EP0098454A2 - 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
EP0098454A2
EP0098454A2 EP83106070A EP83106070A EP0098454A2 EP 0098454 A2 EP0098454 A2 EP 0098454A2 EP 83106070 A EP83106070 A EP 83106070A EP 83106070 A EP83106070 A EP 83106070A EP 0098454 A2 EP0098454 A2 EP 0098454A2
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EP
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Prior art keywords
gelatin
layer
compound
compounds
layers
Prior art date
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Application number
EP83106070A
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German (de)
English (en)
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EP0098454B1 (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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Publication of EP0098454A3 publication Critical patent/EP0098454A3/de
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Publication of EP0098454B1 publication Critical patent/EP0098454B1/fr
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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 as well as 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- ⁇ -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,
  • 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.
  • the use of the compounds mentioned for photographic purposes is associated with a number of serious disadvantages. Some of these compounds are photographically active and are therefore unsuitable for hardening photographic materials, others influence the physical properties, e.g. the fragility of the gelatin layers so disadvantageous that they cannot be used. Others cause discoloration or a change in pH during the curing reaction. In addition, it is particularly important for the hardening of photographic layers that the hardening reaches its maximum as soon as possible after drying, so that the permeability of the material to be hardened to the developer solution does not change continuously, as in the case of mucochloric acid or formaldehyde, for example .
  • 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 " - tris-acryloylhydrotriazine 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.
  • Particular problems arise with the increasingly rapid processing of photographic, especially color photographic, materials, which places increased demands on the mechanical properties and the swelling behavior of the materials.
  • the known hardening agents either caused new difficulties or simply proved unsuitable.
  • 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 not sufficient either 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, but because of their high insolubility in aqueous solutions and the increase in viscosity caused by them, they cannot be used practically.
  • Tris and tetrakissulfonylethyl sulfates have also been described as crosslinking agents. 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 malfunctions during the casting process can be prevented, which are caused by increases in viscosity of the casting solutions due to premature Ver Wetting the gelatin are caused, and by which neither the photographic properties, in particular color photographic materials are adversely affected nor difficulties arise in 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 method for hardening a photographic material consisting of a layer support and at least one gelatin-containing layer applied thereon with a compound reacting with the amino groups of the gelatin as a crosslinking agent, which is characterized in that the casting compound of the gelatin-containing layer (s) or a compound which contains at least one vinylsulfone group and at least one sulfonylethylsulfate group in the form of their salts is incorporated as crosslinker into the gelatin-containing layer (s) attached to the support.
  • 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 Compared to the reaction products of tris or tetrakis vinyl sulfones with aminoalkanesulfonic acids, the compounds according to the invention have the advantage of greater effectiveness. While the water-solubilizing group in the vinyl sulfone and sulfonylethyl sulfates according to the invention can be reversibly split off to form a group reacting with gelatin, in the known compounds a vinyl sulfone group is irreversibly blocked by the reaction with aminoalkanesulfonic acid.
  • crosslinking compounds The production process of the crosslinking compounds is explained below with reference to the production of the compounds 1, 6 and 20. All other connections can be made accordingly.
  • the compound is concentrated in ice water and by adding aqueous sodium bicarbonate solution adjust the pH 5.
  • the aqueous solution is evaporated to dryness in vacuo.
  • the product is triturated with acetone and suction filtered. Yield: 22 g.
  • 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.
  • a spatula tip of dinitrobenzoic acid is added to 741 g of 12.3% solution (91.2 g of compound stage 1) and then, with vigorous stirring, 600 ml of 1% sodium hydroxide solution are added dropwise at room temperature, the pH always between 9-10 is held. The mixture is stirred for 2 hours at room temperature, the pH is then adjusted to 5 with dilute sulfuric acid and the mixture is filtered. In this form the compound is stable for 3 months at room temperature. Based on the analytical determination, the compound obtained contains 2 sulfate groups per molecule. Establishing connection 6
  • 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 DT-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 hardening 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 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 hardening medium 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, e.g. by compounds of ruthenium, rhodium, palladium, iridium, platinum, gold and the like, such as ammonium chloropalladate, potassium chloroplatinate, potassium chloropalladate, or potassium chloroaurate. They 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, for example colorless couplers, colored couplers, stabilizers, such as mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds or zinc compounds, wetting agents, such as dihydroxyalkanes, which improve the film-forming properties
  • Agents for example the particulate high polymers obtained in the emulsion polymerization of alkyl acrylate or alkyl methacrylate / acrylic acid or methacrylic acid, dispersed in water, styrene / maleic acid mixed polymers or styrene / maleic anhydride half-alkyl ester mixed polymers, coating aids such as polyethylene glycol lauryl ether, and various other photographic additives, as well as various other additives contain.
  • 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 determined at pH Values 6 and 6.5, examined.
  • 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 .
  • 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.
  • Table 1 It can be seen from Table 1 that 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 / values did not change. The hardeners remained inert towards the halosilver emulsion even after the layers had been stored for a long time.
  • the curing system of the invention is inert to the emulsion and color couplers in this application.
  • the results are shown in the table below.
  • 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 of a photographic paper emulsion which contained 80 g of gelatin and 35 g of halogen silver per liter and each 3% by weight of a crosslinking agent according to the invention were poured onto polyethylene-coated paper substrates which had been provided with an adhesive layer.
  • 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.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
DE19823224983 DE3224983A1 (de) 1982-07-03 1982-07-03 Verfahren zur haertung photographischer gelatine mit sulfonyl-ethylsulfatgruppenhaltigen vinylsulfonen
DE3224983 1982-07-03

Publications (3)

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

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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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0282865A1 (fr) * 1987-03-17 1988-09-21 Agfa-Gevaert AG Agents durcisseurs pour protéines, couche liante durcie à l'aide de ces agents et matériau d'enregistrement photographique contenant une telle couche

Families Citing this family (10)

* 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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5067640A (fr) * 1973-10-17 1975-06-06
DE2635518A1 (de) * 1975-08-09 1977-03-10 Konishiroku Photo Ind Verfahren zum haerten von photographischer gelatine und dessen anwendung zur herstellung eines photographischen silberhalogenidmaterials
EP0031959A1 (fr) * 1980-01-08 1981-07-15 Agfa-Gevaert AG Procédé pour le durcissement de couches de gélatine photographique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2943807A1 (de) * 1979-10-30 1981-05-14 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur haertung eines photographischen materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5067640A (fr) * 1973-10-17 1975-06-06
DE2635518A1 (de) * 1975-08-09 1977-03-10 Konishiroku Photo Ind Verfahren zum haerten von photographischer gelatine und dessen anwendung zur herstellung eines photographischen silberhalogenidmaterials
EP0031959A1 (fr) * 1980-01-08 1981-07-15 Agfa-Gevaert AG Procédé pour le durcissement de couches de gélatine photographique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JAPANESE PATENTS GAZETTE, Woche X04, 3. März 1976, Seite 6, Zusammenfassung Nr. 06100X/04, Derwent Publications, London, GB; & JP - A - 50 067 640 (KONISHIROKU PHOTO)(06-06-1975) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0282865A1 (fr) * 1987-03-17 1988-09-21 Agfa-Gevaert AG Agents durcisseurs pour protéines, couche liante durcie à l'aide de ces agents et matériau d'enregistrement photographique contenant une telle couche

Also Published As

Publication number Publication date
DE3371708D1 (en) 1987-06-25
US4543324A (en) 1985-09-24
CA1248391A (fr) 1989-01-10
EP0098454B1 (fr) 1987-05-20
JPS5918944A (ja) 1984-01-31
EP0098454A3 (en) 1985-04-03
DE3224983A1 (de) 1984-01-05

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