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EP0274017A2 - Antistatic photographic support material - Google Patents

Antistatic photographic support material Download PDF

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Publication number
EP0274017A2
EP0274017A2 EP19870116068 EP87116068A EP0274017A2 EP 0274017 A2 EP0274017 A2 EP 0274017A2 EP 19870116068 EP19870116068 EP 19870116068 EP 87116068 A EP87116068 A EP 87116068A EP 0274017 A2 EP0274017 A2 EP 0274017A2
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EP
European Patent Office
Prior art keywords
support material
photographic
material according
mol
photographic support
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19870116068
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German (de)
French (fr)
Other versions
EP0274017B1 (en
EP0274017A3 (en
Inventor
Eckehard Säverin
Hans-Udo Tyrakowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Felex Schoeller Jr and GmbH and Co KG
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
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Application filed by Felix Schoeller Jr Foto und Spezialpapiere GmbH, Felex Schoeller Jr and GmbH and Co KG filed Critical Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority to AT87116068T priority Critical patent/ATE78938T1/en
Publication of EP0274017A2 publication Critical patent/EP0274017A2/en
Publication of EP0274017A3 publication Critical patent/EP0274017A3/en
Application granted granted Critical
Publication of EP0274017B1 publication Critical patent/EP0274017B1/en
Anticipated expiration legal-status Critical
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings

Definitions

  • Backing materials for photographic layers are usually provided with an antistatic layer on the back in order to prevent them from becoming damaged during processing of the material, e.g. build up static charges on the surface during watering with photosensitive emulsions or after passing through the bath.
  • the discharges would lead to exposure of the photographic layer, so that undesired markings in the image become visible.
  • the static charge also causes the images to adhere to one another during sorting, so that further processing is disrupted.
  • the back layer of the photographic material should also meet the following requirements: - Low dirt pick-up when the photographic material passes through roller transport developing machines, in which dirt films from the developer's oxidation products are easily deposited. - Highest possible abrasion resistance and resistance in alkaline developer solutions, which is important, for example, when the photographic material passes through processing machines equipped with rollers. - Good printability when printing with conventional printing inks as well as good lettering. - Good adhesive tape adhesion, since when the photographic material passes through modern development machines, the next roll in each case is glued to the previous roll and the adhesive adhesion must be ensured when the glue point passes through processing baths.
  • hydrophobic components have the disadvantage of high dirt absorption and low antistatic activity
  • hydrophilic components have low adhesive tape adhesion, poor printability and insufficient bath strength result.
  • EP-AO 160 912 discloses a photographic material with a silver halide emulsion layer on one side of a polyolefin-coated paper support and an antistatic layer on the other side of the support, in which the antistatic layer contains a sodium magnesium silicate, a sodium polystyrene sulfonate and certain succinic acid half-esters.
  • the conductivity in this combination is such that the desired antistatic properties are sufficient.
  • the material also has a relative low dirt absorption.
  • the object of the present invention is to provide a photographic material of the type mentioned at the beginning, the antistatic coated back of which at the same time has good properties with regard to all of the above five requirements.
  • the antistatic layer contains a colloidal aluminum-modified silica, an alkali salt of an organic polyacid, for example sodium polystyrene sulfonate as a conductivity agent, an aqueous one Dispersion of copolymers of acrylic acid alkyl esters with a content of free carboxyl groups of 1 -10 mol% and free hydroxyl groups of 0 - 20 mol% as a binder, and a trifunctional aziridine as a crosslinking agent.
  • an alkali salt of an organic polyacid for example sodium polystyrene sulfonate
  • an aqueous one Dispersion of copolymers of acrylic acid alkyl esters with a content of free carboxyl groups of 1 -10 mol% and free hydroxyl groups of 0 - 20 mol% as a binder and a trifunctional aziridine as a crosslinking agent.
  • crosslinking agents for plastic dispersions containing free carboxyl groups.
  • this backside coating according to the invention shows both sufficient conductivity and thus good antistatic properties, low dirt absorption with regard to the mostly dark-colored oxidation products of developer solutions, good abrasion and water resistance when passing through acidic and alkaline development baths, good printability with commercially available printing inks and good writing properties as well as good adhesive tape adhesion even with chemical and mechanical stress.
  • the sum of the polar groups does not exceed 25 mol% of the copolymer of acrylic acid esters.
  • a terpolymer of styrene, C1-C4-alkyl acrylate and 10% methacrylic acid is provided as a binder.
  • the effectiveness of the combination of the specific binder according to the invention and the crosslinking agent is increased by sodium magnesium silicate of the montmorillonite type additionally contained in the antistatic layer.
  • the proportions of the components are based on the dry layer as follows: colloidal silica: 23 - 70% by weight Alkaline salt of polyacid: 3 - 30% by weight Polymer binder: 30 - 70% by weight Montmorillonite: 0 - 30 wt:% Aziridine: 2-18% by weight
  • the layer application (dry) is 0.2 - 1.0 g / m2, in particular 0.2 - 0.5 g / m2.
  • the support material for photographic layers according to the invention is produced in particular by slowly mixing the individual components in the sequence water-alcohol mixture, montmorillonite, colloidals, aluminum-modified silica, copolymer dispersion, alkali salt of organic polyacid, aziridine, the desired pH - Sets the value with ammonia solution, applies the casting solution thus obtained in the desired layer thickness and then dries.
  • the antistatic properties are tested by measuring the surface resistance with an electrode according to DIN 53482.
  • samples are printed with standard color ribbons.
  • the samples were printed in a 30 sec commercial developer dipped and rinsed briefly with water. Then you apply finger friction to the printed back. It is checked whether the print is blurred or whether discoloration occurs due to the washing out of a color component of the printing ink.
  • a print smeared after developer bath and friction is either due to poor adhesion of the print on the back of the photographic material or to low abrasion resistance of the back coating. The latter, i.e. damage due to abrasion of the back surface, can be seen when viewed against the light.
  • the sample is provided with a commercially available adhesive tape (eg 3 M adhesive tape 8422) and this is fixed with a defined weight (8 kg roll). Then the pattern is cut into 1.5 cm wide strips and the adhesive tape is partially peeled off.
  • the sample prepared in this way is clamped in a breaking load tester in which the adhesive tape is removed from the base at an angle of 180 ° at a speed of 20 cm / min. The force required to pull off is measured. Since the adhesive tape adhesion must be sufficient even under mechanical stress in developing solutions, a drop of water is placed on the boundary between the photographic material and the adhesive tape before the adhesive tape is peeled off.
  • Table 1 below contains examples of compositions of mixtures for antistatic layers according to the invention. The associated test values are contained in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A base material for photographic layers with an antistatic back coating contains at least four components: a. a colloidal aluminium-modified silica b. an alkali metal salt of an organic polybasic acid c. an aqueous dispersion of alkyl acrylate copolymers containing 1-10 mol% of free carboxyl groups and 0-20 mol% of free hydroxyl groups d. a trifunctional aziridine as a crosslinking agent. A process for the preparation thereof is also described. <??>The antistatic back of the photographic material according to the invention shows low pick-up of soil when passing through developing machines with roll transport, high wear resistance and stability in alkaline developer solutions, good printability when printed with conventional printing inks, good lettering capacity and also good adhesion of adhesive tapes.

Description

Trägermaterialien für fotografische Schichten sind üblicherweise auf der Rückseite mit einer antista­tischen Schicht versehen, um zu verhindern, daß sich während der Verarbeitung des Materials, d.h. während des Begießens mit lichtempfindlichen Emulsionen oder auch nach dem Bäderdurchgang bei Sortiervorgängen auf der Oberfläche statische Ladungen aufbauen. Die Entladungen würden zur Belichtung der fotografischen Schicht führen, so daß unerwünschte Markierungen im Bild sichtbar werden. Die statische Aufladung führt außerdem während des Sortierens zur Haftung der Bilder aneinander, so daß die weitere Verarbeitung gestört wird.Backing materials for photographic layers are usually provided with an antistatic layer on the back in order to prevent them from becoming damaged during processing of the material, e.g. build up static charges on the surface during watering with photosensitive emulsions or after passing through the bath. The discharges would lead to exposure of the photographic layer, so that undesired markings in the image become visible. The static charge also causes the images to adhere to one another during sorting, so that further processing is disrupted.

Neben den genannten antistatischen Eigenschaften soll die rückseitige Schicht des fotografischen Ma­terials gleichzeitig folgende Anforderungen erfüllen:
- Geringe Schmutzaufnahme beim Durchgang des fotografischen Materials durch Walzentransport­entwicklungsmaschinen, bei dem sich leicht Schmutzfilme aus den Oxydationsprodukten des Entwicklers ablagern.
- Möglichst hohe Abriebfestigkeit und Beständigkeit in alkalischen Entwicklerlösungen, die z.B. beim Durch­gang des fotografischen Materials durch mit Walzen ausgerüstete Verarbeitungsmaschinen bedeutsam ist.
- Gute Bedruckbarkeit beim Bedrucken mit herkömm­lichen Druckfarben sowie gute Beschriftbarkeit.
- Gute Klebebandhaftung, da beim Durchlauf des fotografischen Materials durch moderne Entwick­lungsautomaten die jeweils nächstfolgende Rolle an die vorhergehende Rolle geklebt wird und die Klebehaftung beim Durchgang der Klebestelle durch Entwicklungsbäder gewährleistet sein muß.In addition to the antistatic properties mentioned, the back layer of the photographic material should also meet the following requirements:
- Low dirt pick-up when the photographic material passes through roller transport developing machines, in which dirt films from the developer's oxidation products are easily deposited.
- Highest possible abrasion resistance and resistance in alkaline developer solutions, which is important, for example, when the photographic material passes through processing machines equipped with rollers.
- Good printability when printing with conventional printing inks as well as good lettering.
- Good adhesive tape adhesion, since when the photographic material passes through modern development machines, the next roll in each case is glued to the previous roll and the adhesive adhesion must be ensured when the glue point passes through processing baths.

Es ist in der Praxis sehr schwierig, diese Eigen­schaften gleichzeitig zu verwirklichen, weil die dafür bekannten Komponenten die Materialeigenschaf­ten zum Teil gegensätzlich beeinflussen.Hydrophobe Komponenten haben beispielsweise den Nachteil einer hohen Schmutzaufnahme und geringer antistatischer Wirksamkeit, während hydrophile Komponenten eine geringe Klebebandhaftung, schlechte Bedruckbarkeit und ungenügende Bäderfestigkeit ergeben.In practice, it is very difficult to achieve these properties at the same time, because the components known for this influence the material properties in part, e.g. hydrophobic components have the disadvantage of high dirt absorption and low antistatic activity, while hydrophilic components have low adhesive tape adhesion, poor printability and insufficient bath strength result.

Es ist bekannt, daß die statische Aufladung der rück­seitigen Schicht durch Mattierungsmittel vermindert werden kann, weil durch sie die Adhäsion zweier aufein­anderliegender fotografischer Materialien herabgesetzt wird. Weiter ist bekannt, daß die bereits vorhandene statische Aufladung durch elektrisch leitende Zusätze in der Schicht entfernt wird. So ist z.B. aus der EP-A-O 160 912 ein fotografisches Material mit einer Silberhalogenidemulsionsschicht auf einer Seite eines polyolefinbeschichteten Papierträgers und einer antistatischen Schicht auf der anderen Seite des Trägers bekannt, bei dem die antistatische Schicht ein Natriummagnesiumsilikat, ein Natriumpolystyrolsulfonat und bestimmte Bernsteinsäurehalbester enthält. Die Leitfähigkeit ist bei dieser Kombination so, daß die gewünschten antistatischen Eigenschaften ausreichend sind. Außerdem weist das Material auch eine relativ geringe Schmutzaufnahme auf. Dies geht jedoch einher mit Verlusten bei den anderen erforderlichen Eigen­schaften. Da antistatisch wirksame Stoffe wegen der ionischen Leitfähigkeit in der Regel wasserlöslich oder zumindest wasserquellbar sind, führt eine gute Leitfähigkeit gewöhnlich zu einer schlechten Haftung der Schicht beim Durchgang durch Bäder. Eine Folge der guten Leitfähigkeit ist also eine verringerte Abrieb­festigkeit sowie eine verschlechterte Klebebandhaftung.It is known that the static charge on the back layer can be reduced by matting agents because it reduces the adhesion of two photographic materials lying on top of one another. It is also known that the static charge already present is removed by electrically conductive additives in the layer. For example, EP-AO 160 912 discloses a photographic material with a silver halide emulsion layer on one side of a polyolefin-coated paper support and an antistatic layer on the other side of the support, in which the antistatic layer contains a sodium magnesium silicate, a sodium polystyrene sulfonate and certain succinic acid half-esters. The conductivity in this combination is such that the desired antistatic properties are sufficient. In addition, the material also has a relative low dirt absorption. However, this is accompanied by losses in the other required properties. Since antistatic substances are generally water-soluble or at least water-swellable because of the ionic conductivity, good conductivity usually leads to poor adhesion of the layer when passing through baths. A consequence of the good conductivity is therefore a reduced resistance to abrasion and a deterioration in adhesive tape adhesion.

Es ist nun grundsätzlich schwierig, ein fotografisches Material zu erhalten, das bezüglich aller der oben genannten fünf Eigenschaften den Anforderungen ent­spricht. Polare Oberflächen sind nämlich zwar leit­fähig (antistatische Eigenschaft) und zeigen eine geringe Schmutzaufnahme, aber mit zunehmender Pola­rität nehmen die Abriebfestigkeit und die Klebeband­haftung durch Einwirkung der Bäder ab. Umgekehrt führte bislang eine Verbesserung der Klebebandhaftung zu Verlusten hinsichtlich der Leitfähigkeit und zu erhöhter Schmutzaufnahme des fotografischen Materials.It is now fundamentally difficult to obtain a photographic material that meets the requirements for all of the above five properties. Indeed, polar surfaces are conductive (antistatic property) and show little dirt pick-up, but with increasing polarity, the abrasion resistance and the adhesive tape decrease due to the action of the baths. Conversely, an improvement in adhesive tape adhesion has led to losses in terms of conductivity and increased dirt absorption of the photographic material.

Die Aufgabe der vorliegenden Erfindung besteht darin, ein fotografisches Material der eingangs genannten Art zu schaffen, dessen antistatisch beschichtete Rückseite gleichzeitig gute Eigenschaften hinsicht­lich aller der oben genannten fünf Anforderungen auf­weist.The object of the present invention is to provide a photographic material of the type mentioned at the beginning, the antistatic coated back of which at the same time has good properties with regard to all of the above five requirements.

Dazu enthält die antistatische Schicht eine kolloi­dale aluminiummodifizierte Kieselsäure, ein Alkali­salz einer organischen Polysäure, z.B. Natriumpoly­styrolsulfonat als Leitfähigkeitsmittel, eine wässrige Dispersion von Copolymeren von Acrylsäure-Alkylestern mit einem Gehalt an freien Carboxylgruppen von 1 -­10 Mol-% und an freien Hydroxylgruppen von 0 - 20 Mol-% als Bindemittel, sowie ein trifunktionelles Aziridin als Vernetzungsmittel.For this purpose, the antistatic layer contains a colloidal aluminum-modified silica, an alkali salt of an organic polyacid, for example sodium polystyrene sulfonate as a conductivity agent, an aqueous one Dispersion of copolymers of acrylic acid alkyl esters with a content of free carboxyl groups of 1 -10 mol% and free hydroxyl groups of 0 - 20 mol% as a binder, and a trifunctional aziridine as a crosslinking agent.

Letztere sind als Vernetzungsmittel für freie Carboxyl­gruppen enthaltende Kunststoffdispersionen bekannt.The latter are known as crosslinking agents for plastic dispersions containing free carboxyl groups.

Wie Vergleichsversuche gezeigt haben, zeigt dieser erfindungsgemäße Rückseitenstrich sowohl ausreichende Leitfähigkeit und somit gute antistatische Eigenschaf­ten, geringe Schmutzaufnahme hinsichtlich der meist dunkel gefärbten Oxydationsprodukte von Entwickler­lösungen, gute Abrieb- und Wasserfestigkeit beim Durchgang durch saure und alkalische Entwicklungsbäder, gute Bedruckbarkeit mit handelsüblichen Druckfarben und gute Beschriftbarkeit sowie gute Klebebandhaftung auch bei chemischer und mechanischer Beanspruchung. Vorzugsweise überschreitet die Summe der polaren Gruppen nicht 25 Mol-% des Copolymeren von Acryl­säureestern.As comparative experiments have shown, this backside coating according to the invention shows both sufficient conductivity and thus good antistatic properties, low dirt absorption with regard to the mostly dark-colored oxidation products of developer solutions, good abrasion and water resistance when passing through acidic and alkaline development baths, good printability with commercially available printing inks and good writing properties as well as good adhesive tape adhesion even with chemical and mechanical stress. Preferably, the sum of the polar groups does not exceed 25 mol% of the copolymer of acrylic acid esters.

Gemäß einer bevorzugten Ausführungsform der Erfin­dung ist als Bindemittel ein Terpolymeres aus Styrol, C₁-C₄-Alkylacrylat und 10 % Methacrylsäure vorgesehen. Gemäß einer wieteren bevorzugten Ausführungsform der Erfindung wird die Wirksamkeit der Kombination aus dem erfindungsgemäßen spezifischen Bindemittel und dem Vernetzungsmittel durch in der antistatischen Schicht zusätzlich enthaltenes Natriummagnesiumsili­kat des Montmorillonittyps erhöht.According to a preferred embodiment of the invention, a terpolymer of styrene, C₁-C₄-alkyl acrylate and 10% methacrylic acid is provided as a binder. According to a further preferred embodiment of the invention, the effectiveness of the combination of the specific binder according to the invention and the crosslinking agent is increased by sodium magnesium silicate of the montmorillonite type additionally contained in the antistatic layer.

Die Mengenverhältnisse der Komponenten sind jeweils bezogen auf die trockene Schicht folgende:
kolloidale Kieselsäure:      23 - 70 Gew.%
Alkalisalz der Polysäure:      3 - 30 Gew.%
Polymer-Binder:      30 - 70 Gew.%
Montmorillonit:      0 - 30 Gew:%
Aziridin:      2 - 18 Gew.%The proportions of the components are based on the dry layer as follows:
colloidal silica: 23 - 70% by weight
Alkaline salt of polyacid: 3 - 30% by weight
Polymer binder: 30 - 70% by weight
Montmorillonite: 0 - 30 wt:%
Aziridine: 2-18% by weight

Der Schichtauftrag (trocken) liegt bei 0,2 - 1,0 g/m², insbesondere 0,2 - 0,5 g/m².The layer application (dry) is 0.2 - 1.0 g / m², in particular 0.2 - 0.5 g / m².

Die Herstellung des erfindungsgemäßen Trägermaterials für fotografische Schichten erfolgt insbesondere in der Weise, daß man die Einzelkomponenten in der Reihen­folge Wasser-Alkohol-Gemisch, Montmorillonit, Kolloi­dale, aluminiummodifizierte Kieseläure, Copolymerdis­persion, Alkalisalz der organischen Polysäure, Aziridin langsam unter Rühren vermischt, den gewünschten pH-Wert mit Ammoniaklösung einstellt, die so erhaltene Gießlö­sung in der gewünschten Schichtdicke aufträgt und anschließend trocknet.The support material for photographic layers according to the invention is produced in particular by slowly mixing the individual components in the sequence water-alcohol mixture, montmorillonite, colloidals, aluminum-modified silica, copolymer dispersion, alkali salt of organic polyacid, aziridine, the desired pH - Sets the value with ammonia solution, applies the casting solution thus obtained in the desired layer thickness and then dries.

Die Prüfung der antistatischen Eigenschaften erfolgt durch Messung des Oberflächenwiderstands mit einer Elektrode nach DIN 53482.The antistatic properties are tested by measuring the surface resistance with an electrode according to DIN 53482.

Zur Prüfung der Bedruckbarkeit und der Abrieb­und Bäderfestigkeit werden Muster mit handelsüblichen Farbbändern bedruckt. Zur Prüfung der Muster auf chemische und mechanische Beanspruchungen, wie sie während des Entwicklungsvorganges auftreten, wurden die Muster nach dem Bedrucken 30 sec in einen handelsüblichen Entwickler getaucht und mit Wasser kurz abgespült. Anschließend werden mit dem Finger Friktionen auf die bedruckte Rückseite ausgeübt. Es wird geprüft, ob dabei der Druck verwischt wird oder Verfärbungen durch Auswaschen einer Farbkomponente der Druckfarbe auftreten. Ein nach Entwicklerbad und Friktion verwischter Druck ist entweder auf schlechte Haftung des Drucks auf der Rückseite des fotografischen Materials oder auf geringe Abriebfestigkeit der rückseitigen Beschichtung zurückzuführen. Letztere, also Beschädigungen durch Abrieb der rückseitigen Oberfläche lassen sich bei Betrachtung im Gegenlicht erkennen.To test the printability and the abrasion and bath resistance, samples are printed with standard color ribbons. To test the samples for chemical and mechanical stresses, as they occur during the development process, the samples were printed in a 30 sec commercial developer dipped and rinsed briefly with water. Then you apply finger friction to the printed back. It is checked whether the print is blurred or whether discoloration occurs due to the washing out of a color component of the printing ink. A print smeared after developer bath and friction is either due to poor adhesion of the print on the back of the photographic material or to low abrasion resistance of the back coating. The latter, i.e. damage due to abrasion of the back surface, can be seen when viewed against the light.

Zur Überprüfung der Klebebandhaftung wird das Muster mit einem handelsüblichen Klebeband (z.B. 3 M-Klebe­band 8422) versehen und dieses mit einem definierten Gewicht (8 kg-Rolle) fixiert. Anschließend wird das Muster in 1,5 cm breite Streifen geschnitten und das Klebeband teilweise abgezogen. Die so präparierte Probe wird in einen Bruchlasttester eingespannt, in dem das Klebeband von der Unterlage in einem Winkel von 180° mit einer Geschwindigkeit von 20 cm/min abgezogen wird. Die zum Abziehen benötigte Kraft wird gemessen. Da die Klebebandhaftung auch bei mechanischer Beanspruchung in Entwicklungslösungen ausreichend sein muß, wird vor dem Abziehen des Klebebands ein Tropfen Wasser auf die Grenze zwischen dem fotografischen Material und dem Klebeband gegeben.To check the adhesive tape adhesion, the sample is provided with a commercially available adhesive tape (eg 3 M adhesive tape 8422) and this is fixed with a defined weight (8 kg roll). Then the pattern is cut into 1.5 cm wide strips and the adhesive tape is partially peeled off. The sample prepared in this way is clamped in a breaking load tester in which the adhesive tape is removed from the base at an angle of 180 ° at a speed of 20 cm / min. The force required to pull off is measured. Since the adhesive tape adhesion must be sufficient even under mechanical stress in developing solutions, a drop of water is placed on the boundary between the photographic material and the adhesive tape before the adhesive tape is peeled off.

Zur Prüfung der Schmutzaufnahmefähigkeit wird ein handelsüblicher Color-Entwickler mit einer Füllhöhe von ca. 2 cm in eine offene Schale gefüllt und über eine Woche an der Luft stehen gelassen. Nach dieser Zeit hat sich an der Oberfläche eine dunkle Teerschicht aus Oxydationsprodukten gebildet. Diese teerartige Oberfläche wird mit dem zu prüfenden Muster abgezogen. Anschließend wird das Muster unter fließendem Wasser abgewaschen und an der Luft getrocknet. Das Ausmaß der Schmutzaufnahme läßt sich durch die Verfärbung auf der Rückseite visuell gut beurteilen.To check the dirt absorption capacity, a commercially available color developer with a filling height of approx. 2 cm is placed in an open bowl and left in the air for a week. After this time, a dark tar layer of oxidation products formed on the surface. This tar-like surface is peeled off with the sample to be tested. The pattern is then washed under running water and air dried. The degree of dirt pick-up can be assessed visually by the discoloration on the back.

Die nachfolgende Tabelle 1 enthält beispielhaft Zu­sammensetzungen von Mischungen für erfindungsgemäße antistatische Schichten. Die zugehörigen Prüfwerte sind in Tabelle 2 enthalten.

Figure imgb0001
Figure imgb0002
 Table 1 below contains examples of compositions of mixtures for antistatic layers according to the invention. The associated test values are contained in Table 2.
Figure imgb0001
Figure imgb0002

Claims (8)

1. Trägermateial für fotografische Schichten mit antistatischem Rückseitenstrich, dadurch gekennzeichnet, daß der Rückseitenstrich we­nigstens die folgenden Komponenten enthält: a) Eine kolloidale aluminiummodifizierte Kiesel­säure b) Ein Alkalisalz einer organischen Polysäure c) Eine wässrige Dispersion von Copolymeren von Acrylsäurealkylester mit einem Gehalt an freien Carboxylgruppen von 1 - 10 Mol-% und an freien Hydroxylgruppen von 0 - 20 Mol-% d) Ein trifunktionelles Aziridin als Vernetzungs­mittel. 1. Backing material for photographic layers with an antistatic backside coating, characterized in that the backing coating contains at least the following components: a) A colloidal aluminum-modified silica b) An alkali salt of an organic polyacid c) An aqueous dispersion of copolymers of acrylic acid alkyl ester with a free carboxyl group content of 1-10 mol% and free hydroxyl groups of 0-20 mol% d) A trifunctional aziridine as a crosslinking agent. 2. Fotografisches Trägermaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Summe der polaren Gruppen in c) 25 Mol-% nicht überschreitet.2. Photographic support material according to claim 1, characterized in that the sum of the polar groups in c) does not exceed 25 mol%. 3. Fotografisches Trägermaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Copolymer ein Terpolymeres aus Styrol, C₁-C₄-Alkylacrylat und 10 % Methacrylsäure ist.3. Photographic support material according to claim 1 or 2, characterized in that the copolymer is a terpolymer of styrene, C₁-C₄ alkyl acrylate and 10% methacrylic acid. 4. Fotografisches Trägermaterial nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die antistatische Schicht zusätzlich ein Natriummagnesium­silikat des Montmorillonittyps enthält.4. Photographic support material according to one of claims 1 to 3, characterized in that the antistatic layer additionally contains a sodium magnesium silicate of the montmorillonite type. 5. Fotografisches Trägermaterial nach Anspruch 1, da­durch gekennzeichnet, daß das Alkalisalz einer or­ganischen Polysäure ein Alkalisalz von Polystyrol­sulfonsäure oder Naphthalinsulfonsäure oder ein Alkalicellulosesulfat ist.5. Photographic support material according to claim 1, characterized in that the alkali salt of an organic polyacid is an alkali salt of polystyrene sulfonic acid or naphthalenesulfonic acid or an alkali cellulose sulfate. 6. Fotografisches Trägermaterial nach Anspruch 1, dadurch gekennzeichnet, daß das Trägermaterial ein polyolefinbeschichtetes Papier ist.6. Photographic support material according to claim 1, characterized in that the support material is a polyolefin-coated paper. 7. Fotografisches Trägermaterial nach einem der An­sprüche 1 bis 6, gekennzeichnet durch folgende Mengenverhältnisse der Komponenten jeweils be­zogen auf die trockene Schicht:
kolloidale Kieselsäure:      23 - 70 Gew.%
Alkalisalz der Polysäure:      3 - 30 Gew.%
Polymer-Binder:      30 - 70 Gew.%
Montmorillonit:      0 - 30 Gew:%
Aziridin:      2 - 18 Gew.%7. Photographic support material according to one of claims 1 to 6, characterized by the following quantitative ratios of the components, in each case based on the dry layer:
colloidal silica: 23 - 70% by weight
Alkaline salt of polyacid: 3 - 30% by weight
Polymer binder: 30 - 70% by weight
Montmorillonite: 0 - 30 wt:%
Aziridine: 2-18% by weight 8. Verfahren zur Herstellung eines Trägermaterials für fotografische Schichten nach einem der An­sprüche 1 bis 7, dadurch gekennzeichnet, daß man die Einzelkomponenten in der Reihenfolge Lösungsmitttel-Gemisch, Montmorillonit, kolloi­dale, aluminiummodifizierte Kieselsäure, Copoly­merdispersion, Alkalisalz der organischen Poly­säure, Aziridin langsam unter Rühren vermischt, den gewünschten pH-Wert mit Ammoniaklösung ein­stellt, die so erhaltene Gießlösung in der ge­wünschten Schichtdicke aufträgt und anschließend trocknet.8. A method for producing a support material for photographic layers according to one of claims 1 to 7, characterized in that slowly adding the individual components in the order solvent mixture, montmorillonite, colloidal, aluminum-modified silica, copolymer dispersion, alkali metal salt of organic polyacid, aziridine mixed, adjusted the desired pH with ammonia solution, applied the casting solution thus obtained in the desired layer thickness and then dried.
EP87116068A 1987-01-06 1987-10-31 Antistatic photographic support material Expired - Lifetime EP0274017B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87116068T ATE78938T1 (en) 1987-01-06 1987-10-31 ANTISTATIC PHOTOGRAPHIC SUPPORT.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3700183 1987-01-06
DE19873700183 DE3700183A1 (en) 1987-01-06 1987-01-06 ANTISTATIC PHOTOGRAPHIC CARRIER MATERIAL

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EP0274017A2 true EP0274017A2 (en) 1988-07-13
EP0274017A3 EP0274017A3 (en) 1990-02-28
EP0274017B1 EP0274017B1 (en) 1992-07-29

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US (1) US5104779A (en)
EP (1) EP0274017B1 (en)
JP (1) JPS63173044A (en)
AT (1) ATE78938T1 (en)
DE (2) DE3700183A1 (en)
ES (1) ES2033285T3 (en)
GR (2) GR920300032T1 (en)

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EP0430110A2 (en) * 1989-11-29 1991-06-05 Konica Corporation Method for providing antistatic layer
WO1991008513A2 (en) * 1989-12-05 1991-06-13 Eastman Kodak Company Print retaining coatings and coating compositions for the preparation thereof
EP0438621A1 (en) * 1987-10-23 1991-07-31 Felix Schoeller jr. Papierfabrik GmbH & Co. KG Backing layer composition for photographic support
DE4101475A1 (en) * 1991-01-19 1992-07-23 Schoeller F Jun Gmbh Co Kg COATING COMPOSITION FOR THE BACK PAGE OF PHOTOGRAPHIC SUPPORT MATERIALS AND METHOD FOR THE PRODUCTION THEREOF
AU628250B2 (en) * 1990-01-26 1992-09-10 E.I. Du Pont De Nemours And Company Element having improved adhesion of auxiliary layers to film supports containing antistatic layers
WO1992017817A1 (en) * 1991-03-28 1992-10-15 E.I. Du Pont De Nemours And Company Antistatic antihalation backing layer with improved properties
US5221555A (en) * 1991-12-12 1993-06-22 Felix Schoeller, Jr. Gmbh & Co. Kg Reverse side coating of photographic support materials
EP0616252A2 (en) * 1993-03-16 1994-09-21 FELIX SCHOELLER JR. FOTO- UND SPEZIALPAPIERE GmbH &amp; Co. KG. Photographic support
EP0697620A1 (en) * 1994-08-16 1996-02-21 FELIX SCHOELLER JR. FOTO- UND SPEZIALPAPIERE GmbH &amp; Co. KG. Photographic support material comprising a back-side coating
WO1996037551A1 (en) * 1995-05-26 1996-11-28 Siew Puat Yeo Two-component polymer composition

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EP0466982B1 (en) * 1990-07-20 1995-04-12 Agfa-Gevaert N.V. Method for preparing solvent-resistant polymer beads
JP2739393B2 (en) * 1991-07-09 1998-04-15 富士写真フイルム株式会社 Silver halide photographic material
US5589324A (en) * 1993-07-13 1996-12-31 International Paper Company Antistatic layer for photographic elements comprising polymerized polyfunctional aziridine monomers
US5491013A (en) * 1994-08-31 1996-02-13 Rexam Industries Corp. Static-dissipating adhesive tape
US5723276A (en) * 1996-09-11 1998-03-03 Eastman Kodak Company Coating compositions for photographic paper
FR2760754B1 (en) * 1997-03-12 2003-06-06 Kodak Pathe ANTISTATIC COMPOSITION AND PHOTOGRAPHIC PRODUCT CONTAINING A LAYER OF THIS COMPOSITION
US5849472A (en) * 1997-03-13 1998-12-15 Eastman Kodak Company Imaging element comprising an improved electrically-conductive layer
US5955190A (en) * 1997-09-29 1999-09-21 Eastman Kodak Company Antistatic layer for photographic paper
US5981126A (en) * 1997-09-29 1999-11-09 Eastman Kodak Company Clay containing electrically-conductive layer for imaging elements
US5891611A (en) * 1997-09-29 1999-04-06 Eastman Kodak Company Clay containing antistatic layer for photographic paper
GB2449306A (en) * 2007-05-18 2008-11-19 Univ Sheffield Composite particles
TW202213835A (en) * 2020-06-26 2022-04-01 美國芝加哥洛約拉大學 Surface-modified electron transport layer of organic light-emitting diode

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Cited By (15)

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US5232824A (en) * 1987-10-23 1993-08-03 Felix Schoeller Jr. Gmbh & Co. K.G. Coating mass for the back of photographic support materials
EP0438621A1 (en) * 1987-10-23 1991-07-31 Felix Schoeller jr. Papierfabrik GmbH & Co. KG Backing layer composition for photographic support
EP0430110A3 (en) * 1989-11-29 1991-07-24 Konica Corporation Method for providing antistatic layer
EP0430110A2 (en) * 1989-11-29 1991-06-05 Konica Corporation Method for providing antistatic layer
WO1991008513A3 (en) * 1989-12-05 1991-08-08 Eastman Kodak Co Print retaining coatings and coating compositions for the preparation thereof
WO1991008513A2 (en) * 1989-12-05 1991-06-13 Eastman Kodak Company Print retaining coatings and coating compositions for the preparation thereof
AU628250B2 (en) * 1990-01-26 1992-09-10 E.I. Du Pont De Nemours And Company Element having improved adhesion of auxiliary layers to film supports containing antistatic layers
US5318886A (en) * 1991-01-19 1994-06-07 Felix Schoeller, Jr. Gmbh & Co. Reverse side coating of photographic support materials
DE4101475A1 (en) * 1991-01-19 1992-07-23 Schoeller F Jun Gmbh Co Kg COATING COMPOSITION FOR THE BACK PAGE OF PHOTOGRAPHIC SUPPORT MATERIALS AND METHOD FOR THE PRODUCTION THEREOF
WO1992017817A1 (en) * 1991-03-28 1992-10-15 E.I. Du Pont De Nemours And Company Antistatic antihalation backing layer with improved properties
US5221555A (en) * 1991-12-12 1993-06-22 Felix Schoeller, Jr. Gmbh & Co. Kg Reverse side coating of photographic support materials
EP0616252A2 (en) * 1993-03-16 1994-09-21 FELIX SCHOELLER JR. FOTO- UND SPEZIALPAPIERE GmbH &amp; Co. KG. Photographic support
EP0616252A3 (en) * 1993-03-16 1995-08-02 Schoeller Felix Jun Foto Photographic support.
EP0697620A1 (en) * 1994-08-16 1996-02-21 FELIX SCHOELLER JR. FOTO- UND SPEZIALPAPIERE GmbH &amp; Co. KG. Photographic support material comprising a back-side coating
WO1996037551A1 (en) * 1995-05-26 1996-11-28 Siew Puat Yeo Two-component polymer composition

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ES2033285T3 (en) 1993-03-16
GR3005814T3 (en) 1993-06-07
GR920300032T1 (en) 1992-09-11
EP0274017B1 (en) 1992-07-29
DE3780791D1 (en) 1992-09-03
US5104779A (en) 1992-04-14
EP0274017A3 (en) 1990-02-28
ATE78938T1 (en) 1992-08-15
JPS63173044A (en) 1988-07-16
DE3700183A1 (en) 1988-07-14

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