EP0098454B1 - Procédé pour le tannage de la gélatine photographique avec des vinylsulfones contenant des groupes sulfonyl-éthylsulfates - Google Patents

Procédé pour le tannage de la gélatine photographique avec des vinylsulfones contenant des groupes sulfonyl-éthylsulfates Download PDF

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Publication number
EP0098454B1
EP0098454B1 EP83106070A EP83106070A EP0098454B1 EP 0098454 B1 EP0098454 B1 EP 0098454B1 EP 83106070 A EP83106070 A EP 83106070A EP 83106070 A EP83106070 A EP 83106070A EP 0098454 B1 EP0098454 B1 EP 0098454B1
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EP
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Prior art keywords
gelatin
cross
compounds
group
layers
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Expired
Application number
EP83106070A
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German (de)
English (en)
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EP0098454A2 (fr
EP0098454A3 (en
Inventor
Wolfgang Dr. Himmelmann
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Agfa Gevaert AG
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Agfa Gevaert AG
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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

  • the invention relates to a method for hardening photographic gelatin or photographic layers containing such gelatin.
  • metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and 1,4-diketones such as cyclohexanedione-1,2 and quinones and chlorides of 2-basic organic Acids, the anhydrides of tetracarboxylic acids, compounds with several reactive vinyl groups such as vinyl sulfones, acrylamides, compounds with at least two easily cleavable, heterocyclic 3-membered rings such as ethylene oxide and ethylene imine, polyfunctional methanesulfonic acid esters and bis-a-chloroacylamido compounds.
  • metal salts such as chromium, aluminum or zirconium salts, aldehydes and halogen-containing aldehyde compounds, in particular formaldehyde, dialdehydes and mucochloric acid, 1,2- and
  • high molecular weight curing agents such as e.g. Polyacrolein or its derivatives or copolymers and alginic acid derivatives are known, which are used specifically as layer-limited curing agents.
  • crosslinking agents for gelatin also have a skin-damaging effect, e.g. the ethyleneimine compounds, so that their use is not appropriate for physiological reasons alone.
  • hardening agents for photographic gelatin layers are compounds with two or more acrylic acid amido groups in the molecule, N, N ', N "-trisacryloylhydrotriazine or methylenebisacrylamide.
  • the hardening of the compounds is good after some time, but the compounds are sparingly soluble in water, which can lead to irregularities in the hardening within the layer.
  • DE-C 1 100 942 aromatic vinyl sulfone compounds and DE-A 1 147 733 have disclosed nitrogen or oxygen as heteroatoms containing heterocyclic vinyl sulfone compounds.
  • DE-C 1 808 685 and DE-A 2 348 194 describe bis - vinylsulfonylalkyl compounds as curing agents.
  • the known vinyl sulfone compounds have proven to be disadvantageous as curing agents in several respects. They are either not sufficiently water-soluble and require special measures to enable their use in photographic gelatin layers, or they adversely affect the drying behavior of the layers. It has been found to be particularly disadvantageous that these compounds increase the viscosity of the casting solution in such a way that the casting is considerably disturbed.
  • Tris and tetrakis vinyl sulfones are described (DE-A-25 45 722), but because of their high insolubility in aqueous solutions and the increase in viscosity caused by them, they cannot be used practically.
  • By partially reacting tris and tetrakis vinyl sulfones with aminoalkyl sulfonic acids water-soluble compounds are obtained, but the curing effect is greatly reduced by this reaction.
  • Tris and tetrakissulfonylethyl sulfates have also been described as crosslinking agents (EP-A-0 031 959). However, they have the disadvantage that hardening only begins after a long storage period or after treatment with alkaline baths. The compounds have a high molecular weight and the addition of salt to the layers is unreasonably increased.
  • the invention has for its object to develop a hardening process for photographic, gelatin-containing layers by which disturbances during the casting process can be prevented, which are caused by increased viscosity of the casting solutions by premature crosslinking of the gelatin, and by which neither the photographic properties, in particular color photographic materials Adversely affected, difficulties will arise during the later processing of the materials in photographic baths. Very good solubility and quick curing after the layers have dried should be achieved.
  • the invention relates to a process for curing a group consisting of a layer support and at least one attached thereto gelatin-containing layer, photonraphischen material with a reacting with the amino groups of the gelatin compound as a crosslinker, which is characterized in that the Begußmasse the aqueous layer gelatinehal t (s ) or the gelatin-containing layer (s) attached to the support is incorporated as a crosslinker, a compound which contains at least one vinylsulfone group and at least one sulfonylethylsulfate group in the form of their salts, and that the crosslinking occurs at pH values between 6 and 7 Drying of the gelatin-containing layers is carried out.
  • the compounds according to the invention have the advantage of being able to cure quickly even without the addition of pH-increasing compounds (PH 9).
  • the compounds according to the invention do not increase the viscosity of the casting solution at generally customary casting pH values of 6-7.
  • the compounds according to the invention have the advantage of greater effectiveness. While the water-solubilizing group in the vinylisulfone-sulfonylethyl sulfates according to the invention can be split off reversibly to form a group reacting with gelatin, in the known compounds a vinylsulfone group is irreversibly blocked by the reaction with aminoalkanesulfonic acid.
  • the compound is concentrated in ice water and the pH is adjusted to 5 by adding aqueous sodium bicarbonate solution. The aqueous solution is evaporated to dryness in vacuo. The product is triturated with acetone and suction filtered. Yield: 22 g. According to NMR measurement, the compound contains no vinyl sulfone groups.
  • n / 10 hydrochloric acid An approximately 15% solution is prepared by dissolving the compound from stage 1. The exact concentration of tetrasulfate is determined with a sample via the hydrolysis reaction. To do this, an excess of n / 10 sodium hydroxide solution is added to a precisely neutralized sample. After hydrolysis of the tetrasulfate, back titration is carried out with n / 10 hydrochloric acid.
  • hydroxyethyl sulfone compounds required for the reaction can be described in a known manner, as described in Ullmann vol. 14, p. 620, in Houben-Weyl, vol. IX, p. 247, or in DE-PS 965 902, for example via the Corresponding haloalkanes can be prepared by reaction with hydroxyalkyl mercaptans and oxidation of the sulfides formed to give the hydroxyethyl sulfones with H 2 0 2 .
  • the crosslinking agents used according to the invention can be added to the casting solution either some time before the coating or immediately before the coating by metering devices.
  • the compounds can also be added to a coating solution which is applied as a curing coating after the finished photographic material has been prepared.
  • the finished layer structure can also be drawn through a solution of the crosslinking agent and thereby receives the necessary amount of crosslinking agent.
  • the crosslinkers of the invention are introduced into the overall structure via the intermediate layers.
  • the crosslinkers are generally used in the process of the invention in an amount of 0.1 to 15% by weight and preferably 1 to 10% by weight, based on the dry weight of the gelatin in the coating solution.
  • the time of addition to the coating solution is not critical, but silver halide emulsions will expediently be added to the hardener after chemical ripening.
  • photographic layers are to be understood very generally as layers which are used in the context of photographic materials, for example light-sensitive silver halide emulsion layers, protective layers, filter layers, antihalo layers, backing layers or very generally photographic auxiliary layers.
  • light-sensitive emulsion layers for which the curing method according to the invention is excellently suitable there may be mentioned, for example, layers which are based on non-sensitized emulsions, X-ray emulsions and other spectrally sensitized emulsions.
  • the hardening process of the invention has proven itself for hardening the gelatin layers used for the various black and white and color photographic processes, such as negative, positive and diffusion transfer processes or printing processes.
  • the process according to the invention has proven to be particularly advantageous for the curing of photographic layer dressings which are intended for carrying out color photographic processes, e.g. those which contain emulsion layers with color couplers or emulsion layers which are intended for treatment with solutions which contain color couplers.
  • the effect of the compounds used in the manner according to the invention is not impaired by the usual photographic additives.
  • the hardeners are also indifferent to photographically active substances, such as water-soluble and emulsified water-insoluble color components, stabilizers, sensitizers and the like. Furthermore, they have no adverse effect on the light-sensitive silver halide emulsion.
  • the emulsion layers can contain any known silver halides as light-sensitive components, such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, silver chlorobiodobromide and the like.
  • the emulsions can be chemically sensitized by noble metal compounds, for example by compounds of ruthenium, rhodium, palladium, iridium, platinum, gold and the like, such as ammonium chloropalladate, potassium chloroplatinate, potassium chloropallada t , or potassium chloroaurate.
  • Bie can also contain special sensitizers such as sulfur compounds, tin (II) salts, polyamines or polyalkylene oxide compounds.
  • the emulsions can be optically sensitized with cyanine dyes, merocyanine dyes and mixed cyanine dyes.
  • the emulsions can be a wide variety of couplers, e.g. colorless couplers, colored couplers, stabilizers such as mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds or zinc compounds, wetting agents such as dihydroxyalkanes, agents which improve film formation properties, e.g. the particulate high polymers obtained in the emulsion polymerization of alkyl acrylate or alkyl methacrylate / acrylic acid or methacrylic acid, styrene / maleic acid mixed polymers or styrene / maleic anhydride half alkyl ester mixed polymers, obtained in water.
  • Coating aids such as polyethylene glycol lauryl ether, as well as various other photographic additives.
  • the couplers e.g. Purple couplers of the 5-pyrazolone type, cyan couplers of the naphthol or phenol type and yellow couplers of the closed ketomethylene type, so-called 2-valent and 4-valent couplers, which are derived from the above-mentioned couplers, and so-called masking couplers with an arylazo group on the active one Contained spot, no color changes occur in the photographic materials.
  • the crosslinking agents of the invention are particularly distinguished from the known hardeners of the vinylsulfonyl type in that they in no case increase the viscosity of the casting solutions by premature crosslinking in solution. This disadvantageous behavior is found in known vinyl sulfone hardeners, especially in compounds with more than 2 reactive vinyl sulfonyl groups.
  • the casting solutions can only be kept for a short time and a considerable technical effort is required to overcome the resulting difficulties.
  • the viscosities at 40 ° C were measured every hour.
  • the mixtures were digested at 40 ° C. for a long time (approx. 5 hours).
  • the behavior of the samples was examined at pH 6 and 6.5.
  • the pH values were adjusted using a buffer mixture of primary potassium phosphate and secondary sodium phosphate (6, 6.5).
  • the results are shown in Figure 1.
  • the dash-dotted curves 1 and 2 apply to the compound 19 according to the invention and to the pH values 6 (curve 1), 6.5 (curve 2).
  • the dashed curves 5 (pH 6) and 6 (pH 6.5) apply to the comparison compound VV1, the curves 3 (pH 6) and 4 (pH 6.5) to the comparison compound VV2.
  • the comparison compound VV1 crosslinks the gelatin according to curve 6 at a pH of 6.5 after 4 hours.
  • Comparative compound VV2 causes crosslinking in about 4 hours (curve 3) at pH 6 and after 2 hours at pH 6.5 (curve 4).
  • the mixture was stirred well and poured onto a prepared cellulose triacetate base with a conventional casting machine and dried.
  • the material was each one day at 23 ° C and 3 days under tropical conditions 36 ° C / 90% rel. Moisture stored and then tested for crosslinking by determining the layer melting point, the wet scratch resistance and the swelling factor. Good crosslinking is evident from a high layer melting point, high wet scratch resistance and a low swelling factor.
  • test specimen is developed as a black sheet in a conventional color development process and weighed after the final bath after the excess water has been wiped off. The sample is then dried and weighed again. The difference from the area of the test object to 1 m2 converts the water absorption per m 2 .
  • the swelling is measured gravimetrically after treatment of a test strip in distilled water at 22 ° C. for 10 minutes. It is denoted by the swelling factor:
  • a metal tip of a defined size is passed over the wet layer and loaded with increasing weight.
  • the wet scratch resistance is indicated by the weight at which the tip leaves a visible scratch mark on the layer; a high weight corresponds to a high wet scratch resistance.
  • the compounds 1 and 3 according to the invention produce boil-resistant layers (layer melting points above 100 ° C.) and high wet scratch resistance after only 1 day of storage, in contrast to the completely sulfated comparison compounds VV 3 and VV 4, which only after 3 show hardening during tropical storage.
  • the compounds according to the invention act much faster and thus differ significantly from the comparison compounds.
  • the casting solutions can be left to stand for one hour without increasing the viscosity, a sign of the desired low reaction of the compounds according to the invention with gelatin in solution.
  • the layers showed no serious differences compared to the uncured layer after development and fixation. Sensitivity, fog values and the y values did not change. The hardeners remained inert towards the halosilver emulsion even after the layers had been stored for a long time.
  • Aqueous solutions of 1/200 mol per 100 ml of compound 1, 20 and 6 were applied to the dried layer package and the layer structure was then dried.
  • the layers were examined for crosslinking after 5 days of storage at 22 ° C. with exclusion of moisture and after climate and tropical storage.
  • the table shows that the entire layer structure is hardened by the diffusing hardening system.
  • the individual layers are hardened homogeneously. There is no decrease in the hardening intensity depending on the distance from the surface. The result proves the excellent diffusibility of the compounds according to the invention.
  • the curing system of the invention is inert to the emulsion and color couplers in this application.
  • the table shows that the melting point rises to over 100 ° C. within a few days.
  • the photographic materials hardened in this way are therefore suitable for processing at 38-50 ° C after a short storage period.
  • the photographic properties such as fog, sensitivity and gradation are not changed.
  • samples were contained a crosslinker of the invention a photographic paper emulsion 80 g of gelatin and 35 g of silver halide per liter and 3 wt .-%, respectively, molded.
  • the usual pouring aids such as wetting agents, stabilizers and opt.
  • Sensitizers were previously added to the emulsion samples.
  • the layer melting points were determined directly after drying.
  • the layer melting points were determined after passing through a 22 ° C. photographic developer bath for black and white materials.
  • the example shows that the curing agents according to the invention crosslink relatively quickly and the crosslinking in the alkaline developer solution is not reduced again but is increased.

Claims (5)

1. Procédé de durcissement d'un matériau photographique constitué d'un support de couches et d'au moins une couche de gélatine appliquée sur ce support, avec, comme agent de réticulation, un composé réagissant avec les groupes amino de la gélatine, caractérisé en ce que, à la masse de coulée de la ou des couches contenant de la gélatine ou à la ou aux couches contenant de la gélatine et appliquées sur le support de couches, on incorpore, comme agent de réticulation, un composé contenant au moins un groupe vinylsulfone et au moins un groupe sulfonyléthylsulfate comme groupe hydrosolubilisant sous forme de leurs sels, tandis que l'on effectue la réticulation à des pH compris entre 6 et 7 après séchage des couches contenant de la gélatine.
2. Procédé selon la revendication 1, caractérisé en ce que, comme agent de réticulation, on utilise un composé répondant à la formule générale suivante:
(-Y-SO2-CH2-CH2-OSO3⊖ Me⊕s)n
Z
(-Y-SOy-CH =CH2)m
dans laquelle
Z = un radical d'hydrocarbure 2 à n + m-valent, aliphatique, saturé ou à insaturation oléfinique, à chaîne droite ou ramifiée, éventuellement substitué, comportant 1 à 9 atomes de carbone et pouvant contenir des groupes oxy, un radical 2 à n + m-valent, aromatique éventueliement substitué ou hétérocyclique ou carbocyclique entièrement ou partiellement hydrogéné, ou le groupe
NaS03-0-C=,
H
Y = une liaison simple, un groupe alkylène ramifié ou non comportant 1 à 4 atomes de carbone et dont la chaîne peut être interrompue et substituée par des groupes imino, carbonyle et oxy,
n = un nombre entier de 1 à 3,
m = un nombre entier de 1 à 3,
Me⊕ = un ion d'un métal alcalin.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que la solution d'application contenant l'agent de réticulation a un pH de 5-7.
4. Procédé selon les revendications 1-2, caractérisé en ce que l'agent de réticulation est introduit dans au moins une des solutions de coulée de structures à plusieurs couches en une quantité calculée de telle sorte que, dans le paquet total de couches, on règle une concentration de 0,5-5% d'agent de réticulation, calculé sur la gélatine.
5. Procédé selon la revendication 1, caractérisé en ce qu'on effectue le durcissement à des pH compris entre 6,5 et 7.
EP83106070A 1982-07-03 1983-06-22 Procédé pour le tannage de la gélatine photographique avec des vinylsulfones contenant des groupes sulfonyl-éthylsulfates Expired EP0098454B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3224983 1982-07-03
DE19823224983 DE3224983A1 (de) 1982-07-03 1982-07-03 Verfahren zur haertung photographischer gelatine mit sulfonyl-ethylsulfatgruppenhaltigen vinylsulfonen

Publications (3)

Publication Number Publication Date
EP0098454A2 EP0098454A2 (fr) 1984-01-18
EP0098454A3 EP0098454A3 (en) 1985-04-03
EP0098454B1 true EP0098454B1 (fr) 1987-05-20

Family

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Application Number Title Priority Date Filing Date
EP83106070A Expired EP0098454B1 (fr) 1982-07-03 1983-06-22 Procédé pour le tannage de la gélatine photographique avec des vinylsulfones contenant des groupes sulfonyl-éthylsulfates

Country Status (5)

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US (1) US4543324A (fr)
EP (1) EP0098454B1 (fr)
JP (1) JPS5918944A (fr)
CA (1) CA1248391A (fr)
DE (2) DE3224983A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60237445A (ja) * 1984-05-10 1985-11-26 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS61100743A (ja) * 1984-10-24 1986-05-19 Fuji Photo Film Co Ltd ゼラチンの硬化方法
JPS61128240A (ja) * 1984-11-28 1986-06-16 Fuji Photo Film Co Ltd ゼラチンの硬化方法
DE3523360A1 (de) * 1985-06-29 1987-01-08 Agfa Gevaert Ag Lichtempfindliches fotografisches aufzeichnungsmaterial
DE3608998A1 (de) * 1986-03-18 1987-10-01 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
JPH0612408B2 (ja) * 1986-05-09 1994-02-16 富士写真フイルム株式会社 ゼラチンの硬化方法
DE3708541A1 (de) * 1987-03-17 1988-10-13 Agfa Gevaert Ag Haertungsmittel fuer proteine, eine damit gehaertete bindemittelschicht und ein eine solche schicht enthaltendes fotografisches aufzeichnungsmaterial
JPS63241539A (ja) * 1987-03-30 1988-10-06 Fuji Photo Film Co Ltd ゼラチンの硬化方法
JPH0823667B2 (ja) * 1987-04-30 1996-03-06 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH0293641A (ja) * 1988-09-30 1990-04-04 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5187259A (en) * 1990-11-14 1993-02-16 Eastman Kodak Company Chain extended gelatin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5236007B2 (fr) * 1973-10-17 1977-09-13
JPS5221059A (en) * 1975-08-09 1977-02-17 Konishiroku Photo Ind Co Ltd Method for hardening gelatin
DE2943807A1 (de) * 1979-10-30 1981-05-14 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur haertung eines photographischen materials
DE3000407A1 (de) * 1980-01-08 1981-07-09 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur haertung photographischer gelatine

Also Published As

Publication number Publication date
DE3371708D1 (en) 1987-06-25
CA1248391A (fr) 1989-01-10
JPS5918944A (ja) 1984-01-31
EP0098454A2 (fr) 1984-01-18
US4543324A (en) 1985-09-24
DE3224983A1 (de) 1984-01-05
EP0098454A3 (en) 1985-04-03

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