EP0281146B1 - Verfahren und Zusammensetzung zum Härten von Gelatine - Google Patents

Verfahren und Zusammensetzung zum Härten von Gelatine Download PDF

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Publication number
EP0281146B1
EP0281146B1 EP19880103347 EP88103347A EP0281146B1 EP 0281146 B1 EP0281146 B1 EP 0281146B1 EP 19880103347 EP19880103347 EP 19880103347 EP 88103347 A EP88103347 A EP 88103347A EP 0281146 B1 EP0281146 B1 EP 0281146B1
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Prior art keywords
substituted
carbon atoms
unsubstituted
gelatin
hardening
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EP19880103347
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French (fr)
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EP0281146A1 (de
Inventor
Chung Yuan C/O Eastman Kodak Company Chen
Edgar Erick C/O Eastman Kodak Company Riecke
Kenneth George C/O Eastman Kodak Company Harbison
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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

  • This invention relates to a method and hardener composition for hardening gelatin, particularly in photographic elements.
  • Gelatin is commonly used as a vehicle in photographic materials. Quite often, numerous layers in photographic elements, such as light-sensitive silver halide layers, filter layers, backing layers, antihalation layers, and overcoat layers, use gelatin as the primary binder.
  • Photographic elements are generally processed in aqueous processing solutions. Such processing results in excessive swelling and loss of strength of the gelatin binder unless the gelatin has been hardened. If the processing solution is maintained at a warm temperature, e.g., 40°C, the gelatin binder can dissolve, causing the layers of the element to disintegrate, unless the gelatin has been hardened.
  • a warm temperature e.g. 40°C
  • a number of compounds have been used to harden gelatin. These include formaldehyde and free aldehydes as described in U.S. Patent 3,232,764, active esters as described in U.S. Patent 3,542,558, epoxy compounds as described in U.S. Patent 3,047,394, aziridines as described in U.S. Patent 2,950,197, and others well-known in the art. These compounds harden, or crosslink, gelatin, thus increasing its mechanical strength and reducing the swellability and solubility of the gelatin in aqueous processing solutions.
  • hardening compounds are, however, subject to a number of disadvantages. Some take an exceedingly long time after being cast and dried to give the desired degree of gelatin hardening, requiring elements containing gelatin hardened with those compounds to be aged for an extended time while the hardening process is completed. In other words, these hardeners exhibit after-hardening. Additionally, a number of compounds exhibit adverse effects on the photographic properties of elements in which they are used. Such adverse effects can include an increase in fog or a reduction in light sensitivity or photographic speed.
  • the present invention provides for hardening of gelatin by combining it with a compound of the formula:
  • R1 represents hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aralkyl of 7 to 20 carbon atoms, substituted or unsubstituted aryl of 6 to 20 carbon atoms, substituted or unsubstituted alkenyl, of 2 to 20 carbon atoms, -YR7, with Y representing sulfur or oxygen, and R7, R8, R9, R10, and R11 each independently representing substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aralkyl of 7 to 20 carbon atoms, substituted or unsubstituted aryl of 6 to 20 carbon atoms, or substituted or unsubstituted alkenyl of 2 to 20 carbon atoms.
  • R8 and R9, or R10 and R11 may together form a substituted or unsubstituted ring structure.
  • R10 and R11 may each also represent hydrogen.
  • R1 together with R2 may form a substituted or unsubstituted heterocyclic ring.
  • R2 and R3 each independently represents substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aralkyl of 7 to 20 carbon atoms, substituted or unsubstituted aryl of 6 to 20 carbon atoms, or substituted or unsubstituted alkenyl of 2 to 20 carbon atoms, or, combined with R1 or each other, forms a substituted or unsubstituted hererocyclic ring.
  • R4, R5, and R6 are defined as are R1, R2, and R3, respectively, and are the same as or different from R1, R2, or R3.
  • X ⁇ represents an anion or an anionic portion of the compound to form an intramolecular salt.
  • R1 represents hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aralkyl or 7 to 20 carbon atoms, substituted or unsubstituted aryl of 6 to 20 carbon atoms, substituted or unsubstituted alkenyl of 2 to 20 carbon atoms, -YR7, with Y representing sulfur or oxygen, and R7 R8, R9, R10, and R11 each independently representing substituted or unsubstituted alkyl of 1 to 20 carbon atoms, substituted or unsubstituted aralkyl of 7 to 20 carbon atoms, substituted or unsubstituted aryl of 6 to 20 carbon atoms, or substituted or unsubstituted alkenyl or 2 to 20 carbon atoms.
  • R8 and R9, or R10 and R11 may together form a substituted or unsubstituted ring structure.
  • R10 and R11 may each also represent hydrogen.
  • R1 together with R2 may form a substituted or unsubstituted heterocyclic ring, which may be further condensed with another ring.
  • R1 examples include hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms (e.g., methyl, ethyl, butyl, 2-ethylhexyl, or dodecyl), substituted or unsubstituted aralkyl of from 7 to 20 carbon atoms (e.g.
  • R1 can combine R2 or R3 to form a substituted or unsubstituted heterocyclic ring of 5 to 8 atoms.
  • This ring contains the nitrogen atom to which R2 and R3 are attached in formula (I) and may contain an additional nitrogen atom, or an oxygen or sulfur atom.
  • Such rings include pyridine, quinoline, isoquinoline, thiazole, benzothiazole, thiazoline, oxazole, benzoxazole, imidazole, benzimidazole, and oxazoline.
  • R7, R8, R9, R10, and R11 are substituted or unsubstituted alkyl of 1 to 20 carbon atoms (e.g., methyl, ethyl, butyl, 2-ethylhexyl, or dodecyl), substituted or unsubstituted aralkyl of from 7 to 20 carbon atoms (e.g., benzyl, phenethyl), substituted or unsubstituted aryl of from 6 to 20 carbon atoms (e.g., phenyl, naphthyl), or substituted or unsubstituted alkenyl of from 2 to 20 carbon atoms (e.g., vinyl, propenyl).
  • alkyl of 1 to 20 carbon atoms e.g., methyl, ethyl, butyl, 2-ethylhexyl, or dodecyl
  • R8 and R9, or R10 and R11 can also combine to form a substituted or unsubstituted ring structure of 5 to 8 atoms.
  • the R8-R9 ring contains the nitrogen atom to which R8 and R9 are attached, and may also contain an additional nitrogen atom, or an oxygen or sulfur atom.
  • the R10-R11 ring may also contain one or more nitrogen atoms, and oxygen atom, a sulfur atom, or any combination thereof. Examples of such rings include pyrrolidine, piperadine, and morpholine.
  • R2 or R3 may each be hydrogen, substituted or unsubstituted alkyl of 1 to 20 carbon atoms (e.g., methyl, ethyl, butyl, 2-ethylhexyl, or dodecyl), substituted or unsubstituted aralkyl of from 7 to 20 carbon atoms (e.g., benzyl, phenthyl), substituted or unsubstituted aryl of from 6 to 20 carbon atoms (e.g., phenyl, naphthyl), or substituted or unsubstituted alkenyl of from 2 to 20 carbon atoms (e.g., vinyl, propenyl).
  • alkyl of 1 to 20 carbon atoms e.g., methyl, ethyl, butyl, 2-ethylhexyl, or dodecyl
  • substituted or unsubstituted aralkyl of from 7 to 20 carbon atoms
  • R2 and R3 also preferably combine with each other to form a substituted or unsubstituted heterocyclic ring of 5 to 8 atoms.
  • This ring contains the nitrogen atom to which R2 and R3 are attached, and may also contain an additional nitrogen atom, or an oxygen or sulfur atom. Examples of such rings include pyrrolidine, piperadine, and morpholine. Either of R2 or R3 can combine with R1 to form a substituted or unsubstituted heterocyclic ring, as described above in reference to R1.
  • R4, R5, and R6 are defined the same as described above for R1, R2, and R3, respectively.
  • R4, R5, and R6 may each be the same as or different from R1, R2, and R3.
  • X ⁇ represents an anion or an anionic portion of the compound, which forms an intramolecular salt. Any anion that forms a salt compound according to formula (I) that is useful to harden gelatin according to the invention can be used.
  • Preferred anions include a sulfonate ion such as methylsulfonate or p-toluene sulfonate CF3SO ⁇ 3 , BF ⁇ 4 , PF ⁇ 6 , and ClO ⁇ 4 .
  • aralkyl, aryl, alkenyl, and heterocyclic groups groups, also useful as R1, R2, R3, R4, R5, R6, R7, and R8 include substituted alkyl, aralkyl, aryl, alkenyl, and heterocyclic groups.
  • Useful substituents include halogen, alkoxy of from 1 to 20 carbon atoms, aryloxy of from 6 to 20 carbon atoms, a sulfo group, N,N-disubstituted carbamoyl, N,N-disubstituted sulfamoyl, and other groups known to those skilled in the art that do not prevent the compounds from functioning as hardeners according to the invention.
  • the compounds of formula (I) can be made by techniques known to those skilled in the chemical synthesis art. Useful synthesis techniques are described in Journal of the American Chemical Society, 103 , 9839 (1981). The preparation of compounds of formula (I) is further described below in the synthesis examples.
  • the compounds of formula (I) can be used to harden any type of gelatin.
  • Types of gelatin useful in the practice of the present invention include alkali-treated gelatin, acid-treated gelatin, partially phthalated gelatin, double-dipped gelatin (i.e., gelatin treated with both alkali and acid), and the like.
  • gelatin is hardened by combining it with a compound of formula (I).
  • the method of hardening gelatin according to the invention can be advantageously be utilized to harden gelatin in photographic layers.
  • the present invention provides rapid hardening of gelatin with little or no after-hardening while avoiding many of the adverse photographic effects found with prior art hardeners, such as speed loss and fog.
  • the hardening compounds of formula (I) also are not highly hygroscopic as are many prior art hardening compounds, making them easy to handle. Additionally, the gelatin hardened according to the invention exhibits desirable physical properties, such as low tackiness.
  • gelatin is hardened by combining it with a hardening compound according to formula (I).
  • a hardening compound according to formula (I) is accomplished by techniques known to those skilled in the art.
  • the an aqueous solution of the hardening compound can be applied directly to an unhardened gelatin layer that has been coated on a support.
  • the hardening compound can be mixed with a gelatin-containing coating dispersion shortly before coating it onto a support.
  • Another way of using the compounds of formula (I) is to coat the compound in one layer of a photographic element in a manner such that it will diffuse into other layers of the element to harden those other layers.
  • the compounds of formula (I) according to the invention can also be used to partially harden gelatin. This is done, for example, by increasing the chain length of the gelatin, as described in U.S. Patent 4,421,847.
  • the amount of hardener used to harden gelatin according to the present invention will vary according to the purpose for which the gelatin is being used, the degree of hardening desired, and the particular compound of formula (I) that is used. If only a slight amount of hardening is desired, relatively small amounts of hardening compound can be used. If a greater degree of hardening is desired, relatively large amounts of hardener would be used.
  • the amount of hardener used according to the present invention is preferably between 0.01 and 20 weight percent, based on the weight of dry gelatin, and more preferably between 0.05 and 10 weight percent, based on the weight of dry gelatin.
  • the hardening compound of formula (I) that is used in the present invention can be used alone, in combination with another hardening compound according to formula (I), or in combination with any of a number of hardening compounds or hardening accelerators known in the art.
  • known hardening compounds include formaldehyde and free dialdehydes, sulfonate esters, epoxides, blocked active olefins, and others, as described in Research Disclosure, item 17643, section X (1978).
  • Examples of known hardening accelerators include nonprotonic solvents, as described in German OLS 2,417,586, tert-amines and their salts, as described in British Patent 1,269,983, and polyhydric alcohols.
  • the present invention is especially useful for hardening gelatin used in gelatin-containing layers in photographic elements.
  • Such elements are well-known in the art.
  • elements useful in the practice of the present invention include color negative film, color reversal film, color positive film, color print paper, color reversal print paper, black and white film, black and white paper, X-ray rilm, microfilm, and others well-known in the art.
  • Color films and papers generally contain a red-sensitive silver halide layer, a blue-sensitive silver halide layer, and a green-sensitive silver halide layer.
  • the red-sensitive layer usually has a cyan dye-forming coupler associated therewith
  • the blue-sensitive layer usually has a yellow dye-forming coupler associated therewith
  • the green-sensitive layer usually has a magenta dye-forming coupler associated therewith.
  • Photographic elements with which the present invention is useful generally include, in addition to the above-described light-sensitive layers, various additional layers, such as filter layers, subbing layers, interlayers, antihalation layers, and the like, as described in Research Disclosure, item 17643 (1978).
  • This Research Disclosure item also describes various addenda, such as surfactants and other coating aids, dye stabilizers, antifoggants, development inhibitor releasing compounds, filter dyes, optical brighteners, antistatic compounds, and the like, that can be included in photographic elements useful in the present invention, either in separate layers or in any of the above-described layers.
  • the gelatin-containing layers in photographic elements that are advantageously hardened by treatment with the compounds of formula (I) may utilize gelatin as the only binder in the layers, or the gelatin may be combined with other materials.
  • materials include, for example, dispersions of water insoluble or slightly soluble polymers, or hydrophilic colloidal polymer materials.
  • materials include acrylate polymers, vinyl alcohol polymers, halogenated styrene polymers, poly(sulfonic acid), poly(sulfinic acid), and others described in detail in Research Disclosure, item 17643, section IX (1978).
  • a test material was prepared by coating a layer containing a mixture of gelatin at a level of 9.69 g/m2 and colloidal silver at a level of 0.48 g/m2 onto an Estar TM film base.
  • the coated film base was cut into a series of test strips, which were treated with hardening compounds shown in Tables I and II by immersing each strip in an aqueous solution of the compound for 5 minutes, removing the excess solution from the surface of the element, and air-drying at 50°C.
  • the degree of after-hardening was determined by measuring the hardness of the freshly hardened gelatin layer compared to the hardness of a hardened gelatin layer after aging.
  • Hardness of the gelatin layer was measured by gradually immersing the test strip in a 0.8 weight percent aqueous solution of Takamine TM , a proteolytic enzyme, at a rate of 0.51 cm/min. The solution was adjusted to a pH of 7.2 and held at 25°C. The wedge length (the length of the strip from where the gelatin was completely removed to the last part of the strip to contact the enzyme solution) was measured and the hardness of the gelatin layer was calculated using the formula:
  • Compound 21 is compound 8 of U.S. Patent 4,612,280.
  • Compound 22 is compound 1 of EP 162,308. The results of this test are shown in Table III.
  • Table III shows that compounds 1 and 2 of the invention resulted in no evidence of after-hardening, while compounds 19, 20, and 23 resulted in significant after-hardening. Table III also shows that compounds 1 and 2 of the invention yielded a higher degree of hardening than was achieved by an equivalent molar amount of the hardener compounds 19, 20, 21, 22, or 23.

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Claims (12)

  1. Verfahren zur Härtung von Gelatine, bei dem man Gelatine und eine härtende Verbindung zusammenbringt, dadurch gekennzeichnet, daß die Verbindung der Formel entspricht:
    Figure imgb0027
     in der bedeuten:

    R₁ Wasserstoff, substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen, -YR₇,
    Figure imgb0028
     worin bedeuten: Y Schwefel oder Sauerstoff und R₇, R₈, R₉, R₁₀ und R₁₁ jeweils unabhängig voneinander substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen oder substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen, oder R₈ und R₉ gemeinsam einen substituierten oder unsubstituierten heterocyclischen Ring, oder R₁₀ und R₁₁ jeweils unabhängig voneinander Wasserstoff oder gemeinsam eine substituierte oder unsubstituierte Ringstruktur, oder R₁ gemeinsam mit R₂ oder R₃ einen substituierten oder unsubstituierten heterocyclischen Ring,

    R₂ und R₃ jeweils unabhängig voneinander substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen oder substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen, oder gemeinsam mit R₁ oder miteinander einen substituierten oder unsubstituierten heterocyclischen Ring,

    R₄, R₅ und R₆ wie R₁, R₂ beziehungsweise R₃ definiert sind und die gleiche oder eine verschiedene Bedeutung wie R₁, R₂ und R₃ haben und

    X⊖ für ein Anion oder einen anionischen Teil der Verbindung unter Bildung eines intramolekularen Salzes steht.
  2. Verfahren nach Anspruch 1, wobei bedeuten: R₁ und R₄ jeweils unabhängig voneinander Wasserstoff, substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen, -YR₇,
    Figure imgb0029
     worin bedeuten: Y Schwefel oder Sauerstoff und R₇, R₈, R₉, R₁₀ und R₁₁ jeweils unabhängig voneinander substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen oder substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen, oder R₁₀ und R₁₁ jeweils unabhängig voneinander Wasserstoff und R₂, R₃, R₅ und R₆ jeweils unabhängig voneinander substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen oder substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen.
  3. Verfahren nach Ansprüchen 1 oder 2, wobei bedeuten: R₁ und R₄ jeweils unabhängig voneinander Waserstoff, substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen, -YR₇, oder
    Figure imgb0030
     worin bedeuten: Y Schwefel oder Sauerstoff und R₇, R₈ und R₉ jeweils unabhängig voneinander substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen oder substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen und

    R₂, R₃, R₅ und R₆ jeweils unabhängig voneinander substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aralkyl mit 7 bis 20 Kohlenstoffatomen, substituiertes oder unsubstituiertes Aryl mit 6 bis 20 Kohlenstoffatomen oder substituiertes oder unsubstituiertes Alkenyl mit 2 bis 20 Kohlenstoffatomen.
  4. Verfahren nach Ansprüchen 1 bis 3, worin R₁ und R₄ unabhängig voneinander darstellen:
    Figure imgb0031
  5. Verfahren nach Ansprüchen 1 bis 4, worin mindestens eine Kombination von zwei Gliedern von R₁, R₂, R₃, R₄, R₅, R₈, R₉, R₁₀ und R₁₁ eine substituierte oder unsubstituierte Ringstruktur bilden.
  6. Verfahren nach Ansprüchen 1 bis 5, worin mindestens eine Kombination von zwei Gliedern von R₁, R₂, R₃, R₄, R₅ und R₆ einen substituierten oder unsubstituierten heterocyclischen Ring bilden.
  7. Verfahren nach Ansprüchen 1 bis 6, worin mindestens eine Kombination von entweder R₁ und R₂ oder R₄ und R₅ einen substituierten oder unsubstituierten heterocyclischen Ring bilden.
  8. Verfahren nach Ansprüchen 6 oder 7, worin der heterocyclische Ring ein substituierter oder unsubstituierter Pyridyliumring ist.
  9. Verfahren nach Ansprüchen 1 bis 8, worin R₂, R₃, R₅, R₆, R₈ und R₉ jeweils unabhängig voneinander substituiertes oder unsubstituiertes Alkyl mit 1 bis 20 Kohlenstoffatomen darstellen.
  10. Verfahren nach Ansprüchen 1 bis 9, worin R₂, R₃, R₅, R₆, R₈ und R₉ jeweils für Methyl oder Ethyl stehen.
  11. Zusammensetzung mit Gelatine, dadurch gekennzeichnet, daß sie nach dem Verfahren der Ansprüche 1 bis 10 gehärtet ist.
  12. Photographisches Element mit einem Träger, auf dem sich mindestens eine Schicht mit Gelatine befindet, dadurch gekennzeichnet, daß die Gelatine nach der Methode nach den Ansprüchen 1 bis 10 gehärtet ist.
EP19880103347 1987-03-05 1988-03-04 Verfahren und Zusammensetzung zum Härten von Gelatine Expired - Lifetime EP0281146B1 (de)

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