EP0297240A2 - Process for the fabrication of a support for light sensitive material with an anti-coiling layer - Google Patents

Process for the fabrication of a support for light sensitive material with an anti-coiling layer Download PDF

Info

Publication number
EP0297240A2
EP0297240A2 EP19880106625 EP88106625A EP0297240A2 EP 0297240 A2 EP0297240 A2 EP 0297240A2 EP 19880106625 EP19880106625 EP 19880106625 EP 88106625 A EP88106625 A EP 88106625A EP 0297240 A2 EP0297240 A2 EP 0297240A2
Authority
EP
European Patent Office
Prior art keywords
coating
chromium
iii
gelatin
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19880106625
Other languages
German (de)
French (fr)
Other versions
EP0297240A3 (en
EP0297240B1 (en
Inventor
Horst Dipl.-Ing. Westfal
Frits Butters Ruben
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Felix Schoeller Jr Foto und Spezialpapiere GmbH filed Critical Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority to AT88106625T priority Critical patent/ATE71746T1/en
Publication of EP0297240A2 publication Critical patent/EP0297240A2/en
Publication of EP0297240A3 publication Critical patent/EP0297240A3/en
Application granted granted Critical
Publication of EP0297240B1 publication Critical patent/EP0297240B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/131—Anticurl layer

Definitions

  • the invention relates to a method for producing a layer support for light-sensitive materials with an anti-roll layer on the back.
  • gelatin layers Most photographic materials use gelatin to build up the silver halide emulsions, protective layers and backing layers. Gelatin layers, however, swell with water and have little mechanical strength when swollen. For this reason, they are usually hardened using suitable hardening agents. The hardening agents crosslink the gelatin molecules with each other and thereby reduce the water absorption or swellability of the layer, increase the melting point and improve the mechanical strength of the gelatin layer. Hardened gelatin layers are above all resistant to the photographic treatment baths.
  • the light-sensitive gelatin-containing layers on the front of the carrier material are usually opposite gelatin-containing layers on the back of the carrier material.
  • the swelling behavior in the photographic treatment baths and the behavior of the layers during subsequent drying should be kept as identical as possible, so that the material maintains a good flatness during the entire work process and during later use.
  • the layers applied to the back are therefore referred to as anti-roll or anti-curl layers, and their layer thickness depends on the swelling behavior and the layer thickness of the front coating.
  • the anti-roll layers usually also contain various additives. These can be wetting agents such as saponin, matting agents such as silica, plasticizers such as glycerin, organic acids such as citric acid, small amounts of other water-soluble high-polymer compounds such as polyvinyl alcohol or antistatic agents such as sodium nitrate.
  • wetting agents such as saponin, matting agents such as silica, plasticizers such as glycerin, organic acids such as citric acid, small amounts of other water-soluble high-polymer compounds such as polyvinyl alcohol or antistatic agents such as sodium nitrate.
  • the resistance of the anti-roll layers to the photographic treatment baths is achieved by hardening the gelatin with so-called hardening agents.
  • Known hardening agents for gelatin include chromium (III) salts, aldehydes, dialdehyde polysaccharides, polyfunctional epoxides, aziridines, polyfunctional vinyl compounds, triacryl formal, substituted dichlorostriazines and others in chapter 2 of the book "The Theory of the Photographic Process” by TH Substances described by James (London, 1977).
  • the hardening agents are either added to the gelatin-containing solutions before processing or they are applied as a separate solution to the gelatin layer already on a support. In the second case, the hardening agents diffuse into the gelatin layer, where they react with the peptide chains. Both methods can also be combined with one another in such a way that part of the hardening agent is added to the gelatin solution and another part is subsequently applied to the layer.
  • Every hardening agent known hitherto has one or the other disadvantage and does not have the wide range of possible uses, as is particularly desirable in the case of gelatin auxiliary layers which are applied to a support prior to emulsionation and are later in contact with the actual photographic layers.
  • the main disadvantage is that the reaction of most hardeners with gelatin is too slow and further processing of the coated material is often only possible after days or weeks of intermediate storage. Chromium (III) salts are known to also show this time-dependent post-hardening. (Journal for Scientific Photography, Vol. 57, 1963, Issue 9-12, page 155 paragraph 2 and DOS 24 17 779, page 45 paragraph 3).
  • This task also has DOS 2417779, in which the general problem and the solution in the form of two successive layers, the first of which is a gelatin layer and the second is a hard layer tion layer, combined with polysaccharides.
  • Organic compounds are applied in the top coat as curing agents, but are incompatible with polyvinyl alcohol, as described on page 55 of the DOS.
  • the swelling factor is measured after 10 minutes of treatment of a test strip in distilled water at 22 ° C. It is defined According to Examples 1 and 2 of DOS 24 17 779, the layer weight (dry) consists of approximately 60% by weight of gelatin which has been hardened.
  • the lowest swelling factors in DOS are 3.0; based on gelatin this means a water absorption of 5g / 1g gelatin.
  • Gelatin solutions are usually applied warm to the substrate and then pass through a solidification zone in which they convert from the sol form to the gel form. The layers are only dried after this conversion. (Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Volume 18, page 443). This conversion of the gelatin from the sol form to the gel form is an essential step. For example, gelatin solutions can only be hardened with chromium (III) salts if they can react in the gel state. Gelatinesols do not cross-link with chromium (III) salts. (Photographic Science And Engineering, Volume 3, No. 6, Nov.-Dec. 1959, page 277ff).
  • the water absorption of the gelatin layers from DOS 2417779 is certainly the right choice for emulsion layers, but too high for anti-roll layers applied on the back.
  • the swelling capacity required for the trouble-free passage through the development baths is maintained, the water absorption capacity of the anti-roll layer should be as low as possible.
  • Another object of this invention is to dispense with a solidification zone in the coating system for economic reasons and to harden the gelatin solution from the sol form, the time-dependent post-curing known from chromium (III) salts being avoided.
  • the immediate drying of the first coating means that drying begins immediately after the layer has been applied, without the conversion of the sol form of the gelatin into the gel form being carried out.
  • the first coating consists of a gelatin solution which contains hardening agents in the amount and type that can be processed immediately after drying e.g. makes possible in tandem, but is not sufficient for the proper functioning of an anti-roll layer, as described above.
  • the first coating Since the application of the second coating preferably takes place immediately after the drying of the first coating, the first coating must have a strength and surface hardness immediately after it has dried, which allows the second coating to be applied and metered.
  • glyoxal has an accelerating effect on hardening with chromium (III) salts, so that in a special form of the process according to the invention the hardener combination for the first coating of chromium (III) salt and glyoxal in a ratio of 1: 3 up to 3: 1. This makes the gelatin pre-hardened so quickly tet that the second coating solution can be applied without problems in tandem coating systems immediately after drying of the first coating solution.
  • the sequence of process steps according to the invention makes it possible to harden the surface of anti-roll layers that come into contact with the photographic treatment baths in such a way that water absorption of ⁇ 2.5 g water / 1 g gelatin is achieved. At the same time, the depth of the hardened gelatin layer remains so elastic that there are no embrittlement cracks and the flatness of the entire carrier material is preserved.
  • the elasticity of the anti-roll layer can be increased further by adding plasticizers such as glycerin, glycols, sorbitol, montmorillonite and the like to the first coating.
  • Additional hardening agents for the first coating can be all substances corresponding to the state of the art and suitable for photographic processes, provided that they are dosed in combination with chromium (III) salt or chromium (III) salt and glyoxal in such a way that the overall system is quick and intensive reacted enough.
  • a preferred form of the chromium (III) salts is chromium alum, KCr (SO4) 2 ⁇ 12 H2O.
  • the second coating solution contains chromium (III) salts, with chromium alum being preferred.
  • concentration of chromium (III) salt in this solution is preferably between about 0.5% by weight and about 5% by weight and depends on the applied layer thickness, which is predetermined by the mechanical equipment and by the rheology of the solution and the type of chromium salt.
  • the total chromium (III) ion content of the anti-roll layer should be higher than 20 mg Cr / m 2, with more than half of the amount being applied by the second coating. Contrary to the representation from DOS 24 17 779, page 55, it is possible and even particularly advantageous if polyvinyl alcohol is added to this hardener solution. The addition of a fully saponified polyvinyl alcohol improves the rheological behavior of the hardener solution, the layer thickness can be adjusted better, the wetting is flawless and an exact straight edge run of the wet application is possible.
  • Usual auxiliaries as are known in anti-roll layers on the back of layer supports for light-sensitive materials, can also be contained in the anti-roll layer according to the invention, wherein they are preferably added to the first coating solution.
  • a base consisting of 175 g / m2 paper and a layer of 35 g / m2 polyethylene per side was coated with a first coating of the following composition: Water 84.75% by weight Gelatin 12% by weight Sodium nitrate 1% by weight Silica 1% by weight Glycerin 1% by weight Wetting agent 0.1% by weight Citric acid 0.02% by weight Chrome alum 0.1% by weight Triacryloylhexahydrotriazine sodium hydroxide solution up to pH 6.6 0.03% by weight
  • This first coating applied to the back was dried in a hot air duct, the application weight was 6.0 g / m 2.
  • the machine speed for both jobs was 100 m / min.
  • the layer support from Example 1 was used.
  • the composition of the recipe for the first coating was changed as follows:
  • the first coating applied to the back was dried in a hot air duct, the application weight was 8.5 g / m 2.
  • a solution according to recipe 1b was applied to this first coating immediately after it had dried as the second coating and dried in the hot air duct.
  • the application weight was a constant 250 mg / m2.
  • the water absorption based on the amount of gelatin in the anti-roll layer, was determined by gravimetric evaluation after 10 minutes of treatment of a test strip in distilled water at 22 ° C. with subsequent drying Examples Water absorption right away after 4 weeks 1a 3.9 1) 3.3 1) 1b 1.8 1.7 1c 0.9 1.0 1d 0.9 1.0 1e, comparison 2.9 2.6 1f, comparison 3.6 2.8 1g, comparison 2.8 2.3 1h, comparison 3.1 2.6 Comparison of literature example from DOS 2417779 5.0 1) The reason for the relatively high values is the insufficient amount of chromium (III) ions in the second coating.
  • the second coating could be applied smoothly to the first coating using a roller and air brush.
  • doctor strips appeared. Examples Water absorption right away after 4 weeks 2a 0.8 0.8 2 B 2.3 2.4 2c 2.1 2.0 2d 0.6 0.6 2e 0.5 0.6 2f 2.4 2.3 2g, comparison 3.0 2.6
  • the second coating could be applied without problems using a roller and air brush.
  • Examples 2f and 2g were difficult to produce.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Packaging Of Machine Parts And Wound Products (AREA)

Abstract

For a waterproof support for light-sensitive materials with two successive coatings of an anti-curling layer applied to the back, gelatine is dried from the sol form in the first coating and hardened in such a way that, after drying of the first coating, the second coating which contains further hardener can immediately be applied without difficulty. Both coatings contain chromium(III) salts as hardener. <??>The chosen combination of two process steps provides anti-curling layers of extremely low water absorption capacity.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines Schichtträgers für lichtempfindliche Materialien mit einer Antirollschicht auf der Rückseite.The invention relates to a method for producing a layer support for light-sensitive materials with an anti-roll layer on the back.

Bei den meisten fotografischen Materialien wird Gelatine zum Aufbau der Silberhalogenidemulsionen, der Schutz­schichten und der Rückenschichten verwendet. Gelatineschichten quellen jedoch mit Wasser und haben im gequollenen Zustand geringe mechanische Festigkeit. Deshalb werden sie üblicherweise durch geeignete Härtungsmittel gehärtet. Die Härtungsmittel vernetzen die Gelatinemoleküle miteinander und bewirken dadurch eine Verminderung der Wasseraufnahme bzw. Quellfähigkeit der Schicht, eine Erhöhung des Abschmelzpunktes und eine Verbesserung der mechanischen Festigkeit der Gelatineschicht. Gehärtete Gelatineschichten sind vor allem resistent gegenüber den fotografischen Behandlungs­bädern.Most photographic materials use gelatin to build up the silver halide emulsions, protective layers and backing layers. Gelatin layers, however, swell with water and have little mechanical strength when swollen. For this reason, they are usually hardened using suitable hardening agents. The hardening agents crosslink the gelatin molecules with each other and thereby reduce the water absorption or swellability of the layer, increase the melting point and improve the mechanical strength of the gelatin layer. Hardened gelatin layers are above all resistant to the photographic treatment baths.

Den lichtempflindlichen gelatinehaltigen Schichten auf der Vorderseite des Trägermaterials liegen meistens gelatinehaltige Schichten auf der Rückseite des Trägermaterials gegenüber. Durch Einsatz des gleichen Bindemittels Gelatine auf beiden Seiten des Träger­materials soll das Quellverhalten in den fotografischen Behandlungsbädern und das Verhalten der Schichten bei anschließender Trocknung möglichst identisch gehalten werden, so daß während des gesamten Arbeitsprozesses sowie bei der späteren Verwendung das Material eine gute Planlage beibehält. Die auf die Rückseite aufgebrachten Schichten werden deshalb als Antiroll- oder Anticurl­schichten bezeichnet, und ihre Schichtdicke hängt ab vom Quellverhalten und von der Schichtdicke der Vorderseiten­beschichtung.The light-sensitive gelatin-containing layers on the front of the carrier material are usually opposite gelatin-containing layers on the back of the carrier material. By using the same gelatin binder on both sides of the carrier material, the swelling behavior in the photographic treatment baths and the behavior of the layers during subsequent drying should be kept as identical as possible, so that the material maintains a good flatness during the entire work process and during later use. The layers applied to the back are therefore referred to as anti-roll or anti-curl layers, and their layer thickness depends on the swelling behavior and the layer thickness of the front coating.

Üblicherweise enthalten die Antirollschichten noch verschiedene Zusatzstoffe. Diese können sein Netzmittel wie Saponin, Mattierungsmittel wie Kieselsäure, Weich­macher wie Glycerin, organische Säuren wie Zitronensäure, kleine Mengen anderer wasserlöslicher hochpolymerer Verbindungen wie Polyvinylalkohol oder Antistatika wie Natriumnitrat.The anti-roll layers usually also contain various additives. These can be wetting agents such as saponin, matting agents such as silica, plasticizers such as glycerin, organic acids such as citric acid, small amounts of other water-soluble high-polymer compounds such as polyvinyl alcohol or antistatic agents such as sodium nitrate.

Die Resistenz der Antirollschichten gegenüber den fotografischen Behandlungsbädern wird erreicht durch Härtung der Gelatine mit sogenannten Härtungsmitteln.The resistance of the anti-roll layers to the photographic treatment baths is achieved by hardening the gelatin with so-called hardening agents.

Zu den bekannten Härtungsmitteln für Gelatine gehören Chrom(III)-salze, Aldehyde, Dialdehydpolysaccharide, polyfunktionelle Epoxide, Aziridine, polyfunktionelle Vinylverbindungen, Triacrylformal, substituierte Dichlor­s-Triazine und andere in Kap.2 des Buches "The Theory of the Photographic Process" von T.H.James (London, 1977) beschriebene Substanzen.Known hardening agents for gelatin include chromium (III) salts, aldehydes, dialdehyde polysaccharides, polyfunctional epoxides, aziridines, polyfunctional vinyl compounds, triacryl formal, substituted dichlorostriazines and others in chapter 2 of the book "The Theory of the Photographic Process" by TH Substances described by James (London, 1977).

Die Härtungsmittel werden entweder den gelatinehaltigen Lösungen vor der Verarbeitung zugesetzt oder sie werden als gesonderte Lösung auf die bereits auf einem Träger befindliche Gelatineschicht aufgetragen. Im zweiten Fall diffundieren die Härtungsmittel in die Gelatineschicht, wo sie mit den Peptidketten in Reaktion treten. Beide Verfahren können auch in der Weise miteinander kombiniert werden, daß ein Teil des Härtungsmittels der Gelatine­lösung zugesetzt und ein anderer Teil nachträglich auf die Schicht gebracht wird.The hardening agents are either added to the gelatin-containing solutions before processing or they are applied as a separate solution to the gelatin layer already on a support. In the second case, the hardening agents diffuse into the gelatin layer, where they react with the peptide chains. Both methods can also be combined with one another in such a way that part of the hardening agent is added to the gelatin solution and another part is subsequently applied to the layer.

Alle als Härtungsmittel gebräuchlichen Substanzen haben aber ein bevorzugtes Verwendungsgebiet und sind für andere Anwendungen nicht optimal. D.h. alle genannten Härtungs­mittel sind mit einem oder mehreren Nachteilen behaftet. Aliphatische Aldehyde und Diketone eignen sich nicht für farbfotografische Schichten, weil sie mit üblichen Farb­kupplern oder anderen Emulsionszusätzen in Reaktion treten können. Polyepoxide, Triazine und Polysaccharide eignen sich zwar gut für farbfotografische Schichten, reagieren aber sehr langsam und sind deshalb nicht für solche Gelatineschichten geeignet, die kurz nach Trock­nung der Schicht bereits mechanisch beansprucht werden sollen, beispielsweise in einem weiteren Beschichtungs­vorgang. Andere Härtungsmittel, z.B. Chromsalze, sind so reaktionsfähig, daß eine damit versetzte Gelatinelösung bereits während der Verarbeitung einen Viskositätsan­stieg zeigt. Wieder andere Härtungsmittel sind nicht ausreichend diffusionsfest und verändern den Härtungszu­stand benachbarter Schichten während der Lagerung.However, all substances commonly used as hardening agents have a preferred area of use and are not optimal for other applications. This means that all of the hardening agents mentioned have one or more disadvantages. Aliphatic aldehydes and diketones are not suitable for color photographic layers because they can react with conventional color couplers or other emulsion additives. Although polyepoxides, triazines and polysaccharides are well suited for color photographic layers, they react very slowly and are therefore not suitable for gelatin layers which are to be mechanically stressed shortly after the layer has dried, for example in a further coating process. Other hardening agents, such as chromium salts, are so reactive that a gelatin solution mixed with them shows an increase in viscosity during processing. Still other hardening agents are not sufficiently resistant to diffusion and change the hardening state of adjacent layers during storage.

Jedes bisher bekannte Härtungsmittel hat also den einen oder anderen Nachteil und besitzt nicht die breite Anwendungsmöglichkeit, wie sie vor allem bei Gelatine­hilfsschichten erwünscht ist, die vor der Emulsionierung auf einem Träger aufgebracht werden und später mit den eigentlichen fotografischen Schichten in Kontakt sind. Hauptnachteil ist jedoch, daß die Reaktion der meisten Härtungsmittel mit Gelatine zu langsam erfolgt und vielfach erst nach Tagen oder Wochen der Zwischenlagerung eine weitere Verarbeitung des beschichteten Materials möglich ist. Chrom(III)-salze zeigen bekannterweise eben­falls diese zeitabhängige Nachhärtung. (Zeitschrift für wissenschaftliche Photographie, Bd. 57, 1963, Heft 9-12, Seite 155 Abs.2 und DOS 24 17 779, Seite 45 Abs.3).Every hardening agent known hitherto has one or the other disadvantage and does not have the wide range of possible uses, as is particularly desirable in the case of gelatin auxiliary layers which are applied to a support prior to emulsionation and are later in contact with the actual photographic layers. The main disadvantage, however, is that the reaction of most hardeners with gelatin is too slow and further processing of the coated material is often only possible after days or weeks of intermediate storage. Chromium (III) salts are known to also show this time-dependent post-hardening. (Journal for Scientific Photography, Vol. 57, 1963, Issue 9-12, page 155 paragraph 2 and DOS 24 17 779, page 45 paragraph 3).

Erstrebenswert ist der Einsatz von Härtungsmitteln, die schnell wirken und bei Lagerung ihren Härtungszustand nicht mehr verändern. Diese Aufgabe hat auch DOS 2417779, in der die allgemeine Problematik und die Lösung in Form von zwei nacheinander aufzutragenden Schichten, von denen die erste eine Gelatineschicht und die zweite eine Här­ tungsschicht, kombiniert mit Polysacchariden, ist. Als Härtungsmittel werden organische Verbindungen im Deckstrich aufgetragen, die jedoch unverträglich sind mit Polyvinylalkohol, wie auf Seite 55 der DOS beschrieben ist. Als wesentliches Merkmal der Beurteilung der gehärteten Schichten wird der Quellfaktor nach 10 Minuten Behandlung eines Probestreifens in destilliertem Wasser bei 22°C gemessen. Er ist definiert

Figure imgb0001
Nach den Beispielen 1 und 2 der DOS 24 17 779 besteht das Schichtgewicht (trocken) aus ca. 60 Gew.-% Gelatine, die gehärtet wurde.It is desirable to use hardening agents that act quickly and do not change their hardening state when stored. This task also has DOS 2417779, in which the general problem and the solution in the form of two successive layers, the first of which is a gelatin layer and the second is a hard layer tion layer, combined with polysaccharides. Organic compounds are applied in the top coat as curing agents, but are incompatible with polyvinyl alcohol, as described on page 55 of the DOS. As an essential feature of the assessment of the hardened layers, the swelling factor is measured after 10 minutes of treatment of a test strip in distilled water at 22 ° C. It is defined
Figure imgb0001
 According to Examples 1 and 2 of DOS 24 17 779, the layer weight (dry) consists of approximately 60% by weight of gelatin which has been hardened.

Die niedrigsten Quellfaktoren liegen in der DOS bei 3,0; bezogen auf Gelatine bedeutet das eine Wasseraufnahme von 5g/1g Gelatine.The lowest swelling factors in DOS are 3.0; based on gelatin this means a water absorption of 5g / 1g gelatin.

Üblicherweise werden Gelatinelösungen warm auf Schicht­träger aufgetragen und durchlaufen dann eine Erstarrungs­zone, in der sie sich von der Sol-Form in die Gel-Form umwandeln. Erst nach dieser Umwandlung werden die Schich­ten getrocknet. (Ullmanns Encyklopädie der technischen Chemie, 4.Auflage, Band 18, Seite 443). Diese Umwandlung der Gelatine von der Sol-Form in die Gel-Form ist ein wesentlicher Schritt. Gelatinelösungen sind beispiels­weise nur dann mit Chrom(III)-salzen härtbar, wenn sie im Gel-Zustand reagieren können. Gelatinesole vernetzen nicht mit Chrom(III)-salzen. (Photographic Science And Engineering, Volume 3, Nr.6, Nov.-Dez. 1959, Seite 277ff). Deshalb ist zur Erreichung eines hohen Schmelzbereiches und einer hohen Festigkeit von Gelatine­beschichtungen vor der eigentlichen Trocknung der aufge­tragenen Lösungen die beschriebene Erstarrungszone Stand der Technik. Die Umwandlung der Sol-Form in die Gel-Form nimmt im allgemeinen über 2 min. in Anspruch, wobei Tem­ peraturen von unter 30°C notwendig sind. Dieses verlangt zwangsläufig langsame Beschichtungsmaschinengeschwindig­keiten oder lange Erstarrungszonen.Gelatin solutions are usually applied warm to the substrate and then pass through a solidification zone in which they convert from the sol form to the gel form. The layers are only dried after this conversion. (Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Volume 18, page 443). This conversion of the gelatin from the sol form to the gel form is an essential step. For example, gelatin solutions can only be hardened with chromium (III) salts if they can react in the gel state. Gelatinesols do not cross-link with chromium (III) salts. (Photographic Science And Engineering, Volume 3, No. 6, Nov.-Dec. 1959, page 277ff). Therefore, in order to achieve a high melting range and a high strength of gelatin coatings before the applied solutions actually dry, the solidification zone described is state of the art. The conversion of the sol form to the gel form generally takes over 2 minutes. claim, wherein Tem temperatures below 30 ° C are necessary. This inevitably requires slow coating machine speeds or long solidification zones.

Die Wasseraufnahme der Gelatineschichten aus DOS 2417779 ist für Emulsionsschichten sicher richtig gewählt, für rückseitig aufgetragene Antirollschichten aber zu hoch. Je höher die Wasseraufnahme ist, umso mehr Gelatine löst sich aus der Antirollschicht und verunreinigt die photo­graphischen Behandlungsbäder. Bei Erhalt eines notwendi­gen Quellvermögens, das zum störungsfreien Durchlauf durch die Entwicklungsbäder erforderlich ist, sollte das Wasseraufnahmevermögen der Antirollschicht jedoch so gering wie möglich sein.The water absorption of the gelatin layers from DOS 2417779 is certainly the right choice for emulsion layers, but too high for anti-roll layers applied on the back. The higher the water absorption, the more gelatin is released from the anti-roll layer and contaminates the photographic treatment baths. However, if the swelling capacity required for the trouble-free passage through the development baths is maintained, the water absorption capacity of the anti-roll layer should be as low as possible.

Es ist daher die Aufgabe dieser Erfindung, ein Verfahren zur Herstellung von Schichtträgern für lichtempfindliche Materialien mit einer Antirollschicht auf der Rückseite zu entwickeln, die eine Wasseraufnahme von <2,5g Wasser/­1g Gelatine besitzt, gemessen nach einer Einwirkzeit von 10 Minuten durch destilliertes Wasser von 22°C.It is therefore the object of this invention to develop a process for the production of supports for light-sensitive materials with an anti-roll layer on the back, which has a water absorption of <2.5 g water / 1 g gelatin, measured after an exposure time of 10 minutes by distilled water of 22 ° C.

Eine weitere Aufgabe dieser Erfindung ist es, aus wirt­schaftlichen Gründen auf eine Erstarrungszone in der Beschichtungsanlage zu verzichten und die Gelatinelösung aus der Sol-Form heraus zu härten, wobei die bei Chrom­(III)-salzen bekannte zeitabhängige Nachhärtung vermieden werden soll.Another object of this invention is to dispense with a solidification zone in the coating system for economic reasons and to harden the gelatin solution from the sol form, the time-dependent post-curing known from chromium (III) salts being avoided.

Gelöst wird diese Aufgabe durch die in den Ansprüchen angegebenen Verfahrensmaßnahmen und Stoffe.This problem is solved by the process measures and substances specified in the claims.

Es hat sich überraschenderweise gezeigt, daß Chrom(III)-salz, aufgebracht als separater Überzug auf Gelatineschichten, die direkt aus der Sol-Form heraus getrocknet sind, nicht zu der bekannten zeitabhängigen Nachhärtung führt.It has surprisingly been found that chromium (III) salt, applied as a separate coating on gelatin layers which have dried directly out of the sol form, does not depend on the known time-dependent Post-curing leads.

Zur Lösung der Aufgabe gehört auch, daß mit sofortiger Trocknung des ersten Überzugs gemeint ist, daß direkt nach dem Auftragen der Schicht die Trocknung beginnt, ohne daß die Umwandlung der Sol-Form der Gelatine in die Gel-Form durchgeführt wird.Part of the solution to the problem is that the immediate drying of the first coating means that drying begins immediately after the layer has been applied, without the conversion of the sol form of the gelatin into the gel form being carried out.

Der erste Überzug besteht aus einer Gelatinelösung, die Härtungsmittel in der Menge und Art enthält, die eine unmittelbare Weiterverarbeitung nach Trocknung z.B. im Tandemverfahren möglich macht, aber nicht ausreicht für eine ordnungsgemäße Funktion einer Antirollschicht, wie oben beschrieben.The first coating consists of a gelatin solution which contains hardening agents in the amount and type that can be processed immediately after drying e.g. makes possible in tandem, but is not sufficient for the proper functioning of an anti-roll layer, as described above.

Da der Auftrag des zweiten Überzugs bevorzugt unmittel­bar nach dem Trocknen des ersten Überzugs erfolgt, so muß der erste Überzug sofort nach seiner Trocknung eine Festigkeit und Oberflächenhärte aufweisen, die es er­laubt, den zweiten Überzug anzutragen und zu dosieren.Since the application of the second coating preferably takes place immediately after the drying of the first coating, the first coating must have a strength and surface hardness immediately after it has dried, which allows the second coating to be applied and metered.

Werden für Auftrag und Dosierung der Lösung des zweiten Überzugs Auftragsaggregate eingesetzt, die die Oberfläche des ersten Überzugs mechanisch stark beanspruchen, so können sich Festigkeit und Härte des ersten Überzugs als unzureichend erweisen. Dieses ist beispielsweise der Fall, wenn zur Dosierung Rollrakel eingesetzt werden.If application units are used for the application and metering of the solution of the second coating which mechanically stress the surface of the first coating, the strength and hardness of the first coating may prove to be insufficient. This is the case, for example, when roller doctor blades are used for metering.

Es hat sich gezeigt, daß Glyoxal eine beschleunigende Wirkung auf die Härtung mit Chrom(III)-salzen hat, so daß in einer speziellen Form des erfindungsgemäßen Verfahrens die Härterkombination für den ersten Überzug Chrom(III)-salz und Glyoxal im Verhältnis 1:3 bis 3:1 besteht. Dadurch wird die Gelatine so schnell vorgehär­ tet, daß in Tandembeschichtungsanlagen unmittelbar nach Trocknung der ersten Überzugslösung störungsfrei die zweite Überzugslösung aufgetragen werden kann.It has been shown that glyoxal has an accelerating effect on hardening with chromium (III) salts, so that in a special form of the process according to the invention the hardener combination for the first coating of chromium (III) salt and glyoxal in a ratio of 1: 3 up to 3: 1. This makes the gelatin pre-hardened so quickly tet that the second coating solution can be applied without problems in tandem coating systems immediately after drying of the first coating solution.

Durch die erfindungsgemäße Aufeinanderfolge von Verfah­rensschritten wird es erst möglich, die Oberfläche von Antirollschichten, die in Kontakt kommt mit den foto­grafischen Behandlungsbädern, so zu härten, daß Wasser­aufnahmen von <2,5g Wasser/1g Gelatine erreicht werden. Gleichzeitig bleibt die gehärtete Gelatineschicht in der Tiefe so elastisch, daß keine Versprödungsrisse auftreten und die Planlage des gesamten Trägermaterials erhalten bleibt.The sequence of process steps according to the invention makes it possible to harden the surface of anti-roll layers that come into contact with the photographic treatment baths in such a way that water absorption of <2.5 g water / 1 g gelatin is achieved. At the same time, the depth of the hardened gelatin layer remains so elastic that there are no embrittlement cracks and the flatness of the entire carrier material is preserved.

Die Elastizität der Antirollschicht kann noch dadurch erhöht werden, daß dem ersten Überzug Weichmacher zuge­setzt werden wie Glyzerin, Glykole, Sorbit, Montmorillo­nite u.ä..The elasticity of the anti-roll layer can be increased further by adding plasticizers such as glycerin, glycols, sorbitol, montmorillonite and the like to the first coating.

Zusätzliche Härtungsmittel für den ersten Überzug können alle dem Stand der Technik entsprechende und für foto­grafische Verfahren geeignete Stoffe sein, sofern diese kombiniert mit Chrom(III)-salz oder Chrom(III)-salz und Glyoxal so dosiert werden, daß das Gesamtsystem schnell und intensiv genug reagiert. Eine bevorzugte Form der Chrom(III)-salze ist Chromalaun, KCr(SO₄)₂·12 H₂O.Additional hardening agents for the first coating can be all substances corresponding to the state of the art and suitable for photographic processes, provided that they are dosed in combination with chromium (III) salt or chromium (III) salt and glyoxal in such a way that the overall system is quick and intensive reacted enough. A preferred form of the chromium (III) salts is chromium alum, KCr (SO₄) ₂ · 12 H₂O.

Als besonders gut abgestimmt auf den erfindungsgemäßen Chrom(III)-salz-haltigen zweiten Überzug hat sich im ersten Überzug die Härtungsmittelmischung von Chrom(III)-salz:Glyoxal = 3:1 bis 1:3 in einer Zusatz­menge von 0,06 Gew.-% bis 0,18 Gew.-% Cr³⁺bezogen auf Gelatine erwiesen. Mit dieser Rezeptur für den ersten Überzug können beide Schichten auch in einer Tandem-­Streichmaschine mit Walzenantrag und Rakeldosierung nacheinander aufgetragen werden.The hardening agent mixture of chromium (III) salt: glyoxal = 3: 1 to 1: 3 in an additional amount of 0.06% has proven to be particularly well matched to the second coating containing chromium (III) salt according to the invention. -% to 0.18 wt .-% Cr³⁺ based on gelatin proven. With this recipe for the first coating, both layers can also be applied in succession in a tandem coating machine with roller application and knife metering.

Die zweite Überzugslösung enthält Chrom(III)-salze, wobei Chromalaun bevorzugt ist. Die Konzentration dieser Lösung an Chrom(III)-salz liegt vorzugsweise zwischen etwa 0,5 Gew.-% und etwa 5 Gew.-% und hängt ab von der aufgetragenen Schichtdicke, die durch die maschinentech­nische Einrichtung und durch die Rheologie der Lösung vorgegeben wird und von der Art des Chromsalzes.The second coating solution contains chromium (III) salts, with chromium alum being preferred. The concentration of chromium (III) salt in this solution is preferably between about 0.5% by weight and about 5% by weight and depends on the applied layer thickness, which is predetermined by the mechanical equipment and by the rheology of the solution and the type of chromium salt.

Der Gesamtgehalt an Chrom(III)-ionen der Antirollschicht soll erfindungsgemäß höher als 20 mg Cr/m² sein, wobei mehr als die Hälfte der Menge durch den zweiten Überzug aufgetragen wird. Entgegen der Darstellung aus DOS 24 17 779, Seite 55, ist es möglich, und sogar besonders vorteilhaft, wenn dieser Härterlösung Polyvinylalkohol zugesetzt wird. Der Zusatz eines voll verseiften Poly­vinylalkohols verbessert das rheologische Verhalten der Härterlösung, es läßt sich die Schichtdicke besser ein­stellen, die Benetzung ist einwandfrei und es wird ein exakter gradliniger Kantenlauf des Naßauftrags möglich.According to the invention, the total chromium (III) ion content of the anti-roll layer should be higher than 20 mg Cr / m 2, with more than half of the amount being applied by the second coating. Contrary to the representation from DOS 24 17 779, page 55, it is possible and even particularly advantageous if polyvinyl alcohol is added to this hardener solution. The addition of a fully saponified polyvinyl alcohol improves the rheological behavior of the hardener solution, the layer thickness can be adjusted better, the wetting is flawless and an exact straight edge run of the wet application is possible.

Übliche Hilfsmittel, wie sie in Antirollschichten auf der Rückseite von Schichtträgern für lichtempfindliche Materialien bekannt sind, können auch in der erfindungs­gemäßen Antirollschicht enthalten sein, wobei sie bevorzugt der ersten Überzugslösung zugesetzt werden.Usual auxiliaries, as are known in anti-roll layers on the back of layer supports for light-sensitive materials, can also be contained in the anti-roll layer according to the invention, wherein they are preferably added to the first coating solution.

Die folgenden Beispiele sollen die Ausführungen verdeut­lichen.The following examples are intended to clarify the explanations.

Beispiel 1example 1

Ein Schichtträger bestehend aus 175 g/m² Papier und je einer Schicht von 35 g/m² Polyethylen pro Seite wurde mit einem ersten Überzug folgender Zusammensetzung beschichtet:
Wasser      84,75 Gew.-%
Gelatine      12 Gew.-%
Natriumnitrat      1 Gew.-%
Kieselsäure      1 Gew.-%
Glyzerin      1 Gew.-%
Netzmittel      0,1 Gew.-%
Zitronensäure      0,02 Gew.-%
Chromalaun      0,1 Gew.-%
Triacryloylhexahydrotriazin Natronlaugelösung bis pH 6,6      0,03 Gew.-%A base consisting of 175 g / m² paper and a layer of 35 g / m² polyethylene per side was coated with a first coating of the following composition:
Water 84.75% by weight
Gelatin 12% by weight
Sodium nitrate 1% by weight
Silica 1% by weight
Glycerin 1% by weight
Wetting agent 0.1% by weight
Citric acid 0.02% by weight
Chrome alum 0.1% by weight
Triacryloylhexahydrotriazine sodium hydroxide solution up to pH 6.6 0.03% by weight

Dieser auf die Rückseite aufgetragene erste Überzug wurde im Heißluftkanal getrocknet, das Auftragsgewicht betrug 6,0 g/m².This first coating applied to the back was dried in a hot air duct, the application weight was 6.0 g / m 2.

Auf diesen ersten Überzug wurden unmittelbar nach seiner Trocknung einer der folgenden zweiten Überzüge aufgetragen:

  • a) 1 Gew.-% KCr(SO₄)₂·12H₂O (Chromalaun)
    1 Gew.-% Polyvinylalkohol (PVA), vollverseift, mittlerer Polymerisationsgrad = 5100
    98 Gew.-% Wasser
  • b) 3 Gew.-% Chromalaun
    1 Gew.-% PVA, wie bei 1a
    96 Gew.-% Wasser
  • c) 5 Gew.-% Chromalaun
    1 Gew.-% PVA, wie bei 1a
    94 Gew.-% Wasser
  • d) 5 Gew.-% Chromalaun
    95 Gew.-% Wasser
  • e) 5 Gew.-% Formaldehyd
    95 Gew.-% Wasser
  • f) 5 Gew.-% Natriumsalz des 2-Hydroxy-4,6dichlor-s-triazin
    95 Gew.-% Wasser
  • g) 5 Gew.-% Glyoxal
    95 Gew.-% Wasser
  • h) 5 Gew.-% Mucochlorsäure
    95 Gew.-% Wasser
One of the following second coatings was applied to this first coating immediately after it had dried:
  • a) 1% by weight KCr (SO₄) ₂ · 12H₂O (chrome alum)
    1% by weight polyvinyl alcohol (PVA), fully saponified, average degree of polymerization = 5100
    98% by weight of water
  • b) 3% by weight of chrome alum
    1 wt% PVA as in 1a
    96% by weight of water
  • c) 5% by weight of chrome alum
    1 wt% PVA as in 1a
    94% by weight water
  • d) 5% by weight of chrome alum
    95% by weight of water
  • e) 5% by weight of formaldehyde
    95% by weight of water
  • f) 5% by weight sodium salt of 2-hydroxy-4,6dichloro-s-triazine
    95% by weight of water
  • g) 5% by weight glyoxal
    95% by weight of water
  • h) 5% by weight of mucochloric acid
    95% by weight of water

Der auf der Rückseite aufgetragene zweite Überzug wurde im Heißluftkanal getrocknet. Das Auftragsgewicht betrug bei

  • a) 180 mg/m²
  • b) 260 mg/m²
  • c) 320 mg/m²
  • d) 280 mg/m²
  • e) 280 mg/m²
  • f) 280 mg/m²
  • g) 265 mg/m²
  • h) 270 mg/m²
The second coating applied on the back was dried in a hot air duct. The order weight was
  • a) 180 mg / m²
  • b) 260 mg / m²
  • c) 320 mg / m²
  • d) 280 mg / m²
  • e) 280 mg / m²
  • f) 280 mg / m²
  • g) 265 mg / m²
  • h) 270 mg / m²

Die Maschinengeschwindigkeit bei beiden Aufträgen war 100 m/min..The machine speed for both jobs was 100 m / min.

Beispiel 2Example 2

Der Schichtträger aus Beispiel 1 wurde eingesetzt. Die Zusammensetzung der Rezeptur des ersten Überzugs wurde folgendermaßen verändert:
The layer support from Example 1 was used. The composition of the recipe for the first coating was changed as follows:

GrundrezeptBasic recipe

Gelatine      12 Gew.-%
Natriumnitrat      1 Gew.-%
Kieselsäure      3 Gew.-%
Glyzerin      1 Gew.-%
Netzmittel      0,1 Gew.-%
Zitronensäure      0,02 Gew.-% Weitere Zusätze in Gew.-%: Chromalaun Chrom(III)-chlorid-6-hydrat Triacrylhexahydrotriazin Formaldehyd Glyoxal a 0,09 - - - 0,09 b 0,045 - - - 0,045 c 0,045 - - - 0,135 d 0,135 - - - 0,045 e - 0,09 - - 0,09 f 0,045 - 0,03 - - g - - - 0,045 0,09 Jeweils Wasser zu 100 Gew.-% ergänzt. Gelatin 12% by weight
Sodium nitrate 1% by weight
Silica 3% by weight
Glycerin 1% by weight
Wetting agent 0.1% by weight
Citric acid 0.02% by weight Other additives in% by weight: Chrome alum Chromium (III) chloride 6-hydrate Triacrylhexahydrotriazine formaldehyde Glyoxal a 0.09 - - - 0.09 b 0.045 - - - 0.045 c 0.045 - - - 0.135 d 0.135 - - - 0.045 e - 0.09 - - 0.09 f 0.045 - 0.03 - - G - - - 0.045 0.09 100% by weight of water added.

Der pH-Wert wurde auf pH = 6,6 eingestellt (NaOH). Der auf die Rückseite aufgetragene erste Überzug wurde im Heißluftkanal getrocknet, das Auftragsgewicht betrug 8,5 g/m².The pH was adjusted to pH = 6.6 (NaOH). The first coating applied to the back was dried in a hot air duct, the application weight was 8.5 g / m 2.

Auf diesen ersten Überzug wurde unmittelbar nach seiner Trocknung als zweiter Überzug eine Lösung gemäß Rezeptur 1b aufgetragen und im Heißluftkanal getrocknet. Das Auf­tragsgewicht betrug konstant 250 mg/m².A solution according to recipe 1b was applied to this first coating immediately after it had dried as the second coating and dried in the hot air duct. The application weight was a constant 250 mg / m².

Die Maschinengeschwindigkeit bei beiden Aufträgen war 100 m/min.. Aus den Beispielen 1 und 2 ergeben sich folgende Beziehungen: Beispiele 1. Überzug 2.Überzug Gesamtgehalt Härter,bezogen auf Gelatine Chrom(III)-ionen, bezogen auf Gelatine Chrom(III)-ionen Chrom(III)-ionen Chrom(III)-ionen (Gew.-%) (Gew.-%) (mg/m²) (mg/m²) (mg/m²) 1a 1,1 0,09 4,1 9 13 b 1,1 0,09 4,1 20 24 c 1,1 0,09 4,1 28 32 d 1,1 0,09 4,1 29 33 e 1,1 0,09 4,1 0 4 f 1,1 0,09 4,1 0 4 g 1,1 0,09 4,1 0 4 h 1,1 0,09 4,1 0 4 2a 1,5 0,08 4,6 19 24 b 0,8 0,04 2,3 19 21 c 1,5 0,04 2,3 19 21 d 1,5 0,12 6,9 19 26 e 1,5 0,15 8,6 19 28 f 0,6 0,04 2,3 19 21 g 0,8 0,00 0,0 19 19 The machine speed for both jobs was 100 m / min. The following relationships result from Examples 1 and 2: Examples 1st coating 2. Coating Total salary Harder, based on gelatin Chromium (III) ions, based on gelatin Chromium (III) ions Chromium (III) ions Chromium (III) ions (% By weight) (% By weight) (mg / m²) (mg / m²) (mg / m²) 1a 1.1 0.09 4.1 9 13 b 1.1 0.09 4.1 20th 24th c 1.1 0.09 4.1 28 32 d 1.1 0.09 4.1 29 33 e 1.1 0.09 4.1 0 4th f 1.1 0.09 4.1 0 4th G 1.1 0.09 4.1 0 4th H 1.1 0.09 4.1 0 4th 2a 1.5 0.08 4.6 19th 24th b 0.8 0.04 2.3 19th 21st c 1.5 0.04 2.3 19th 21st d 1.5 0.12 6.9 19th 26 e 1.5 0.15 8.6 19th 28 f 0.6 0.04 2.3 19th 21st G 0.8 0.00 0.0 19th 19th

Prüfergebnisse:Test results:

Die Wasseraufnahme, bezogen auf die Gelatinemenge in der Antirollschicht, wurde ermittelt durch gravi­metrische Auswertung nach 10 Minuten Behandlung eines Probestreifens in destilliertem Wasser von 22°C mit anließender Trocknung Beispiele Wasseraufnahme sofort nach 4 Wochen 1a 3,9 1) 3,3 1) 1b 1,8 1,7 1c 0,9 1,0 1d 0,9 1,0 1e,Vergleich 2,9 2,6 1f,Vergleich 3,6 2,8 1g,Vergleich 2,8 2,3 1h,Vergleich 3,1 2,6 Vergleich Literaturbeispiel aus DOS 2417779 5,0 1) Ursache der relativ hohen Werte ist die unzureichende Menge an Chrom(III)-ionen im zweiten Überzug. The water absorption, based on the amount of gelatin in the anti-roll layer, was determined by gravimetric evaluation after 10 minutes of treatment of a test strip in distilled water at 22 ° C. with subsequent drying Examples Water absorption right away after 4 weeks 1a 3.9 1) 3.3 1) 1b 1.8 1.7 1c 0.9 1.0 1d 0.9 1.0 1e, comparison 2.9 2.6 1f, comparison 3.6 2.8 1g, comparison 2.8 2.3 1h, comparison 3.1 2.6 Comparison of literature example from DOS 2417779 5.0 1) The reason for the relatively high values is the insufficient amount of chromium (III) ions in the second coating.

Der zweite Überzug ließ sich störungsfrei mittels Walze und Luftbürste auf den ersten Überzug auftragen. Beim Einsatz des Drahtrakels zur Dosierung der Lösung des zweiten Überzugs traten Rakelstreifen auf. Beispiele Wasseraufnahme sofort nach 4 Wochen 2a 0,8 0,8 2b 2,3 2,4 2c 2,1 2,0 2d 0,6 0,6 2e 0,5 0,6 2f 2,4 2,3 2g, Vergleich 3,0 2,6 The second coating could be applied smoothly to the first coating using a roller and air brush. When using the wire doctor to meter the solution of the second coating, doctor strips appeared. Examples Water absorption right away after 4 weeks 2a 0.8 0.8 2 B 2.3 2.4 2c 2.1 2.0 2d 0.6 0.6 2e 0.5 0.6 2f 2.4 2.3 2g, comparison 3.0 2.6

Der zweite Überzug ließ sich bei den Beispielen 2a bis 2e störungsfrei mittels Walze und Luftbürste auftragen. Die Beispiele 2f und 2g waren nur unter Schwierigkeiten herstellbar.In Examples 2a to 2e, the second coating could be applied without problems using a roller and air brush. Examples 2f and 2g were difficult to produce.

Beim Einsatz eines Drahtrakels zur Dosierung der Lösung des zweiten Überzugs traten bei den Beispielen 2b und 2c leichte Rakelstreifen auf, und die Beispiele 2f und 2g ließen sich nicht nehr herstellen. Nur die Beispiele 2a, 2d und 2e gaben auch bei Dosierung mit Drahtrakel keine Probleme.When using a wire doctor to meter the solution of the second coating, slight doctor marks occurred in Examples 2b and 2c, and Examples 2f and 2g could no longer be produced. Only examples 2a, 2d and 2e gave no problems even when metering with a wire doctor.

Claims (16)

1. Verfahren zur Herstellung eines Schichtträgers für licht­empfindliche Materialien mit Antirollschicht aus Gelatine auf der Rückseite des Schichtträgers, dadurch gekennzeichnet, daß ein erster Überzug aufgetragen wird, der proteinhaltige Bindemittel und Härtungsmittel enthält, von denen mindestens eine Komponente ein Chrom(III)-salz ist und daß dieser erste Überzug ohne vorherige Erstarrung bereits in der Sol-Form getrocknet wird, danach auf den ersten Überzug eine zweite gelatinefreie härtungsmittelhaltige Überzugslösung aufge­tragen wird, die ein Chrom(III)-salz enthält und der zweite Überzug getrocknet wird.1. A method for producing a support for light-sensitive materials with anti-roll layer of gelatin on the back of the support, characterized in that a first coating is applied which contains protein-containing binders and hardeners, at least one component of which is a chromium (III) salt and that this first coating is already dried in the sol form without prior solidification, then a second gelatin-free hardening-containing coating solution which contains a chromium (III) salt is applied to the first coating and the second coating is dried. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß diese härtungsmittelhaltige Lösung Chrom(III)-salz und einen voll verseiften Polyvinylalkohol enthält.2. The method according to claim 1, characterized in that this hardener-containing solution contains chromium (III) salt and a fully saponified polyvinyl alcohol. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der erste Überzug neben Chrom(III)-salzen als Härtungsmittel weitere organische, anorganische oder ein Gemisch beider Härtungsmittel enthält.3. The method according to claim 1, characterized in that the first coating contains in addition to chromium (III) salts as a curing agent further organic, inorganic or a mixture of both curing agents. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der erste Überzug Glyoxal in einem Massenverhältnis von Chrom(III)-salz:Glyoxal = 3:1 bis 1:3 enthält.4. The method according to claim 1, characterized in that the first coating contains glyoxal in a mass ratio of chromium (III) salt: glyoxal = 3: 1 to 1: 3. 5. Verfahren nach Anspruch 1 und 3, dadurch gekennzeichnet, daß die Konzentration des Härtungsmittels im ersten Überzug 0,5 bis 2,0 Gew.-% der Gelatinemenge ist.5. The method according to claim 1 and 3, characterized in that the concentration of the curing agent in the first coating is 0.5 to 2.0 wt .-% of the amount of gelatin. 6. Verfahren nach Anspruch 1 und 3, dadurch gekennzeichnet, daß das Härtungsmittel im ersten Überzug 0,06 bis 0,18 Gew.-% Cr³⁺, bezogen auf die Gelatinemenge, enthält.6. The method according to claim 1 and 3, characterized in that the curing agent in the first coating contains 0.06 to 0.18 wt .-% Cr³⁺, based on the amount of gelatin. 7. Verfahren nach Anspruch 2 und 6, dadurch gekennzeichnet, daß das Chrom(III)-salz Chromalaun der Formel KCr(SO₄)₂.12 H₂O ist.7. The method according to claim 2 and 6, characterized in that the chromium (III) salt is chrome alum of the formula KCr (SO₄) ₂.12 H₂O. 8. Verfahren nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß das Auftragsgewicht des ersten Überzuges nach dem Trocknen zwischen 1,0 und 10 g/m² liegt.8. The method according to claim 1 to 7, characterized in that the application weight of the first coating after drying is between 1.0 and 10 g / m². 9. Verfahren nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß der erste Überzug übliche Zusätze der Rückseitenbeschich­tungen, wie Mattierungsmittel, Antistatika und/oder Netzmittel enthält.9. The method according to claim 1 to 8, characterized in that the first coating contains conventional additives of the back coatings, such as matting agents, antistatic agents and / or wetting agents. 10. Verfahren nach Anspruch 1 bis 9, dadurch gekennzeichnet, daß der erste Überzug Weichmacher enthält.10. The method according to claim 1 to 9, characterized in that the first coating contains plasticizers. 11. Verfahren nach Anspruch 1 bis 10, dadurch gekennzeichnet, daß der erste Überzug eine organische Säure enthält, die mit Chromionen Komplexe bilden kann.11. The method according to claim 1 to 10, characterized in that the first coating contains an organic acid which can form complexes with chromium ions. 12. Verfahren nach Anspruch 1 bis 11, dadurch gekennzeichnet, daß der erste Überzug vor dem Auftragen in der Lösung einen pH-Wert von 6,3 bis 6,9 aufweist.12. The method according to claim 1 to 11, characterized in that the first coating has a pH of 6.3 to 6.9 before application in the solution. 13. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Massenverhältnis von Chrom(III)-salz:Polyvinylalkohol (voll verseift) = 1:1 bis 30:1 ist.13. The method according to claim 2, characterized in that the mass ratio of chromium (III) salt: polyvinyl alcohol (fully saponified) = 1: 1 to 30: 1. 14. Verfahren nach Anspruch 1 bis 13, dadurch gekennzeichnet, daß das Auftragsgewicht des zweiten Überzuges nach dem Trock­nen zwischen 0,1 und 1,0 g/m² liegt.14. The method according to claim 1 to 13, characterized in that the application weight of the second coating after drying is between 0.1 and 1.0 g / m². 15. Schichtträger für lichtempfindliche Materialien mit Antirollschicht, hergestellt nach dem Verfahren gemäß Anspruch 1 bis 14, dadurch gekennzeichnet, daß der Schicht­träger in der rückseitigen Antirollschicht einen Gehalt an Chrom(III)-ionen besitzt, der höher als 20 mg Cr/m² ist.15. support for light-sensitive materials with anti-roll coating, produced by the process according to claims 1 to 14, characterized in that the support in the back anti-roll coating has a chromium (III) ion content which is higher than 20 mg Cr / m². 16. Härtungsmittelhaltige Überzugslösung für proteinhaltige Schichten für fotografische Zwecke, dadurch gekennzeichnet, daß sie Chrom-III-salz und voll verseiften Polyvinylalkohol enthält.16. hardening agent-containing coating solution for protein-containing layers for photographic purposes, characterized in that it contains chromium III salt and fully saponified polyvinyl alcohol.
EP88106625A 1987-07-02 1988-04-26 Process for the fabrication of a support for light sensitive material with an anti-coiling layer Expired - Lifetime EP0297240B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88106625T ATE71746T1 (en) 1987-07-02 1988-04-26 PROCESS FOR MANUFACTURING A COATING FOR LIGHT-SENSITIVE MATERIALS WITH ANTI-ROLL COATING.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3721808 1987-07-02
DE19873721808 DE3721808A1 (en) 1987-07-02 1987-07-02 METHOD FOR PRODUCING A LAYER SUPPORT FOR LIGHT-SENSITIVE MATERIALS WITH ANTIROLL LAYER

Publications (3)

Publication Number Publication Date
EP0297240A2 true EP0297240A2 (en) 1989-01-04
EP0297240A3 EP0297240A3 (en) 1989-03-29
EP0297240B1 EP0297240B1 (en) 1992-01-15

Family

ID=6330718

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88106625A Expired - Lifetime EP0297240B1 (en) 1987-07-02 1988-04-26 Process for the fabrication of a support for light sensitive material with an anti-coiling layer

Country Status (9)

Country Link
US (1) US4977065A (en)
EP (1) EP0297240B1 (en)
JP (1) JP2710629B2 (en)
CN (1) CN1029803C (en)
AT (1) ATE71746T1 (en)
AU (1) AU609495B2 (en)
DE (2) DE3721808A1 (en)
ES (1) ES2028166T3 (en)
GR (1) GR3003701T3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0604732A1 (en) * 1992-12-30 1994-07-06 Felix Schoeller jr. Papierfabrik GmbH & Co. KG Carrier for photo sensitive material with anti-coiling layer coated on the backside

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4308440C2 (en) * 1993-03-17 2003-07-10 Schoeller Felix Jun Papier Photographic support
US5368894A (en) * 1993-06-08 1994-11-29 Minnesota Mining And Manufacturing Company Method for producing a multilayered element having a top coat
US5376401A (en) * 1993-06-11 1994-12-27 Eastman Kodak Company Minimization of slide instabilities by variations in layer placement, fluid properties and flow conditions
US5358834A (en) * 1993-09-23 1994-10-25 Eastman Kodak Company Photographic element provided with a backing layer
EP2428840A1 (en) * 2010-09-10 2012-03-14 Felix Schoeller jr Foto- und Spezialpapiere GmbH & Co. KG Support material for photographic silver halide double coated paper
CN102221774B (en) * 2011-05-23 2013-03-06 乐凯胶片股份有限公司 Plastic coated paper base with antistatic bottom layers on two sides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2593912A (en) * 1948-11-19 1952-04-22 Gen Aniline & Film Corp Photographic film containing hardened gelatin
FR1481785A (en) * 1965-06-02 1967-05-19 Fuji Photo Film Co Ltd Photographic layers containing gelatin and a reaction product of polyvinyl alcohol with ethylene oxide
FR1575417A (en) * 1967-08-22 1969-07-18
EP0021749A1 (en) * 1979-06-15 1981-01-07 EASTMAN KODAK COMPANY (a New Jersey corporation) Method of manufacture of flexible photographic materials having anticurl and antistatic layers

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2576820A (en) * 1944-11-03 1951-11-27 Gen Aniline & Film Corp Reversible gel composition comprising polyvinyl alcohol and method of preparation
DE2417779A1 (en) * 1974-04-11 1975-10-30 Agfa Gevaert Ag PROCESS FOR CURING PHOTOGRAPHICAL COATINGS
US4196001A (en) * 1974-07-24 1980-04-01 Eastman Kodak Company Antistatic layer for photographic elements
DE2601377C2 (en) * 1976-01-15 1985-03-28 Agfa-Gevaert Ag, 5090 Leverkusen Process for the preparation of outer back and front layers on photographic materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2593912A (en) * 1948-11-19 1952-04-22 Gen Aniline & Film Corp Photographic film containing hardened gelatin
FR1481785A (en) * 1965-06-02 1967-05-19 Fuji Photo Film Co Ltd Photographic layers containing gelatin and a reaction product of polyvinyl alcohol with ethylene oxide
FR1575417A (en) * 1967-08-22 1969-07-18
EP0021749A1 (en) * 1979-06-15 1981-01-07 EASTMAN KODAK COMPANY (a New Jersey corporation) Method of manufacture of flexible photographic materials having anticurl and antistatic layers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0604732A1 (en) * 1992-12-30 1994-07-06 Felix Schoeller jr. Papierfabrik GmbH & Co. KG Carrier for photo sensitive material with anti-coiling layer coated on the backside
DE4244529A1 (en) * 1992-12-30 1994-07-07 Schoeller Felix Jun Papier Layer support for light-sensitive materials with anti-roll coating on the back
US5374510A (en) * 1992-12-30 1994-12-20 Felix Schoeller, Jr. Papierfabriken Support material for light sensitive materials with back anticurl layer

Also Published As

Publication number Publication date
GR3003701T3 (en) 1993-03-16
CN1029803C (en) 1995-09-20
EP0297240A3 (en) 1989-03-29
DE3721808A1 (en) 1989-01-12
JP2710629B2 (en) 1998-02-10
AU609495B2 (en) 1991-05-02
CN1030649A (en) 1989-01-25
ES2028166T3 (en) 1992-07-01
JPS6424248A (en) 1989-01-26
DE3721808C2 (en) 1991-06-13
US4977065A (en) 1990-12-11
EP0297240B1 (en) 1992-01-15
ATE71746T1 (en) 1992-02-15
DE3867729D1 (en) 1992-02-27
AU1859788A (en) 1989-01-05

Similar Documents

Publication Publication Date Title
DE975629C (en) Process for making photographic films
DE1202293C2 (en) Method of making a planographic printing plate
DE720339C (en) Vinyl acetate resin binder photographic layer and method of preparation
EP0297240B1 (en) Process for the fabrication of a support for light sensitive material with an anti-coiling layer
DE1957625C2 (en) Photographic material
DE711190C (en) Photographic film and method of manufacture
DE837955C (en) Hardened photographic films with improved properties
EP0395785B1 (en) Support for light-sensitive materials with an anti-curling layer coated on the backside
DE2820108C2 (en)
DE3727293C2 (en)
DE3518113A1 (en) CARRIER MATERIAL FOR THERMALLY DEVELOPABLE PHOTOGRAPHIC LAYERS
DE1900331A1 (en) Backing element, particularly for photographic and magnetic tape purposes
DE1807450A1 (en) Photographic layers containing gelatin with improved physical properties
DE2241400A1 (en) LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL
DE1522438A1 (en) Antistatic layer for photographic materials
DE1254346B (en) Process for the production of water-insoluble gelatin layers
DE1928356A1 (en) Photographic silver halide emulsion with reduced swelling
EP0604732B1 (en) Carrier for photo sensitive material with anti-coiling layer coated on the backside
DE838688C (en) Light sensitive silver halide colloid layers for tanning development
DE69023267T2 (en) Process for producing a silver halide photographic material.
AT109399B (en) Method of hardening colloids.
DE549380C (en) Process for hardening the gelatin layer of blank film intended for the suction pressure process (imbibition pressure)
DE449811C (en) Method of hardening colloids
DE1810017C3 (en) Process for making a diazotype material
DE1284290B (en) Process for curing photographic gelatin layers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19890414

17Q First examination report despatched

Effective date: 19900831

ITF It: translation for a ep patent filed

Owner name: DE DOMINICIS & MAYER S.R.L.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FELIX SCHOELLER JR. FOTO- UND SPEZIALPAPIERE GMBH

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 71746

Country of ref document: AT

Date of ref document: 19920215

Kind code of ref document: T

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3867729

Country of ref document: DE

Date of ref document: 19920227

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19920403

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19920408

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19920428

Year of fee payment: 5

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2028166

Country of ref document: ES

Kind code of ref document: T3

EPTA Lu: last paid annual fee
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3003701

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930410

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19930422

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19930426

Ref country code: AT

Effective date: 19930426

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19930427

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19931031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19940427

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19940427

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3003701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950103

EUG Se: european patent has lapsed

Ref document number: 88106625.2

Effective date: 19941110

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990301

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000313

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000320

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20000323

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000327

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000405

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010426

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20010430

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010525

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010525

BERE Be: lapsed

Owner name: FELIX SCHOELLER JR. FOTO- UND SPEZIALPAPIERE G.M.

Effective date: 20010430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011101

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010426

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20011101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050426