EP0297240B1 - 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 PDFInfo
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- EP0297240B1 EP0297240B1 EP88106625A EP88106625A EP0297240B1 EP 0297240 B1 EP0297240 B1 EP 0297240B1 EP 88106625 A EP88106625 A EP 88106625A EP 88106625 A EP88106625 A EP 88106625A EP 0297240 B1 EP0297240 B1 EP 0297240B1
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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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
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- 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 one another 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 working 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-side 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.
- a method for producing a photographic material which consists of a flexible support which carries a hydrophilic, colloidal layer on one side and a special anti-roll layer on the other side.
- the anti-roll and the antistatic layer are applied by means of tandem engraving coating, the anti-roll layer containing a hydrophilic, colloidal substance and the antistatic layer containing an antistatic and a hardening agent which acts as a hardener for the hydrophilic, colloidal substance in the anti-roll layer and that the curing agent diffuses from the antistatic layer into the anti-roll layer.
- the colloidal layer is gelatin, which is converted from the sol form to the gel form.
- the first gelatin layer contains a chromium (III) salt and the second hardening layer applied thereon contains formaldehyde as hardening agent.
- Each 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 auxiliary gelatin 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 hardening agents 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 layers to be applied one after the other, the first a gelatin layer and the second a hardening 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 solidification zone described is state of the art.
- the conversion of the sol form to the gel form generally takes over 2 minutes. claim, where temperatures below 30 ° C are necessary. This inevitably requires slow coating machine speeds or long solidification zones.
- the water absorption of the gelatin layers from DOS 2417779 is certainly chosen correctly 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-hardening 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.
- the gelatin is pre-hardened so quickly that the second coating solution can be applied without problems in tandem coating systems immediately after the 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 these 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 intense 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 this solution of chromium (III) salt 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: Basic recipe 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 Nasser added.
- 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 machine speed for both jobs was 100 m / min.
- 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.
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- 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)
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Abstract
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 one another 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 working 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-side 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.
Aus der europäischen Patentschrift 0 021 749 ist ein Verfahren zur Herstellung eines fotografischen Materials bekannt, welches aus einem flexiblen Träger besteht der auf einer Seite eine hydrophile, kolloidale Schicht trägt und auf der anderen Seite eine besondere Antirollschicht. Bei diesem Verfahren sind die Antiroll- und die antistatische Schicht mittels Tandemgravur-coating aufgetragen, wobei die Antirollschicht einen hydrophilen, kolloidalen Stoff enthält und die antistatische Schicht ein Antistatikum und ein Härtungsmittel, welches als Härter für den hydrophilen, kolloidalen Stoff in der Antirollschicht wirkt und daß das Härtungsmittel aus der antistatischen Schicht in die Antirollschicht diffundiert. Bei diesem Schichtaufbau handelt es sich bei der kolloidalen Schicht um Gelatine, die dabei von der Sol-Form in die GelForm umgewandelt wird. Die erste Gelatineschicht enthält ein Chrom(III)salz und die zweite darauf aufgetragene Härtungsschicht enthält Formaldehyd als Härtungsmittel.From European patent specification 0 021 749 a method for producing a photographic material is known which consists of a flexible support which carries a hydrophilic, colloidal layer on one side and a special anti-roll layer on the other side. In this method, the anti-roll and the antistatic layer are applied by means of tandem engraving coating, the anti-roll layer containing a hydrophilic, colloidal substance and the antistatic layer containing an antistatic and a hardening agent which acts as a hardener for the hydrophilic, colloidal substance in the anti-roll layer and that the curing agent diffuses from the antistatic layer into the anti-roll layer. In this layer structure, the colloidal layer is gelatin, which is converted from the sol form to the gel form. The first gelatin layer contains a chromium (III) salt and the second hardening layer applied thereon contains formaldehyde as hardening agent.
Alle als Härtungsmittels gebräuchlichen Substanzen haben aber ein bevorzugtes Verwendungsgebiet und sind für andere Anwendungen nicht optimal. D.h. alle gennanten 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 curing agents have a preferred area of use and are not optimal for other applications. This means that all 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).Each 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 auxiliary gelatin 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 hardening agents 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 Härtungsschicht, 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
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 layers to be applied one after the other, the first a gelatin layer and the second a hardening 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
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 GelForm 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 Temperaturen 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, where 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 chosen correctly 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-hardening 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 inadequate. 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 vorgehärtet, 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. As a result, the gelatin is pre-hardened so quickly that the second coating solution can be applied without problems in tandem coating systems immediately after the 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 these 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 intense 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 this solution of chromium (III) salt 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.
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
- 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
- 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.
Der Schichtträger aus Beispiel 1 wurde eingesetzt. Die Zusammensetzung der Rezeptur des ersten Überzugs wurde folgendermaßen verändert:
Weitere Zusätze in Gew.-%:
Jeweils Nasser zu 100 Gew.-% ergänzt.The layer support from Example 1 was used. The composition of the recipe for the first coating was changed as follows:
Other additives in% by weight:
100% by weight of Nasser 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..
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
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.
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 appeared 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 (15)
- A process for the manufacture of a base for light-sensitive materials, wherein a first coating comprising at least one protein-containing binder and hardeners, at least one of which is a Cr(III) salt, is applied to the back of a base as an anti-coiling layer and dried, and wherein a second gelatine-free coating comprising a Cr(III) salt as hardener is applied to the anti-coiling layer and dried, characterized in that the first coating is dried directly in the sol form without prior solidification.
- A process according to Claim 1, characterized in that the second coating additionally comprises a fully saponified polyvinyl alcohol.
- A process according to Claim 1, characterized in that the first coating comprises other organic and/or inorganic hardeners in addition to chromium(III) salts.
- A process according to Claim 1, characterized in that the first coating comprises glyoxal as another hardener in addition to the chromium(III) salt, in a weight ratio of chromium(III) salt:glyoxal = 3:1 to 1:3.
- A process according to Claims 1 and 3, characterized in that the concentration of the hardener in the first coating is 0.5 to 2.0% by weight of the amount of gelatine.
- A process according to Claims 1 and 3, characterized in that the hardener in the first coating contains 0.06 to 0.18% by weight of Cr³⁺, based on the amount of gelatine.
- A process according to Claims 2 and 6, characterized in that the chromium(III) salt is chrome alum of the formula KCr(SO₄)₂·12H₂O.
- A process according to Claims 1 to 7, characterized in that the weight of the first coating after drying is between 1.0 and 10 g/m².
- A process according to Claims 1 to 8, characterized in that the first coating comprises flatting agents, antistatic agents, plasticizers, an organic acid which can form complexes with chromium ions, and/or wetting agents.
- A process according to Claims 1 to 9, characterized in that the coating solution for the first coating has a pH of 6.3 to 6.9.
- A process according to Claim 2, characterized in that the weight ratio chromium(III) salt:polyvinyl alcohol = 1:1 to 30:1.
- A process according to Claims 1 to 11 , characterized in that the weight of the second coating after drying is between 0.1 and 1.0 g/m².
- A process according to Claim 1, characterized in that gelatine is used as the protein-containing binder.
- A base for light-sensitive materials with an anti-coiling layer, characterized in that the base is manufactured by a process according to Claims 1 to 12 and, in the anti-coiling layer on the back, has a content of chromium(III) ions which is greater than 20 mg Cr/m².
- A coating solution containing hardeners, for protein-containing layers used for photographic purposes, characterized in that it comprises chromium(III) salt and a fully saponified polyvinyl alcohol.
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 |
|---|---|---|---|
| DE19873721808 DE3721808A1 (en) | 1987-07-02 | 1987-07-02 | METHOD FOR PRODUCING A LAYER SUPPORT FOR LIGHT-SENSITIVE MATERIALS WITH ANTIROLL LAYER |
| DE3721808 | 1987-07-02 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0297240A2 EP0297240A2 (en) | 1989-01-04 |
| EP0297240A3 EP0297240A3 (en) | 1989-03-29 |
| EP0297240B1 true 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) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (7)
| 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 |
| 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 |
| CH486049A (en) * | 1967-08-22 | 1970-02-15 | Ciba Geigy | Use of a combination of two hardening agents to harden film formers for photographic purposes |
| 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 |
-
1987
- 1987-07-02 DE DE19873721808 patent/DE3721808A1/en active Granted
-
1988
- 1988-04-26 ES ES198888106625T patent/ES2028166T3/en not_active Expired - Lifetime
- 1988-04-26 DE DE8888106625T patent/DE3867729D1/en not_active Expired - Lifetime
- 1988-04-26 EP EP88106625A patent/EP0297240B1/en not_active Expired - Lifetime
- 1988-04-26 AT AT88106625T patent/ATE71746T1/en not_active IP Right Cessation
- 1988-06-28 JP JP63158239A patent/JP2710629B2/en not_active Expired - Lifetime
- 1988-06-30 AU AU18597/88A patent/AU609495B2/en not_active Ceased
- 1988-06-30 CN CN88104001A patent/CN1029803C/en not_active Expired - Fee Related
- 1988-06-30 US US07/213,911 patent/US4977065A/en not_active Expired - Fee Related
-
1992
- 1992-01-30 GR GR920400134T patent/GR3003701T3/el unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3867729D1 (en) | 1992-02-27 |
| DE3721808C2 (en) | 1991-06-13 |
| AU1859788A (en) | 1989-01-05 |
| EP0297240A3 (en) | 1989-03-29 |
| EP0297240A2 (en) | 1989-01-04 |
| JP2710629B2 (en) | 1998-02-10 |
| US4977065A (en) | 1990-12-11 |
| JPS6424248A (en) | 1989-01-26 |
| ES2028166T3 (en) | 1992-07-01 |
| GR3003701T3 (en) | 1993-03-16 |
| CN1030649A (en) | 1989-01-25 |
| CN1029803C (en) | 1995-09-20 |
| AU609495B2 (en) | 1991-05-02 |
| ATE71746T1 (en) | 1992-02-15 |
| DE3721808A1 (en) | 1989-01-12 |
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