EP0395785B1 - Support for light-sensitive materials with an anti-curling layer coated on the backside - Google Patents
Support for light-sensitive materials with an anti-curling layer coated on the backside Download PDFInfo
- Publication number
- EP0395785B1 EP0395785B1 EP89108096A EP89108096A EP0395785B1 EP 0395785 B1 EP0395785 B1 EP 0395785B1 EP 89108096 A EP89108096 A EP 89108096A EP 89108096 A EP89108096 A EP 89108096A EP 0395785 B1 EP0395785 B1 EP 0395785B1
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- EP
- European Patent Office
- Prior art keywords
- support
- triazine
- weight
- layer
- solution
- 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.)
- Expired - Lifetime
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Classifications
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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
- G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/30—Hardeners
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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 layer support and a method for producing a layer support for light-sensitive materials with an anti-roll layer on the back.
- gelatin layers 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 called anti-roll, anti-curl or non-curling layers. 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, N-methylol compounds, dialdehyde polysaccharides, polyfunctional epoxides, aziridines, polyfunctional vinyl compounds, triacryl formal, substituted dichloro-s-triazines and others in Chap. 2 of the book "The Theory of the Photographic Process” by T.H. 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 carrier. In the second case, the hardening agents diffuse into the gelatin layer, where they react with the petid 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.
- 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 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 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.
- DE-A-3 721 808 describes rapid curing by applying two successive coatings, the second upper coating being formed from a curing agent solution of chromium salts.
- EP-A-303 789 has further described the synergistic effect of a hardener premix consisting of 1,2,3-triazine and formaldehyde.
- This premix achieves faster and better gelatin hardening than the addition of the individual components without premixing.
- the hardening reaction is accelerated by adding urea.
- this recipe led to photographic fog in color emulsions.
- this new hardening agent combination it was not possible to achieve an anti-roll coating with the required low water absorption capacity. This did not succeed even if additional aliphatic polyhydric alcohols were added to the anti-roll solution.
- the ratio of the triazine-formaldehyde premix to the N-methylol compound is 1: 2.5 to 1:10.
- the amount of total hardener (triazine-formaldehyde premix and N-methylol compound) is 3-6 g / 100 g protein.
- the amount of aliphatic polyhydric alcohol is 30-50 g / 100 g protein.
- the anti-roll layer solution can contain all other usual additives such as matting agents (e.g. silica), antistatic agents (e.g. inorganic salts), optical brighteners (e.g. stilbene derivatives), wetting agents (e.g. saponin) and the like.
- matting agents e.g. silica
- antistatic agents e.g. inorganic salts
- optical brighteners e.g. stilbene derivatives
- wetting agents e.g. saponin
- the anti-roll coating solution can be applied using all customary application and metering methods, such as roller application, engraving or nipping methods, with subsequent air brush or roller doctor metering if necessary.
- the anti-roll layer solution applied to the back of the support is dried directly from the sol mold, that is to say without prior gelation of the solution.
- a layer support consisting of 175 g / m2 paper and a layer of 35 g / m2 polyethylene per side was coated with the following anti-roll solution.
- the anti-roll layer solution was applied to the back of the polyethylene-coated support by means of a roller application device and knife metering and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C.
- the application weight after drying was 4.2 g / m2.
- the web speed was 130 m / min.
- a support consisting of 180 g / m2 paper and a layer of 35 g / m2 polyethylene on the front and 28 g / m2 polyethylene on the back was coated with the following anti-roll solution:
- the anti-roll layer solution was applied with an air brush to the back of the polyethylene-coated support, gelled in a cooling zone at 8 ° C. air temperature and dried in two stages at air temperatures of 32 ° C. and 60 ° C.
- the web speed was 130 m / min, the application weight after drying was 5.0 g / m2.
- a layer support according to Example 1 was coated with the following anti-roll layer solution:
- the anti-roll layer solution was applied to the back of the polyethylene-coated carrier by means of a roller applicator and knife metering and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C.
- the application weight after drying was 3.7 g / m2.
- the web speed was 130 m / min.
- a layer support according to Example 1 was coated with the following anti-roll layer solutions:
- the anti-roll layer solution was applied to the back of the polyethylene-coated support by means of a roller application device and knife metering and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C.
- the application weight after drying was 4.0 ⁇ 0.1 g / m2.
- the web speed was 130 m / min.
- V 2a A layer support according to Example 1 was coated with the following anti-roll layer solution, which corresponds to the formulation from Example 1 of DE-A-37 21 808:
- This coating which was applied to the back using an application device according to Example 1, was dried in a hot air duct at an air temperature of 130 ° C., the application weight was 5.0 g / m 2.
- This second coating applied to the back by means of an application device in accordance with Example 1, was dried in a hot air duct at an air temperature of 130.degree.
- the application weight was 320 mg / m2
- the web speed for both jobs was 100 m / min.
- V 2b A layer support according to Example 1 was coated with the following anti-roll layer solution, which is based on recipes 1 and 3 f from DE-A-37 27 293:
- the anti-roll layer solution was applied to the back of the polyethylene-coated support by means of the application device from Example 1 and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C.
- the web speed was 100 m / min, the application weight after drying was 4.0 g / m2.
- test strip is immersed in distilled water at 22 ° C for 10 minutes and then dried.
- the test strip is weighed before and after drying. The weight difference is based on the amount of gelatin that this test strip has.
- the amount of gelatin is calculated from the recipe, application weight and sample size. The water absorption is given in g water / 1 g gelatin.
Abstract
Description
Die Erfindung betrifft einen Schichtträger sowie ein Verfahren zur Herstellung eines Schichtträgers für lichtempfindliche Materialien mit einer Antirollschicht auf der Rückseite.The invention relates to a layer support and 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 Rückseitenschichten 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. However, gelatin layers 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 lichtempfindlichen 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.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.
Die auf die Rückseite aufgebrachten Schichten werden deshalb als Antiroll-, Anticurl- oder Noncurling-Schichten bezeichnet. Ihre Schichtdicke hängt vom Quellverhalten und von der Schichtdicke der Vorderseitenbeschichtung ab.The layers applied to the back are therefore called anti-roll, anti-curl or non-curling layers. 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 Citronensäure, 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, N-Methylolverbindungen, Dialdehydpolysaccharide, polyfunktionelle Epoxide, Aziridine, polyfunktionelle Vinylverbindungen, Triacrylformal, substituierte Dichlor-s-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, N-methylol compounds, dialdehyde polysaccharides, polyfunctional epoxides, aziridines, polyfunctional vinyl compounds, triacryl formal, substituted dichloro-s-triazines and others in Chap. 2 of the book "The Theory of the Photographic Process" by T.H. 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 Petidketten in Reaktion treten.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 carrier. In the second case, the hardening agents diffuse into the gelatin layer, where they react with the petid chains.
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.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 ein bevorzugtes Verwendungsgebiet und sind für andere Anwendungen nicht optimal, d.h. 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 Gelatineschichten geeignet, die kurz nach Trocknung der Schicht mechanisch beansprucht werden. 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.All substances used as hardening agents have a preferred area of use and are not optimal for other applications, i.e. suffers from 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 mechanically stressed shortly after the layer has dried. Other curing agents, e.g. Chromium salts are so reactive that a gelatin solution added to 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.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 gelatin auxiliary layers which are applied to a support prior to emulsionation and are later in contact with the actual photographic layers.
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.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.
Die DE-A-3 721 808 beschreibt eine schnelle Härtung durch das Auftragen zweier nacheinander erfolgender Beschichtungen, wobei die zweite obere Beschichtung aus einer Härtungsmittellösung von Chromsalzen gebildet wird.DE-A-3 721 808 describes rapid curing by applying two successive coatings, the second upper coating being formed from a curing agent solution of chromium salts.
Diese Offenlegungschrift beschreibt auch aus welchem Grund das Wasseraufnahmevermögen von Antirollschichten geringer sein sollte als das von lichtempfindlichen Emulsionsschichten. Das Wasseraufnahmevermögen der gehärteten Antirollschichten wird in der DE-A-3 721 808 durch gravimetrische Bestimmung eines Probestreifens nach 10 Minuten Behandlung in destilliertem Wasser von 22°C mit anschließender Trocknung ermittelt.This publication also describes the reason why the water absorption capacity of anti-roll layers should be lower than that of light-sensitive emulsion layers. The water absorption capacity of the hardened anti-roll layers is determined in DE-A-3 721 808 by gravimetric determination of a test strip after 10 minutes of treatment in distilled water at 22 ° C. with subsequent drying.
Die angestrebte Wasseraufnahme von weniger als 2,5 g H₂O pro 1 g Gelatine wird gemäß der Offenlegungsschrift nur durch die separat aufgetragene Chrom(III)- salzhaltige Härtungsmittelschicht erreicht. Das hat zur Folge, daß die Rückseite des lichtempfindlichen Schichtträgers je nach Menge und Schichtdicke der Anticurlschicht stets eine unerwünschte schwach grüne Verfärbung aufweist.The desired water absorption of less than 2.5 g H₂O per 1 g gelatin is achieved according to the published patent only by the separately applied chromium (III) - salt-containing hardening agent layer. The result of this is that the back of the light-sensitive substrate always has an undesirable pale green discoloration, depending on the amount and layer thickness of the anti-curl layer.
Außerdem ist ein Auftrag von zwei Schichten aufwendiger und störanfälliger als das Auftragen von nur einer Schicht.Applying two coats is also more complex and prone to malfunction than applying just one coat.
Die Härtung von proteinhaltigen Bindemitteln, insbesondere von Gelatine mit den bekannten Härtungsmitteln bzw. mit verschiedenen Kombinationen von Härtungsmitteln ist Stand der Technik, wenn es sich um die üblichen Anforderungen von Emulsions- und Hilfsschichten handelt. Es ist jedoch kein einstufiges Verfahren zur Herstellung von Antirollschichten mit einer Wasseraufnahme von weniger als 2,5 g H₂O pro 1 g Gelatine und ohne Verwendung von Chrom(III)-Salzen bekannt.The hardening of protein-containing binders, in particular gelatin, with the known hardening agents or with various combinations of hardening agents is state of the art when it comes to the usual requirements of emulsion and auxiliary layers. However, no one-step process for the production of anti-roll layers with a water absorption of less than 2.5 g H₂O per 1 g gelatin and without the use of chromium (III) salts is known.
In der EP-A-303 789 ist weiterhin der synergistische Effekt einer Härtungsmittel-Vormischung aus 1,2,3-Triazin und Formaldehyd beschrieben worden. Diese Vormischung erreicht schnellere und bessere Gelatinehärtung als die Zugabe der Einzelkomponenten ohne Vormischung. In Beispiel 3 dieser Patentanmeldung wird die Härtungsraktion durch Zusatz von Harnstoff noch beschleunigt. Allerdings führte diese Rezeptur zu fotografischem Schleier bei Coloremulsionen. Aber auch mit dieser neuen Härtungsmittelkombination war es nicht möglich, eine Antirollschicht mit dem geforderten geringen Wasseraufnahmevermögen zu erreichen. Das gelang auch dann nicht, wenn zusätzlich aliphatische mehrwertige Alkohole zur Antirollschichtlösung zugemischt wurden.EP-A-303 789 has further described the synergistic effect of a hardener premix consisting of 1,2,3-triazine and formaldehyde. This premix achieves faster and better gelatin hardening than the addition of the individual components without premixing. In example 3 of this patent application, the hardening reaction is accelerated by adding urea. However, this recipe led to photographic fog in color emulsions. But even with this new hardening agent combination it was not possible to achieve an anti-roll coating with the required low water absorption capacity. This did not succeed even if additional aliphatic polyhydric alcohols were added to the anti-roll solution.
Die Aufgabe der Erfindung besteht darin, einen Schichtträger für lichtempfindliche Materialien, enthaltend
- a) 100 Gewichtsteile Proteinbinder oder proteinhaltige Bindemittelmischung und
- b) 0,3 - 1,7 Gewichtsteile eines Reaktionsprodukts aus Triazin und Formaldehyd im Massenverhältnis von 1:0,1 bis 1:0,7,
zur Verfügung zu stellen, dessen rückseitig aufgebrachte Antirollschicht ein Wasseraufnahmevermögen von weniger als 2,5 g H₂O pro 1 g Protein aufweist, gemessen nach 10 Minuten Einwirkzeit von destilliertem Wasser von 22°C.The object of the invention is to contain a support for photosensitive materials
- a) 100 parts by weight of protein binder or protein-containing binder mixture and
- b) 0.3-1.7 parts by weight of a reaction product of triazine and formaldehyde in a mass ratio of 1: 0.1 to 1: 0.7,
To make available, the anti-roll layer applied on the back has a water absorption capacity of less than 2.5 g H₂O per 1 g protein, measured after 10 minutes of distilled water at 22 ° C.
Es ist weiter Aufgabe der Erfindung, ein Verfahren zur Herstellung von Schichtträgern für lichtempfindliche Materialien mit einer proteinhaltigen Antirollschicht auf der Rückseite des Schichtträgers bereitzustellen, mit dem Wasseraufnahmen der gehärteten Antirollschicht unter 2,5 g H₂O pro 1 g Protein, gemessen nach 10 Minuten Einwirkzeit von destilliertem Waser von 22°C, in einem Arbeitsgang und ohne unerwünschte Verfärbung der Antirollschicht erhalten werden.It is a further object of the invention to provide a process for the production of supports for light-sensitive materials with a protein-containing anti-roll layer on the back of the support, with the water absorption of the hardened anti-roll layer under 2.5 g H₂O per 1 g protein, measured after 10 minutes of exposure distilled water of 22 ° C can be obtained in one operation and without undesirable discoloration of the anti-roll layer.
Weiterhin ist es Aufgabe der Erfindung, das Verfahren zur Herstellung dieses Schichtträgers für lichtempfindliche Materialien so zu gestalten, daß ein schleierarmes fotografisches Material entsteht.Furthermore, it is an object of the invention to design the method for producing this layer support for light-sensitive materials in such a way that a low-fog photographic material is produced.
Gelöst werden diese Aufgaben durch einen Schichtträger für lichtempfindliche Materialien mit einer Antirollschicht auf der Rückseite, der mindestens folgende weitere Komponenten enthält:
- c) 2,1 - 5,5 Gewichtsteile einer N-Methylolverbindung,
- d) 30 - 50 Gewichtsteile eines aliphatischen mehrwertigen Alkohols.
- c) 2.1-5.5 parts by weight of an N-methylol compound,
- d) 30-50 parts by weight of an aliphatic polyhydric alcohol.
Das Verhältnis der Komponenten in der Triazin-Formaldehyd-Vormischung entspricht dem der DE-A-37 27 293 und beträgt 1,3,5-Triazin : Formaldehyd = 1:0,1 bis 1:0,7.The ratio of the components in the triazine-formaldehyde premix corresponds to that of DE-A-37 27 293 and is 1,3,5-triazine: formaldehyde = 1: 0.1 to 1: 0.7.
Das Verhältnis der Triazin-Formaldehyd-Vormischung zur N-Methylolverbindung beträgt 1:2,5 bis 1:10.The ratio of the triazine-formaldehyde premix to the N-methylol compound is 1: 2.5 to 1:10.
Die Menge an Gesamthärtungsmittel (Triazin-Formaldehyd-Vormischung und N-Methylolverbindung) ist 3-6 g/100 g Protein. Die Menge an aliphatischem mehrwertigem Alkohol ist 30 - 50 g/100 g Protein.The amount of total hardener (triazine-formaldehyde premix and N-methylol compound) is 3-6 g / 100 g protein. The amount of aliphatic polyhydric alcohol is 30-50 g / 100 g protein.
Die Antirollschichtlösung kann alle sonst üblichen weiteren Zusätze wie Mattierungsmittel (z.B. Kieselsäure), Antistatika (z.B. anorganische Salze), optische Aufheller (z.B. Stilbenderivate), Netzmittel (z.B. Saponin) und ähnliche enthalten.The anti-roll layer solution can contain all other usual additives such as matting agents (e.g. silica), antistatic agents (e.g. inorganic salts), optical brighteners (e.g. stilbene derivatives), wetting agents (e.g. saponin) and the like.
Die Antirollschichtlösung kann mit allen gebräuchlichen Auftrags- und Dosierverfahren, wie beispielsweise Walzenantrag-, Gravur- oder Nipp-Verfahren, mit gegebenenfalls anschließender Luftbürsten- oder Rollrakeldosierung aufgetragen werden.The anti-roll coating solution can be applied using all customary application and metering methods, such as roller application, engraving or nipping methods, with subsequent air brush or roller doctor metering if necessary.
In einer besonders wirtschaftlichen Form des Verfahrens, wird die auf die Rückseite des Schichtträgers aufgetragene Antirollschichtlösung direkt aus der Solform heraus getrocknet, also ohne vorhergehende Gelierung der Lösung.In a particularly economical form of the process, the anti-roll layer solution applied to the back of the support is dried directly from the sol mold, that is to say without prior gelation of the solution.
Es war überraschend, daß eine Kombination der genannten Zusatzstoffe eine so ausgezeichnete schnelle Proteinhärtung ergaben, da weder die gleiche Menge an Einzelkomponenten, noch die bevorzugte Vormischung aus Triazin und Formaldehyd entsprechend gute Härtungsergebnisse lieferten.It was surprising that a combination of the additives mentioned gave such an excellent rapid protein hardening since neither the same amount of individual components nor the preferred premix of triazine and formaldehyde gave correspondingly good hardening results.
Die folgenden Beispiele sollen die Erfindung verdeutlichen, jedoch nicht einschränken:The following examples are intended to illustrate, but not limit, the invention:
Ein Schichtträger bestehend aus 175 g/m² Papier und je einer Schicht von 35 g/m² Polyethylen pro Seite wurde mit folgender Antirollschichtlösung beschichtet.
Die Antirollschichtlösung wurde mittels Walzenauftragsvorrichtung und Rakeldosierung auf die Rückseite des mit Polyethylen beschichteten Trägers aufgetragen und aus der Solform heraus im Heißluftkanal bei einer Lufttemperatur von 130°C getrocknet. Das Auftragsgewicht nach Trocknung betrug 4,2 g/m². Die Bahngeschwindigkeit betrug 130 m/min.The anti-roll layer solution was applied to the back of the polyethylene-coated support by means of a roller application device and knife metering and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C. The application weight after drying was 4.2 g / m². The web speed was 130 m / min.
Ein Schichtträger bestehend aus 180 g/m² Papier und einer Schicht von 35 g/m² Polyethylen auf der Vorderseite und 28 g/m² Polyethylen auf der Rückseite wurde mit folgender Antirollschichtlösung beschichtet:
Die Antirollschichtlösung wurde mittels Luftbürste auf die Rückseite des mit Polyethylen beschichteten Trägers aufgetragen, in einer Kühlzone bei 8°C Lufttemperatur geliert und in zwei Stufen bei Lufttemperaturen von 32°C und 60°C getrocknet. Die Bahngeschwindigkeit betrug 130 m/min, das Auftragsgewicht nach Trocknung betrug 5,0 g/m².The anti-roll layer solution was applied with an air brush to the back of the polyethylene-coated support, gelled in a cooling zone at 8 ° C. air temperature and dried in two stages at air temperatures of 32 ° C. and 60 ° C. The web speed was 130 m / min, the application weight after drying was 5.0 g / m².
Ein Schichtträger gemäß Beispiel 1 wurde mit folgender Antirollschichtlöung beschichtet:
Die Antirollschichtlösung wurde mittels Walzauftragsvorrichtung und Rakeldosierung auf die Rückseite des mit Polyethylen beschichteten Trägers aufgetragen und aus der Solform heraus im Heißluftkanal bei einer Lufttemperatur von 130°C getrocknet. Das Auftragsgewicht nach Trocknung betrug 3,7 g/m². Die Bahngeschwindigkeit betrug 130 m/min.The anti-roll layer solution was applied to the back of the polyethylene-coated carrier by means of a roller applicator and knife metering and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C. The application weight after drying was 3.7 g / m². The web speed was 130 m / min.
Ein Schichtträger gemäß Beispiel 1 wurde mit folgenden Antirollschichtlösungen beschichtet:
Die weiteren Komponenten waren bei
Die Antirollschichtlösung wurde mittels Walzenauftragsvorrichtung und Rakeldosierung auf die Rückseite des mit Polyethylen beschichteten Trägers aufgetragen und aus der Solform heraus im Heißluftkanal bei einer Lufttemperatur von 130°C getrocknet. Das Auftragsgewicht nach Trocknung betrug 4,0 ± 0,1 g/m². Die Bahngeschwindigkeit betrug 130 m/min.The anti-roll layer solution was applied to the back of the polyethylene-coated support by means of a roller application device and knife metering and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C. The application weight after drying was 4.0 ± 0.1 g / m². The web speed was 130 m / min.
V 2a: Ein Schichtträger gemäß Beispiel 1 wurde mit der folgenden Antirollschichtlösung beschichtet, die der Rezeptur aus Beispiel 1 der DE-A-37 21 808 entspricht:
V 2a: A layer support according to Example 1 was coated with the following anti-roll layer solution, which corresponds to the formulation from Example 1 of DE-A-37 21 808:
Dieser, mittels Auftragsvorrichtung entsprechend Beispiel 1 auf die Rückseite aufgetragene Überzug, wurde im Heißluftkanal bei 130°C Lufttemperatur getrocknet, das Auftragsgewicht betrug 5,0 g/m².This coating, which was applied to the back using an application device according to Example 1, was dried in a hot air duct at an air temperature of 130 ° C., the application weight was 5.0 g / m 2.
Auf diesen ersten Überzug wurde unmittelbar nach seiner Trocknung der folgende zweite Überzug aufgetragen:
Dieser, mittels Auftragsvorrichtung entsprechend Beispiel 1 auf die Rückseite aufgetragene zweite Überzug, wurde im Heißluftkanal bei 130°C Lufttemperatur getrocknet. Das Auftragsgewicht betrug 320 mg/m², die Bahngeschwindigkeit bei beiden Aufträgen war 100 m/min.
V 2b: Ein Schichtträger gemäß Beispiel 1 wurde mit der folgenden Antirollschichtlösung beschichtet, die sich an die Rezepturen 1 und 3 f an die DE-A-37 27 293 anlehnt:
V 2b: A layer support according to Example 1 was coated with the following anti-roll layer solution, which is based on recipes 1 and 3 f from DE-A-37 27 293:
Die Antirollschichtlösung wurde mittels Auftragsvorrichtung aus Beispiel 1 auf die Rückseite des mit Polyethylen beschichteten Trägers aufgetragen und aus der Solform heraus im Heißluftkanal bei einer Lufttemperatur von 130°C getrocknet. Die Bahngeschwindigkeit betrug 100 m/min, das Auftragsgewicht nach Trocknung betrug 4,0 g/m².The anti-roll layer solution was applied to the back of the polyethylene-coated support by means of the application device from Example 1 and dried out of the sol mold in a hot air duct at an air temperature of 130 ° C. The web speed was 100 m / min, the application weight after drying was 4.0 g / m².
Ein Probestreifen wird für 10 Minuten in destilliertes Wasser von 22°C getaucht und anschließend getrocknet. Vor und nach der Trocknung wird der Probestreifen gewogen. Die Gewichtsdifferenz wird bezogen auf die Gelatinemenge, die dieser Probestreifen aufweist. Die Gelatinemenge wird aus Rezeptur, Auftragsgewicht und Probengröße errechnet. Die Wasseraufnahme wird angegeben in g Wasser/1 g Gelatine.A test strip is immersed in distilled water at 22 ° C for 10 minutes and then dried. The test strip is weighed before and after drying. The weight difference is based on the amount of gelatin that this test strip has. The amount of gelatin is calculated from the recipe, application weight and sample size. The water absorption is given in g water / 1 g gelatin.
Handelsübliches Colorpapier wird in Kontakt mit der frisch getrockneten Emulsionsschicht 5 Tage bei 50°C inkubiert, dann zusammen mit einer gleich behandelten Blindprobe entwickelt und fixiert und der Schleier gegen den Schleier der Blindprobe ausgewertet, wobei die Note 1 keinen Unterschied bedeutet und die Note 5 eine sehr starke Veränderung.Commercial color paper is incubated in contact with the freshly dried emulsion layer for 5 days at 50 ° C., then developed and fixed together with a blind sample treated in the same way and the veil evaluated against the veil of the blind sample, whereby the grade 1 means no difference and the grade 5 a very strong change.
Claims (7)
- A support for light-sensitive materials with an anti-curl backing on the rear side, the anti-curl backing containing at least the following constituents:a) 100 parts by weight protein binder or protein-containing binder mixture,b) 0.3 - 1.7 parts by weight of a reaction product of triazine and formaldehyde in a mass ratio of 1:0.1 to 1:0.7,
characterised in that the anti-curl backing further containsc) 2.1 - 5.5 parts by weight of an N-methylol compound, andd) 30 - 50 parts by weight of an aliphatic polyvalent alcohol. - A support according to Claim 1, characterised in that the triazine is a 1,3,5-triazine.
- A support according to Claim 1, characterised in that the N-methylol compound is a dimethylol or trimethylol urea or trimethylol melamine.
- A support according to Claim 1, characterised in that the aliphatic polyvalent alcohol has a molecular weight of less than 2000.
- A support according to Claim 1, characterised in that the anti-curl backing contains other conventional additives such as matting agents, wetting agents, optical brighteners, toning dyes or antistatic agents.
- A method for producing a support according to one or more of Claims 1 to 5, characterised in that the reaction product of triazine and formaldehyde which has been matured for at least one hour, an N-methylol compound and an aliphatic polyvalent alcohol are added to an aqueous protein-containing solution and that this anti-curl backing solution is applied to the support and dried.
- A method according to Claim 6, characterised in that a sol form of the applied anti-curl backing solution is dried.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP89108096A EP0395785B1 (en) | 1989-05-05 | 1989-05-05 | Support for light-sensitive materials with an anti-curling layer coated on the backside |
| AT89108096T ATE118622T1 (en) | 1989-05-05 | 1989-05-05 | LAYER CARRIER FOR LIGHT-SENSITIVE MATERIALS AND ANTI-ROLL LAYER ON THE BACK. |
| DE58909012T DE58909012D1 (en) | 1989-05-05 | 1989-05-05 | Layer support for light-sensitive materials and anti-roll layer on the back. |
| US07/510,303 US5100769A (en) | 1989-05-05 | 1990-04-16 | Paper support for light-sensitive materials with an anti-curl layer on the backside |
| JP2111570A JPH0812396B2 (en) | 1989-05-05 | 1990-04-25 | Support for photosensitive material having anti-curl layer on back side |
| CN90102695.6A CN1029428C (en) | 1989-05-05 | 1990-05-04 | Paper support for light-sensitive materials with an anti-curl layer on the backside |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP89108096A EP0395785B1 (en) | 1989-05-05 | 1989-05-05 | Support for light-sensitive materials with an anti-curling layer coated on the backside |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0395785A1 EP0395785A1 (en) | 1990-11-07 |
| EP0395785B1 true EP0395785B1 (en) | 1995-02-15 |
Family
ID=8201325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89108096A Expired - Lifetime EP0395785B1 (en) | 1989-05-05 | 1989-05-05 | Support for light-sensitive materials with an anti-curling layer coated on the backside |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5100769A (en) |
| EP (1) | EP0395785B1 (en) |
| JP (1) | JPH0812396B2 (en) |
| CN (1) | CN1029428C (en) |
| AT (1) | ATE118622T1 (en) |
| DE (1) | DE58909012D1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05297514A (en) * | 1992-04-20 | 1993-11-12 | Konica Corp | Silver halide photographic sensitive material |
| 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 |
| US5358834A (en) * | 1993-09-23 | 1994-10-25 | Eastman Kodak Company | Photographic element provided with a backing layer |
| DE69526734D1 (en) * | 1995-07-31 | 2002-06-20 | Agfa Gevaert Nv | Material for industrial radiography and development processes therefor |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3227578A (en) * | 1961-10-12 | 1966-01-04 | Eastman Kodak Co | Additives to reduce curl in paper |
| GB1127346A (en) * | 1965-06-04 | 1968-09-18 | Fuji Photo Film Co Ltd | Improvements in and relating to photographic material |
| US3515555A (en) * | 1967-03-08 | 1970-06-02 | Eastman Kodak Co | Toning composition for direct positive paper |
| US3549375A (en) * | 1967-05-08 | 1970-12-22 | Gaf Corp | Antistatic photographic film |
| JPS4966329A (en) * | 1972-10-30 | 1974-06-27 | ||
| DE3727293A1 (en) * | 1987-08-17 | 1989-03-02 | Schoeller F Jun Gmbh Co Kg | METHOD FOR CURING GELATINE-CONTAINING PHOTOGRAPHIC LAYERS OR AUXILIARY LAYERS |
-
1989
- 1989-05-05 EP EP89108096A patent/EP0395785B1/en not_active Expired - Lifetime
- 1989-05-05 DE DE58909012T patent/DE58909012D1/en not_active Expired - Fee Related
- 1989-05-05 AT AT89108096T patent/ATE118622T1/en not_active IP Right Cessation
-
1990
- 1990-04-16 US US07/510,303 patent/US5100769A/en not_active Expired - Lifetime
- 1990-04-25 JP JP2111570A patent/JPH0812396B2/en not_active Expired - Fee Related
- 1990-05-04 CN CN90102695.6A patent/CN1029428C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5100769A (en) | 1992-03-31 |
| JPH02304552A (en) | 1990-12-18 |
| DE58909012D1 (en) | 1995-03-23 |
| CN1046985A (en) | 1990-11-14 |
| ATE118622T1 (en) | 1995-03-15 |
| EP0395785A1 (en) | 1990-11-07 |
| CN1029428C (en) | 1995-08-02 |
| JPH0812396B2 (en) | 1996-02-07 |
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