevaert, A.G. Hardening photographic layers containing silver halide with a 1-sulphonyl-4-amino-pyridinium salt
US4119464A (en) * 1976-06-03 1978-10-10 Agfa-Gevaert Aktiengesellschaft Process for hardening photographic layers containing gelatine
US4810625A (en) * 1986-04-25 1989-03-07 Agfa-Gevaert Aktiengesellschaft Photographic material with pyrazolone coupler and oil former
US5034249A (en) * 1986-08-29 1991-07-23 Agfa Gevaert Aktiengesellschaft Process for hardening layers containing proteinaceous binders
US5601971A (en) * 1991-06-18 1997-02-11 Sterling Diagnsotic Imaging, Inc. Hardening of hydrophilic colloids with imidazolium and triazine combinations
US5580959A (en) * 1991-12-26 1996-12-03 Opta Food Ingredients, Inc. Purification of zein from corn gluten meal
US5254673A (en) * 1991-12-26 1993-10-19 Opta Food Ingredients, Inc. Purification of zein from corn gluten meal
WO1993012667A1 (en) * 1991-12-26 1993-07-08 Opta Food Ingredients, Inc. Purification of zein from corn gluten meal
US5378842A (en) * 1993-12-21 1995-01-03 E. I. Du Pont De Nemours And Company Imidazolium hardeners for proteinaceous materials
US5459029A (en) * 1993-12-21 1995-10-17 E. I. Du Pont De Nemours And Company Photographic element hardened with imidazolium hardeners
US5576155A (en) * 1994-10-07 1996-11-19 Sterling Diagnostic Imaging, Inc. Fast-processing photographic recording material for medical radiography
US6028199A (en) * 1995-07-20 2000-02-22 Agfa-Gevaert Nv Hardeners for photographic materials
US6468339B1 (en) 2001-08-23 2002-10-22 Eastman Kodak Company Alumina filled gelatin

Also Published As

Publication number Publication date
GB1383630A (en) 1974-02-12
JPS5612853B2 (cs) 1981-03-25
CA1019615A (en) 1977-10-25
FR2185807A1 (cs) 1974-01-04
JPS4951945A (cs) 1974-05-20
FR2185807B1 (cs) 1976-09-17
CH582897A5 (cs) 1976-12-15
IT988201B (it) 1975-04-10

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