EP0312638A1 - Photographic support material for light-sensitive layers in the form of a plastic-coated paper or a plastic sheet with a writable antistatic back-layer coating - Google Patents

Photographic support material for light-sensitive layers in the form of a plastic-coated paper or a plastic sheet with a writable antistatic back-layer coating Download PDF

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Publication number
EP0312638A1
EP0312638A1 EP19870115556 EP87115556A EP0312638A1 EP 0312638 A1 EP0312638 A1 EP 0312638A1 EP 19870115556 EP19870115556 EP 19870115556 EP 87115556 A EP87115556 A EP 87115556A EP 0312638 A1 EP0312638 A1 EP 0312638A1
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EP
European Patent Office
Prior art keywords
weight
support material
plastic
butadiene
styrene
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
EP19870115556
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German (de)
French (fr)
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EP0312638B1 (en
Inventor
Eckehard Säverin
Hans-Udo Tyrakowski
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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 EP87115556A priority Critical patent/EP0312638B1/en
Priority to ES198787115556T priority patent/ES2037056T3/en
Priority to AT87115556T priority patent/ATE84885T1/en
Priority to DE8787115556T priority patent/DE3783768D1/en
Publication of EP0312638A1 publication Critical patent/EP0312638A1/en
Application granted granted Critical
Publication of EP0312638B1 publication Critical patent/EP0312638B1/en
Priority to GR920300114T priority patent/GR920300114T1/el
Priority to GR930400642T priority patent/GR3007455T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • 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
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

  • the invention relates to a photographic support material for light-sensitive layers in the form of a plastic-coated paper or in the form of a plastic film with a writable antistatic back coating.
  • the paper support normally consists of a wet-strength glued cellulose paper with a so-called baryta layer applied on one side and the light-sensitive emulsion above.
  • the polyolefins now also have properties which are disadvantageous for the production or treatment of such papers.
  • this plastic coating must fulfill certain properties in the course of the production and development of such photographic papers, or it must have properties that these plastics inherently have possess, be suppressed or completely eliminated.
  • the coated photographic material as it passes through the various treatment baths, such as developing and fixing baths, does not pick up and retain any dirt particles on its surface which can form in these photographic treatment baths through oxidation and condensation processes over time.
  • the adhesive tapes serve, among other things, to fasten the photographic papers present in the form of coiled long strips to one another in order to ensure a smooth passage through the processing machine and, finally, in all of this, the antistatic charging of such a hydrophobic coating of the photographic support material is to be prevented, if possible, because the When the plastic-coated photographic support material is unwound and passed through the emulsion casting machines and when the batch is taken off after development, an electrostatic charge takes place, which is discharged when the device reaches a certain value or at appropriate points, which naturally leads to the unusability of the light-sensitive emulsion or can lead to the destruction of the latent image to be developed.
  • Hydrophobic components have the disadvantage of high dirt absorption and low antistatic activity, but strong electrostatic chargeability, while hydrophilic components adversely affect adhesive tape adhesion, are poorly printable and easily detach or swell in the treatment baths.
  • polar surfaces show good conductivity, that is to say antistatic properties, and low dirt absorption, but with increasing polarity, that is to say good antistatic properties, the abrasion resistance and adhesive tape adhesion are in turn adversely affected by the action of the baths.
  • the terpolymer of styrene-butadiene-methacrylate in aqueous suspension with a solids content of preferably 30 to 55% by weight is a latex which specifically fulfills optimal printability, adhesive tape adhesion and minimal soiling (tar stain) of the backing coat of the base paper causes. It is an important ingredient in the recipe because it maintains a balance between non-polar properties, which is important for optimal printability and tape adhesion results, and polar properties, which is important for tar stain reduction.
  • the amount that is added to the back coat should be selected so that the coat retains its strength and invulnerability during treatment in the baths, and on the other hand is only so large that the formulation does not lose its stability. These amounts are between 10 and 30% by weight, based on the total mixture.
  • the monomer ratio of the terpolymer made from styrene-butadiene-methacrylate is in the following ranges: 50-70% by weight styrene 25-40% by weight of butadiene and 5 - 15% by weight methacrylate the polymer being free of carboxyl and hydroxyl groups.
  • the silica with a particle size of 3 to 6 ⁇ m is responsible for being writable with lead.
  • the amount can vary both depending on the pencil hardness used and depending on the other constituents and also on the type of plastic of the back coating. It is preferably between 0.1 and 3.0% by weight solids content, based on the total mixture.
  • the effect is achieved with quantities of 0.1% by weight. If the solids content is above 3.0% by weight, the bond with the binder, which, as already indicated here, becomes the latex is weakened, so that the effect is no longer satisfactory overall.
  • the aluminum-modified colloidal silica sol a sol using water, usually contains 30% by weight solids and is self-binding when dried by condensation of the hydroxyl groups. This connection promotes the printability of the backside coating and contributes to the antistatic finish.
  • the amount used is between 2 and 25% by weight.
  • the component d namely the aqueous solution of the alkali salt of an organic polyacid, is a substance which produces the actual antistatic effect; alkali salts of organic polysulfonic acids are preferably used.
  • alkali salts of organic polysulfonic acids are preferably used.
  • good to very good electrical surface conductivity is achieved both before and after the bath.
  • the prevention of the discoloration in the baths is achieved in particular by the latex and is good to very good in the sense according to the invention.
  • a universally applicable mixture can be composed as follows:
  • Fig. 1 shows strips of photographic base papers with backsheets, in which the product according to the invention is compared with the backside coated photographic base papers listed on the market listed in Table 1. It can be seen that the product according to the invention has very good properties for preventing dirt (tar stain) on the back.
  • the mixture according to the invention is applied to the paper in such an amount that a layer is applied which, when dried, is 0.15 to 1.3 g / m2, but in particular is between 0.2 and 0.6 g / m2.
  • the test of the printability and the abrasion resistance or bath strength was carried out on the basis of samples with standard color ribbons. To test the samples for chemical and mechanical stresses, which can occur during the development process, they were immersed in developer for 30 seconds, wiped with a finger and, after rinsing with water, checked to see whether blurring or discolouration had occurred due to the washing out of a color component. The abrasion resistance was determined by rubbing the finger harder.
  • the test of the adhesive tape adhesive strength was carried out on samples with a commercially available adhesive tape, for example a 3M adhesive tape 8422.
  • the adhesive tape was pressed on and loaded with a weight of 3 kg.
  • the sample was then cut into 1.5 cm wide strips and the adhesive tape of each sample was clamped in a breaking load tester, in which the adhesive tape was removed from the base at an angle of 180 ° at a speed of 20 cm / min. is subtracted. The force required to pull off is measured.

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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)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paper (AREA)

Abstract

The back-layer coating is composed of a terpolymer latex of styrene/butadiene/methacrylate, a hard silica and an aqueous solution of the sodium salt of an organic polybasic acid. The quantities of these substances are selected such that optimum results are obtained with respect to imprintability, inscribability with pencils, low fouling in spent developer baths, low discoloration in the developer, good gluing adhesion and antistatic properties.

Description

Die Erfindung betrifft ein fotografisches Trägermaterial für lichtempfindliche Schichten in Form eines kunststoffbe­schichteten Papiers oder in Form einer Kunststoffolie mit einer beschreibbaren antistatischen Rückseitenbeschichtung.The invention relates to a photographic support material for light-sensitive layers in the form of a plastic-coated paper or in the form of a plastic film with a writable antistatic back coating.

Im Gegensatz zu den früheren barytbeschichteten foto­grafischen Papieren werden in neuerer Zeit als Träger für die lichtempfindlichen Schichten, insbesondere für die lichtempfind­lichen Schichten für die Farbfotografie, Papiere verwendet, die auf ihren Oberflächen, d. h. Vorderseite und Rückseite, mit Polyolefinen beschichtet sind. Die Beschichtung erfolgt vor­zugsweise unter Verwendung von Polyethylen, welches durch Schmelzextrusion über eine Breitschlitzdüse auf die Papier­oberflächen aufextrudiert ist. Ein solcher fotografischer Träger ist beispielsweise beschrieben in der DE-PS 23 44 367.In contrast to the previous barite-coated photographic papers, papers which have been coated on their surfaces, i.e., on the surfaces thereof, in particular for the photosensitive layers for color photography, have recently been used. H. Front and back, coated with polyolefins. The coating is preferably carried out using polyethylene, which is extruded onto the paper surfaces by melt extrusion via a slot die. Such a photographic support is described for example in DE-PS 23 44 367.

Bei den klassischen fotografischen Papieren besteht der Papierträger normalerweise aus einem naßfesten geleimten Zell­stoffpapier mit einer einseitig aufgebrachten sogenannten Barytschicht und der darüber befindlichen lichtempfindlichen Emulsion.In the case of classic photographic papers, the paper support normally consists of a wet-strength glued cellulose paper with a so-called baryta layer applied on one side and the light-sensitive emulsion above.

Nach der Belichtung werden die Papiere entwickelt, fixiert und gewässert und anschließend getrocknet. Für diesen Vorgang ist ein großer Zeitaufwand erforderlich. Aus Gründen der Rationalisierung der Bildentwicklung ging man daher von den klassischen Fotopapieren ab und kam zur Einführung der wasserfesten Papiere, die auf beiden Seiten mit thermopla­ stischen Kunststoffschichten, insbesondere Polyolefinschich­ten, überzogen sind und so den Papierkern flächig gegen das Eindringen von Entwicklungs-, Fixier- und Wässerungsbädern schützen.After exposure, the papers are developed, fixed and watered and then dried. This process takes a lot of time. For reasons of the rationalization of image development, the classic photo papers were therefore abandoned and the introduction of waterproof papers came with thermopla on both sides Plastic plastic layers, in particular polyolefin layers, are coated and thus protect the paper core flat against the penetration of development, fixing and washing baths.

Die Polyolefine haben nun aber auch Eigenschaften, die für die Herstellung bzw. für die Behandlung solcher Papiere nachteilig sind. Abgesehen von den Haftungsproblemen zwischen der Polyolefinoberfläche und den lichtempfindlichen Emulsionen, die durch zusätzliche Maßnahmen und Mittel behebbar sind, muß diese Kunststoffbeschichtung bestimmte Eigenschaften im Laufe der Herstellung und der Entwicklung derartiger fotografischer Papiere erfüllen, bzw. es müssen Eigenschaften, die diese Kunststoffe von Haus aus besitzen, unterdrückt oder völlig eliminiert werden.However, the polyolefins now also have properties which are disadvantageous for the production or treatment of such papers. Apart from the adhesion problems between the polyolefin surface and the light-sensitive emulsions, which can be remedied by additional measures and means, this plastic coating must fulfill certain properties in the course of the production and development of such photographic papers, or it must have properties that these plastics inherently have possess, be suppressed or completely eliminated.

So ist es z. B. notwendig, daß die zu entwickelnden fotografischen Materialien auf derartigen Trägern auf der Rückseite durch Beschreiben oder Bedrucken zu kennzeichnen sind, damit sie bestimmten Auftraggebern und Kunden zuge­ordnet werden können. Die aus einem thermoplastischen Kunst­stoff bestehende, den Papierkern abdichtende hydrophobe Be­schichtung läßt sich aber so wie sie ist nicht beschreiben oder kennzeichnen. Es sind spezielle Maßnahmen und Mittel erforderlich, damit die notwendige Bedruck- oder Beschreib­barkeit bei der maschinellen Verarbeitung des blattförmigen fotografischen Materials ermöglicht wird. Solche Vorschläge sind beispielsweise beschrieben in der europäischen Patent­anmeldung 0 160 912.So it is z. B. necessary that the photographic materials to be developed on such supports are to be labeled on the back by writing or printing so that they can be assigned to specific clients and customers. However, the hydrophobic coating consisting of a thermoplastic and sealing the paper core cannot be described or labeled as it is. Special measures and means are necessary so that the necessary printability or writeability is made possible in the mechanical processing of the sheet-like photographic material. Such proposals are described, for example, in European patent application 0 160 912.

Es ist ferner erforderlich, daß das beschichtete foto­grafische Material beim Durchgang durch die verschiedenen Behandlungsbäder, wie Entwicklungs- und Fixierbäder, keine Schmutzteilchen auf seiner Oberfläche aufnimmt und festhält, die sich in diesen fotografischen Behandlungsbädern durch Oxidation und Kondensationsvorgänge im Laufe der Zeit bilden können.It is also necessary that the coated photographic material, as it passes through the various treatment baths, such as developing and fixing baths, does not pick up and retain any dirt particles on its surface which can form in these photographic treatment baths through oxidation and condensation processes over time.

Ferner ist es erforderlich zu verhindern, daß die Ent­wicklerlösung oder -bäder durch die Mittel, die Beschreib­barkeit, Bedruckbarkeit und dgl. wünschenswerte Eigenschaften bewirken, verunreinigt oder verfärbt werden.Furthermore, it is necessary to prevent the developer solution or baths from being contaminated or discolored by the agents having writability, printability and the like.

Eine andere Notwendigkeit bei der Herstellung eines derartigen fotografischen Trägermaterials ist eine Ausbildung der Beschichtung, die eine gute Haftung von Klebebändern sicher­stellt. Die Klebebänder dienen u. a. zur Befestigung der in Form von aufgewickelten langen Streifen vorliegenden fotografischen Papiere aneinander, um einen glatten Durchlauf durch die Ent­wicklungsmaschine zu gewährleisten und schließlich soll bei all dem möglichst noch die antistatische Aufladung einer solchen hydrophoben Beschichtung des fotografischen Träger­materials verhindert werden, denn beim Abwickeln und beim Durch­gang des kunststoffbeschichteten fotografischen Trägermaterials durch die Emulsionsgießmaschinen und beim Stapelabzug nach der Entwicklung findet eine elektrostatische Aufladung statt, die sich beim Erreichen eines bestimmten Wertes oder an entsprech­enden Stellen an den Einrichtungen unter Blitzbildung entlädt, was natürlich zur Unbrauchbarkeit der lichtempfindlichen Emul­sion bzw. zur Zerstörung des zu entwickelnden latenten Bildes führen kann.Another necessity in the production of such a photographic support material is the formation of the coating, which ensures good adhesion of adhesive tapes. The adhesive tapes serve, among other things, to fasten the photographic papers present in the form of coiled long strips to one another in order to ensure a smooth passage through the processing machine and, finally, in all of this, the antistatic charging of such a hydrophobic coating of the photographic support material is to be prevented, if possible, because the When the plastic-coated photographic support material is unwound and passed through the emulsion casting machines and when the batch is taken off after development, an electrostatic charge takes place, which is discharged when the device reaches a certain value or at appropriate points, which naturally leads to the unusability of the light-sensitive emulsion or can lead to the destruction of the latent image to be developed.

All diese Eigenschaften sind bekannt. Es war bisher schwierig, sie insgesamt zu verwirklichen, weil die zur Lösung angebotenen Maßnahmen und Mittel einander oft wider­sprechen. So ist es z. B. bekannt, aus der oben zitierten europäischen Patentanmeldung 0 160 912, ein solches mit Polyethylen beschichtetes fotografisches Material auf seiner Rückseite mit einer antistatischen Schicht zu versehen, die aus einem Natrium-Magnesium-Silikat, einem Natriumpoly­styrolsulfonat und bestimmten Bernsteinsäurehalbestern besteht. Diese Beschichtung soll die elektrostatische Aufladung ver­hindern und außerdem das Material gegen Schmutzaufnahme schützen.All of these properties are known. It has so far been difficult to achieve them as a whole because the measures and means offered to solve them often contradict each other. So it is z. B. known from the above-cited European patent application 0 160 912 to provide such a polyethylene-coated photographic material on its back with an antistatic layer consisting of a sodium-magnesium-silicate, a sodium polystyrene sulfonate and certain succinic acid half-esters. This coating is intended to prevent electrostatic charging and also to protect the material from dirt.

Hydrophobe Komponenten haben den Nachteil einer hohen Schmutzaufnahme und geringer antistatischer Wirksamkeit aber starke elektrostatische Aufladbarkeit, während hydrophile Komponenten die Klebebandhaftung nachteilig beeinflussen, schlecht bedruckbar sind und in den Behandlungsbädern sich leicht ablösen oder aufquellen.Hydrophobic components have the disadvantage of high dirt absorption and low antistatic activity, but strong electrostatic chargeability, while hydrophilic components adversely affect adhesive tape adhesion, are poorly printable and easily detach or swell in the treatment baths.

Andererseits zeigen polare Oberflächen gute Leitfähig­keit, also antistatische Eigenschaften, und eine geringe Schmutz­aufnahme, aber mit zunehmender Polarität, also guten anti­statischen Eigenschaften, wird wiederum die Abriebfestigkeit und die Klebebandhaftung durch die Einwirkung der Bäder nach­teilig beeinflußt.On the other hand, polar surfaces show good conductivity, that is to say antistatic properties, and low dirt absorption, but with increasing polarity, that is to say good antistatic properties, the abrasion resistance and adhesive tape adhesion are in turn adversely affected by the action of the baths.

Es ist daher Aufgabe der vorliegenden Erfindung, bei einem fotografischen Trägermaterial der eingangs beschriebenen Art eine Rückseitenbeschichtung bzw. einen Rückseitenstrich vorzuschlagen, der in optimaler Weise all den oben aufgeführten Forderungen nach Bedruckbarkeit mit den auf dem Markt befind­lichen Druckbändern, einer Beschreibbarkeit mit Bleistift, möglichst geringer Schmutzaufnahme, einer Verhinderung der Verfärbung der Rückseite im Colorentwickler, einer guten Klebe­bandhaftung während des Entwicklungsprozesses entspricht sowie ausreichende antistatische Eigenschaften aufweist.It is therefore an object of the present invention to propose a backing coating or a backstroke for a photographic support material of the type described at the outset, which optimally meets all of the above requirements for printability with the printing tapes on the market, writeability with pencil, the lowest possible dirt absorption, prevention of discoloration of the back in the color developer, good adhesive tape adhesion during the development process and sufficient antistatic properties.

Erreicht wird das durch einen Rückseitenstrich folgen­der Zusammensetzung:

  • a) Ein Terpolymer-Latex aus Styrol-Butadien-­Methacrylat,
  • b) Kieselsäure (SiO₂) mit einer Teilchengröße von 3 bis 6 µm,
  • c) ein aluminiummodifiziertes kolloidales Kiesel­säuresol sowie
  • d) eine wäßrige Lösung eines Salzes einer organischen Polysäure sowie Wasser,
wobei die Mengen der Stoffe a) bis d) so getroffen sind, daß optimale Bedruckbarkeit mit Bändern, Beschreibbarkeit mit Blei­stiften, geringste Verschmutzung in alten oxidierten Entwick­lungsbädern, geringste Verfärbung im Colorentwickler, optimale Klebebandhaftung und antistatische Eigenschaften erhalten wer­den.This is achieved by a back stroke of the following composition:
  • a) a terpolymer latex made of styrene-butadiene-methacrylate,
  • b) silica (SiO₂) with a particle size of 3 to 6 µm,
  • c) an aluminum-modified colloidal silica sol and
  • d) an aqueous solution of a salt of an organic polyacid and water,
the quantities of substances a) to d) are such that optimum printability with tapes, writeability with pencils, minimal contamination in old oxidized development baths, minimal discoloration in the color developer, optimal adhesive tape adhesion and antistatic properties are obtained.

Das Terpolymer aus Styrol-Butadien-Methacrylat in wäß­riger Suspension mit einem Festkörpergehalt von vorzugsweise 30 bis 55 Gew.-% ist ein Latex, der speziell die Erfüllung optimaler Bedruckbarkeit, Klebebandhaftung und minimaler Ver­schmutzung (Tar Stain) des Rückseitenstriches des Basispapiers bewirkt. Er ist der wichtige Bestandteil in der Rezeptur, da er zwischen unpolaren Eigenschaften, was für optimale Ergeb­nisse bei Bedruckbarkeit und Klebebandhaftung wichtig ist, und polaren Eigenschaften, was für Tar Stain-Reduzierung wichtig ist, die Balance hält. Die Menge, die dem Rückseitenstrich zugemischt wird, ist so zu wählen, daß der Strich noch seine Festigkeit und Unangreifbarkeit bei der Behandlung in den Bädern behält und andererseits nur so groß ist, daß die Rezeptur nicht ihre Stabilität verliert. Diese Mengen liegen zwischen 10 und 30 Gew.-%, bezogen auf die Gesamtmischung.The terpolymer of styrene-butadiene-methacrylate in aqueous suspension with a solids content of preferably 30 to 55% by weight is a latex which specifically fulfills optimal printability, adhesive tape adhesion and minimal soiling (tar stain) of the backing coat of the base paper causes. It is an important ingredient in the recipe because it maintains a balance between non-polar properties, which is important for optimal printability and tape adhesion results, and polar properties, which is important for tar stain reduction. The amount that is added to the back coat should be selected so that the coat retains its strength and invulnerability during treatment in the baths, and on the other hand is only so large that the formulation does not lose its stability. These amounts are between 10 and 30% by weight, based on the total mixture.

Das Monomerverhältnis des Terpolymers aus Styrol-Butadien-­Methacrylat liegt in den folgenden Bereichen:
50 - 70 Gew.-% Styrol
25 - 40 Gew.-% Butadien und
5 - 15 Gew.-% Methacrylat
wobei das Polymer frei von Carboxyl- und Hydroxylgruppen ist.The monomer ratio of the terpolymer made from styrene-butadiene-methacrylate is in the following ranges:
50-70% by weight styrene
25-40% by weight of butadiene and
5 - 15% by weight methacrylate
the polymer being free of carboxyl and hydroxyl groups.

Die Kieselsäure mit einer Teilchengröße von 3 bis 6 µm ist zuständig für die Beschreibbarkeit mit Blei. Auch hier kann die Menge sowohl nach verwendeter Bleistifthärte als auch in Abhängigkeit von den anderen Bestandteilen als auch von der Art des Kunststoffes der Rückseitenbeschichtung variieren. Sie liegt vorzugsweise zwischen 0,1 und 3,0 Gew.-% Festkörperge­halt, bezogen auf die Gesamtmischung.The silica with a particle size of 3 to 6 µm is responsible for being writable with lead. Here, too, the amount can vary both depending on the pencil hardness used and depending on the other constituents and also on the type of plastic of the back coating. It is preferably between 0.1 and 3.0% by weight solids content, based on the total mixture.

Die Wirkung wird schon erreicht bei Mengen von 0,1 Gew.-%. Bei oberhalb 3,0 Gew.-% Festkörpergehalt wird der Verbund mit dem Bindemittel, was hier, wie bereits angedeutet, der Latex ist, geschwächt, so daß die Wirkung nicht mehr insgesamt be­friedigend ist.The effect is achieved with quantities of 0.1% by weight. If the solids content is above 3.0% by weight, the bond with the binder, which, as already indicated here, becomes the latex is weakened, so that the effect is no longer satisfactory overall.

Das aluminiummodifizierte kolloidale Kieselsäuresol, ein Sol unter Verwendung von Wasser, enthält üblicherweise 30 Gew.-% Festkörper und ist bei Trocknung selbstbindend durch Kondensation der Hydroxylgruppen. Diese Verbindung fördert die Bedruckbarkeit des Rückseitenstriches und liefert einen Bei­trag zur antistatischen Ausrüstung. Die eingesetzte Menge liegt zwischen 2 und 25 Gew.-%.The aluminum-modified colloidal silica sol, a sol using water, usually contains 30% by weight solids and is self-binding when dried by condensation of the hydroxyl groups. This connection promotes the printability of the backside coating and contributes to the antistatic finish. The amount used is between 2 and 25% by weight.

Der Bestandteil d), nämlich die wäßrige Lösung des Alkali­salzes einer organischen Polysäure ist eine Substanz, die die eigentliche antistatische Wirkung hervorruft, vorzugsweise werden Alkalisalze organischer Polysulfonsäuren verwendet. In Verbindung mit der aluminiummodifizierten kolloidalen Kiesel­säure wird sowohl eine gute bis sehr gute elektrische Ober­flächenleitfähigkeit vor dem Bäderdurchgang als auch nach dem Bäderdurchgang erreicht.The component d), namely the aqueous solution of the alkali salt of an organic polyacid, is a substance which produces the actual antistatic effect; alkali salts of organic polysulfonic acids are preferably used. In conjunction with the aluminum-modified colloidal silica, good to very good electrical surface conductivity is achieved both before and after the bath.

Die Verhinderung der Verfärbung in den Bädern ist ins­besondere durch den Latex erreicht und ist im erfindungsge­mäßen Sinn angewandt gut bis sehr gut.The prevention of the discoloration in the baths is achieved in particular by the latex and is good to very good in the sense according to the invention.

In der beigefügten Tabelle ist ein Vergleich mit ver­schiedenen anderen am Markt befindlichen Rückseitenbeschich­tungen A - E dargestellt, wobei die erfindungsgemäße Beschich­tung gemäß nachfolgender Rezeptur in der letzten vertikalen Spalte aufgetragen ist. Eine universell anwendbare Mischung kann sich wie folgt zusammensetzen:

Figure imgb0001
Figure imgb0002
Figure imgb0003
 The attached table shows a comparison with various other rear-side coatings A-E on the market, the coating according to the invention being applied in the last vertical column in accordance with the following recipe. A universally applicable mixture can be composed as follows:
Figure imgb0001
Figure imgb0002
Figure imgb0003

In Abb. 1 sind Streifen von fotografischen Basispapieren mit Rückseitenstrichen dargestellt, in der das erfindungsge­mäße Produkt mit den in Tabelle 1 aufgeführten am Markt be­findlichen rückseitenbeschichteten fotografischen Basispapieren verglichen ist. Es ist zu erkennen, daß das erfindungsgemäße Produkt sehr gute Eigenschaften zur Verhinderung des Ver­schmutzens (Tar Stain) der Rückseite besitzt.Fig. 1 shows strips of photographic base papers with backsheets, in which the product according to the invention is compared with the backside coated photographic base papers listed on the market listed in Table 1. It can be seen that the product according to the invention has very good properties for preventing dirt (tar stain) on the back.

Die erfindungsgemäße Mischung wird in einer solchen Menge auf das Papier aufgetragen, daß sich ein Schichtauftrag ergibt, der getrocknet 0,15 bis 1,3 g/m² beträgt, insbesondere aber zwischen 0,2 und 0,6 g/m² liegt.The mixture according to the invention is applied to the paper in such an amount that a layer is applied which, when dried, is 0.15 to 1.3 g / m², but in particular is between 0.2 and 0.6 g / m².

Die Prüfung der Bedruckbarkeit und der Abriebfestigkeit bzw. Bäderfestigkeit wurde anhand von Mustern mit handelsüb­lichen Farbbändern durchgeführt. Zur Prüfung der Muster auf che­mische und mechanische Beanspruchungen, wie sie während des Ent­wicklungsvorganges auftreten können, wurden diese 30 Sekunden lang in Entwickler getaucht, mit dem Finger gewischt und nach Spülung mit Wasser geprüft, ob Verwischungen oder Verfärbungen durch Auswaschen einer Farbkomponente aufgetreten sind. Die Ab­riebfestigkeit wurde durch stärkeres Reiben mit dem Finger fest­gestellt.The test of the printability and the abrasion resistance or bath strength was carried out on the basis of samples with standard color ribbons. To test the samples for chemical and mechanical stresses, which can occur during the development process, they were immersed in developer for 30 seconds, wiped with a finger and, after rinsing with water, checked to see whether blurring or discolouration had occurred due to the washing out of a color component. The abrasion resistance was determined by rubbing the finger harder.

Die Prüfung der Klebebandhaftkraft wurde an Mustern mit einem handelsüblichen Klebeband, z.B. einem 3M-Klebe­band 8422, durchgeführt. Das Klebeband wurd aufgedrückt und mit einem Gewicht von 3 kg belastet. Anschließend wurde das Muster in 1,5 cm breite Streifen geschnitten und das Klebe­band eines jeden Musters in einen Bruchlasttester eingespannt, in welchem 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.The test of the adhesive tape adhesive strength was carried out on samples with a commercially available adhesive tape, for example a 3M adhesive tape 8422. The adhesive tape was pressed on and loaded with a weight of 3 kg. The sample was then cut into 1.5 cm wide strips and the adhesive tape of each sample was clamped in a breaking load tester, in which the adhesive tape was removed from the base at an angle of 180 ° at a speed of 20 cm / min. is subtracted. The force required to pull off is measured.

Zur Prüfung der Schmutzaufnahmefähigkeit (Tar Stain) wird eine handelsüblicher Colorentwickler ca. 2 cm hoch in eine offene Schale gefüllt und eine Woche an der Luft stehen gelassen. Nach dieser Zeit hat sich auf der Oberfläche eine dunklere teerartige Schicht aus Oxidationsprodukten gebildet. Diese teerartige Oberfläche wird mit dem zu prüfenden Muster abgezogen, anschließend das Muster unter fließendem Wasser gewaschen und an der Luft getrocknet. Das Ausmaß der Schmutz­aufnahme wird visuell durch die Verfärbung der Rückseite be­urteilt.To test the dirt absorption capacity (Tar Stain), a commercially available color developer is filled approx. 2 cm high in an open bowl and left to stand in the air for a week. After this time, a darker tar-like layer of oxidation products formed on the surface. This tar-like surface is peeled off with the sample to be tested, then the sample is washed under running water and air-dried. The degree of dirt pick-up is assessed visually by the discoloration of the back.

Claims (4)

1. Fotografisches Trägermaterial für lichtempfindliche Schichten in Form eines kunststoffbeschichteten Papiers oder einer Kunststoffolie mit einer beschreibbaren antistatischen Rückseitenbeschichtung unter Verwendung von silikatischen Verbindungen, dadurch gekennzeichnet, daß der Rückseitenstrich folgende Zusammensetzung hat:
a) Ein Terpolymer-Latex aus Styrol-Butadien-­Methacrylat,
b) Kieselsäure (SiO₂) mit einer Teilchengröße von 3 bis 6 µm,
c) ein aluminiummodifiziertes kolloidales Kiesel­säuresol sowie
d) eine wäßrige Lösung eines Salzes einer organischen Polysäure sowie Wasser,
wobei die Mengen der Stoffe a) bis d) so getroffen sind, daß optimale Bedruckbarkeit mit Bändern, Beschreibbarkeit mit Blei­stiften, geringste Verschmutzung in alten oxidierten Entwick­lungsbädern, geringste Verfärbung im Colorentwickler, optimale Klebebandhaftung und antistatische Eigenschaften erhalten werden.1. Photographic support material for light-sensitive layers in the form of a plastic-coated paper or a plastic film with a writable antistatic back coating using silicate compounds, characterized in that the back coating has the following composition:
a) a terpolymer latex made of styrene-butadiene-methacrylate,
b) silica (SiO₂) with a particle size of 3 to 6 µm,
c) an aluminum-modified colloidal silica sol and
d) an aqueous solution of a salt of an organic polyacid and water,
the quantities of substances a) to d) are such that optimum printability with tapes, writeability with pencils, minimal contamination in old oxidized development baths, minimal discoloration in the color developer, optimal adhesive tape adhesion and antistatic properties are obtained. 2. Fotografisches Trägermaterial nach Anspruch 1, dadurch gekennzeichnet, daß der Rückseitenstrich die folgende Zu­sammensetzung hat: Terpolymer-Latex aus Styrol-Butadien-Methacrylat in Wasser mit einem Festkörpergehalt zwischen 30 und 55 Gew.-% 10 - 30 Gew.-% Kieselsäure (SiO₂) in einer Teilchengröße von 3 bis 6 µm 0,1 - 3.0 Gew.-% aluminiummodifiziertes Kieselsäurehydrosol 8 - 30 Gew.-% Alkalipolystyrolsulfonat, 30%ige wäßrige Lösung 0,5 - 5 Gew.-% Rest entsalztes Wasser in einer Menge, die eine gute streichfähige Konsistenz ergibt.
2. Photographic support material according to claim 1, characterized in that the backside stroke has the following composition: Terpolymer latex made of styrene-butadiene-methacrylate in water with a solids content between 30 and 55% by weight 10 - 30% by weight Silicic acid (SiO₂) in a particle size of 3 to 6 microns 0.1 - 3.0% by weight aluminum modified silica hydrosol 8 - 30% by weight Alkali polystyrene sulfonate, 30% aqueous solution 0.5 - 5% by weight Remainder of demineralized water in an amount that gives a good spreadable consistency.
3. Fotografisches Trägermaterial nach Anspruch 1, dadurch ge­kennzeichnet, daß der Rückseitenstrich die folgende Zusammen­setzung hat: Entsalztes Wasser 67,0 Gew.-% Terpolymer-Latex aus Styrol-Butadien-Methacrylat in wäßriger Form mit 50 % Festkörpergehalt 20,0 Gew.-% Kieselsäure, Teilchengröße 3 bis 6 µm 1,0 Gew.-% aluminiummodifiziertes kolloidales Kieselsäuresol, 30%ig in Wasser, mittlere Teilchengröße 10 bis 15 nm 10,0 Gew.-% Natriumsalz einer Polystyrolsulfonsäure MG 20 000, 30%ige wäßrige Lösung 2,0 Gew.-% 100,0 Gew.-%
3. Photographic support material according to claim 1, characterized in that the backside stroke has the following composition: Desalinated water 67.0% by weight Terpolymer latex made of styrene-butadiene methacrylate in aqueous form with 50% solids content 20.0% by weight Silica, particle size 3 to 6 µm 1.0% by weight Aluminum-modified colloidal silica sol, 30% in water, average particle size 10 to 15 nm 10.0% by weight Sodium salt of a polystyrene sulfonic acid MG 20,000, 30% aqueous solution 2.0% by weight 100.0% by weight
4. Trägermaterial nach Anspruch 1 bis 3, dadurch gekenn­zeichnet, daß das Monomerverhältnis im Terpolymer in den folgenden Bereichen liegt:
50 - 70 Gew.-% Styrol
25 - 40 Gew.-% Butadien und
5 - 15 Gew.-% Methacrylat
und das Polymer frei von Carboxyl- und Hydroxylgruppen ist.4. Support material according to claim 1 to 3, characterized in that the monomer ratio in the terpolymer is in the following ranges:
50-70% by weight styrene
25-40% by weight of butadiene and
5 - 15% by weight methacrylate
and the polymer is free of carboxyl and hydroxyl groups.
EP87115556A 1987-10-23 1987-10-23 Photographic support material for light-sensitive layers in the form of a plastic-coated paper or a plastic sheet with a writable antistatic back-layer coating Expired - Lifetime EP0312638B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP87115556A EP0312638B1 (en) 1987-10-23 1987-10-23 Photographic support material for light-sensitive layers in the form of a plastic-coated paper or a plastic sheet with a writable antistatic back-layer coating
ES198787115556T ES2037056T3 (en) 1987-10-23 1987-10-23 PHOTOGRAPHIC SUPPORT MATERIAL FOR LIGHT SENSITIVE LAYERS IN THE SHAPE OF A PLASTIC COATED PAPER OR IN THE FORM OF A SHEET OF PLASTIC MATERIAL WITH AN ANTI-STATIC COATING ON THE BACK SIDE.
AT87115556T ATE84885T1 (en) 1987-10-23 1987-10-23 PHOTOGRAPHIC SUPPORT MATERIAL FOR LIGHT SENSITIVE LAYERS IN THE FORM OF A PLASTIC COATED PAPER OR A PLASTIC FILM WITH AN ANTISTATIC BACK SIDE COATING THAT CAN BE WRITING ON.
DE8787115556T DE3783768D1 (en) 1987-10-23 1987-10-23 PHOTOGRAPHIC CARRIER MATERIAL FOR LIGHT-SENSITIVE LAYERS IN THE FORM OF A PLASTIC-COVERED PAPER OR A PLASTIC FILM WITH A WRITABLE ANTISTATIC BACK COATING.
GR920300114T GR920300114T1 (en) 1987-10-23 1993-02-17
GR930400642T GR3007455T3 (en) 1987-10-23 1993-03-24

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP87115556A EP0312638B1 (en) 1987-10-23 1987-10-23 Photographic support material for light-sensitive layers in the form of a plastic-coated paper or a plastic sheet with a writable antistatic back-layer coating

Publications (2)

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EP0312638A1 true EP0312638A1 (en) 1989-04-26
EP0312638B1 EP0312638B1 (en) 1993-01-20

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EP (1) EP0312638B1 (en)
AT (1) ATE84885T1 (en)
DE (1) DE3783768D1 (en)
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GR (2) GR920300114T1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0421764A1 (en) * 1989-10-03 1991-04-10 Fuji Photo Film Co., Ltd. Support for photographic printing paper
AU609195B2 (en) * 1987-10-23 1991-04-26 Felix Schoeller Jr. Gmbh & Co. Kg Photographic base material for light-sensitive coatings in the form of plastic-coated paper or plastic foil coated on its backside
WO1991008513A2 (en) * 1989-12-05 1991-06-13 Eastman Kodak Company Print retaining coatings and coating compositions for the preparation thereof
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
US5221555A (en) * 1991-12-12 1993-06-22 Felix Schoeller, Jr. Gmbh & Co. Kg Reverse side coating of photographic support materials
EP0558138A1 (en) * 1992-02-24 1993-09-01 Eastman Kodak Company Photographic paper bearing a print retaining layer and coating compositions for the preparation thereof
GB2449306A (en) * 2007-05-18 2008-11-19 Univ Sheffield Composite particles

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US3769020A (en) * 1971-02-11 1973-10-30 Agfa Gevaert Ag Photographic material with improved properties

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US3769020A (en) * 1971-02-11 1973-10-30 Agfa Gevaert Ag Photographic material with improved properties

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Title
PATENT ABSTRACTS OF JAPAN, Band 9, Nr. 217 (P-385)[1940], 4. September 1985; & JP-A-60 76 744 (FUJI SHASHIN FILM K.K.) 01-05-1985; & US-A-4 705 746 (S. TAMAGAWA et al.); Spalte 3, Zeilen 26-52; Ansprüche *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
AU609195B2 (en) * 1987-10-23 1991-04-26 Felix Schoeller Jr. Gmbh & Co. Kg Photographic base material for light-sensitive coatings in the form of plastic-coated paper or plastic foil coated on its backside
US5156707A (en) * 1989-10-03 1992-10-20 Fuji Photo Film Co., Ltd. Support for photographic printing paper
EP0421764A1 (en) * 1989-10-03 1991-04-10 Fuji Photo Film Co., Ltd. Support for photographic printing paper
WO1991008513A2 (en) * 1989-12-05 1991-06-13 Eastman Kodak Company Print retaining coatings and coating compositions for the preparation thereof
WO1991008513A3 (en) * 1989-12-05 1991-08-08 Eastman Kodak Co Print retaining coatings and coating compositions for the preparation thereof
EP0496037A1 (en) * 1991-01-19 1992-07-29 Felix Schoeller jr. Papierfabrik GmbH & Co. KG Coating mass for the reverse of a photographic substrate and process of preparation thereof
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
US5318886A (en) * 1991-01-19 1994-06-07 Felix Schoeller, Jr. Gmbh & Co. Reverse side coating of photographic support materials
US5221555A (en) * 1991-12-12 1993-06-22 Felix Schoeller, Jr. Gmbh & Co. Kg Reverse side coating of photographic support materials
EP0558138A1 (en) * 1992-02-24 1993-09-01 Eastman Kodak Company Photographic paper bearing a print retaining layer and coating compositions for the preparation thereof
US5244728A (en) * 1992-02-24 1993-09-14 Eastman Kodak Company Antistat layers having print retaining qualities
GB2449306A (en) * 2007-05-18 2008-11-19 Univ Sheffield Composite particles

Also Published As

Publication number Publication date
ES2037056T3 (en) 1993-06-16
GR920300114T1 (en) 1993-02-17
GR3007455T3 (en) 1993-07-30
EP0312638B1 (en) 1993-01-20
DE3783768D1 (en) 1993-03-04
ATE84885T1 (en) 1993-02-15

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