EP0312638B1 - 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
EP0312638B1
EP0312638B1 EP87115556A EP87115556A EP0312638B1 EP 0312638 B1 EP0312638 B1 EP 0312638B1 EP 87115556 A EP87115556 A EP 87115556A EP 87115556 A EP87115556 A EP 87115556A EP 0312638 B1 EP0312638 B1 EP 0312638B1
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EP
European Patent Office
Prior art keywords
water
support material
styrene
butadiene
methacrylate
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EP87115556A
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German (de)
French (fr)
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EP0312638A1 (en
Inventor
Eckehard Säverin
Hans-Udo Tyrakowski
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Felex Schoeller Jr and GmbH and Co KG
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Felex Schoeller Jr and GmbH and Co KG
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Priority to AT87115556T priority Critical patent/ATE84885T1/en
Priority to DE8787115556T priority patent/DE3783768D1/en
Priority to ES198787115556T priority patent/ES2037056T3/en
Priority to EP87115556A priority patent/EP0312638B1/en
Publication of EP0312638A1 publication Critical patent/EP0312638A1/en
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Publication of EP0312638B1 publication Critical patent/EP0312638B1/en
Priority to GR920300114T priority patent/GR920300114T1/el
Priority to GR930400642T priority patent/GR3007455T3/el
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Expired - Lifetime legal-status Critical Current

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/95Photosensitive 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 when passing through the various treatment baths, must not pick up and hold dirt particles on its surface, which can form in the treatment baths over time.
  • Adhesive tapes must adhere well because, among other things, is used to fasten the photographic papers present in long strips to one another in order to ensure a smooth passage through the processing machine. In all of this, the antistatic charging of the hydrophobic coating of the photographic support material should be prevented as far as possible. The electrostatic charge discharges when a certain value is reached with the formation of lightning, which can lead to the destruction of the latent image to be developed.
  • Japanese patent application JP-A-60 76744 discloses a photographic paper with a latex which contains an alkyl diphenyl ether sulfonate and / or a formalin condensation product of the naphthalene sulfonate and colloidal silica and alkali aluminate on the back of the paper coated with polyolefin on both sides.
  • these instructions do not contain any quantities and, in addition, such a coating is obviously only writable and antistatic.
  • Hydrophobic components have the disadvantage of high dirt absorption and low antistatic activity but strong electrostatic chargeability, while hydrophilic components adversely affect tape adhesion, are difficult to print 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 the adhesive tape adhesion are in turn adversely affected by the action of the baths.
  • a 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 which contains a styrene-butadiene-methacrylate copolymer, silica and aluminum compounds, characterized in that the aqueous mixture comprising the back coating results in the following composition: a) a terpolymer latex made from styrene-butadiene methacrylate free of carboxyl and hydroxyl groups and having a solids content of between 30 and 55% by weight, 10 - 30% by weight b) silica (SiO2) with a particle size of 3 - 6 microns 0.1 - 3.0% by weight c) An aluminum-modified colloidal silica sol with an average particle size of 10-15 nm, 30% by weight in water 8 - 30% by weight d) An aqueous solution of an alkali polystyrene sulfonate, 30%
  • the coating ensures 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.
  • the terpolymer which is free of carboxyl and hydroxyl groups, consists of styrene-butadiene-methacrylate in an aqueous suspension with a solids content of 30 to 55% by weight. It is a latex that specifically fulfills optimal printability, adhesive tape adhesion and minimal contamination ( Tar Stain) of the backstroke of the base paper. It is the most 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 backside stroke is chosen so that the stroke still its strength and invulnerability in the 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 (SiO2) with a particle size of 3 to 6 ⁇ m is responsible for being writable with a pencil.
  • 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 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, the latex is weakened, so that the effect is no longer entirely satisfactory.
  • the aluminum-modified colloidal silica sol in water with a particle size of 10 to 15 nm contains 30% by weight solids and is self-binding on drying 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 8 and 30% by weight.
  • the component d), namely the aqueous solution of the alkali salt of an organic polyacid is a substance which produces the actually antistatic effect, alkali salts of organic polysulfonic acids are preferably used.
  • 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: Terpolymer latex made of styrene-butadiene methacrylate in demineralized water free of carboxyl and hydroxyl groups with a solids content of 50% by weight, between 10 - 30% by weight Silicic acid, 10% in water, particle size 3 - 6 ⁇ m 0.1 - 3% by weight Aluminum modified silicic acid hydrosol, 30% in water with a particle size of 10 - 15 nm 8 - 30% by weight Sodium polystyrene sulfonic acid, 30% aqueous solution 0.5 - 5% by weight and demineralized water in an amount that gives a good spreadable consistency.
  • a preferred mixture has the following composition: Desalinated water 67.0% by weight Terpolymer latex made from styrene-butadiene methacrylate in aqueous form with 50% by weight solids content and free of carboxyl and hydroxyl groups 20.0% by weight Silica, particle size 3 - 6 ⁇ m, 1.0% by weight aluminum-modified colloidal silica sol, 30% 10.0% by weight Sodium salt of a polystyrene sulfonic acid MG 20,000, 30% aqueous solution 2.0% by weight 100% by weight
  • 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 soiling (tar stain) on the back.
  • the mixture 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 adhesive tape adhesion was tested on samples using 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.

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. 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 thermoplastischen 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 thermoplastic on both sides Plastic layers, in particular polyolefin layers, are coated and thus protect the paper core flatly 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 marked 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 required 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.

Das beschichtete fotografische Material darf beim Durchgang durch die verschiedenen Behandlungsbäder keine Schmutzteilchen auf seiner Oberfläche aufnehmen und festhalten, die sich in den Behandlungsbädern im Laufe der Zeit bilden können.The coated photographic material, when passing through the various treatment baths, must not pick up and hold dirt particles on its surface, which can form in the treatment baths 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. Desirable properties.

Eine gute Haftung von Klebebändern ist erforderlich, weil sie u.a. zur Befestigung der in langen Streifen vorliegenden fotografischen Papiere aneinander dient, um einen glatten Durchlauf durch die Entwicklungsmaschine zu gewährleisten. Bei all dem soll möglichst noch die antistatische Aufladung der hydrophoben Beschichtung des fotografischen Trägermaterials verhindert werden. Die elektrostatische Aufladung entlädt sich beim Erreichen eines bestimmten Wertes unter Blitzbildung, was zur Zerstörung des zu entwickelnden latenten Bildes führen kann.Adhesive tapes must adhere well because, among other things, is used to fasten the photographic papers present in long strips to one another in order to ensure a smooth passage through the processing machine. In all of this, the antistatic charging of the hydrophobic coating of the photographic support material should be prevented as far as possible. The electrostatic charge discharges when a certain value is reached with the formation of lightning, which can lead to the destruction of the latent image to be developed.

Aus der japanischen Patentanmeldung JP-A-60 76744 ist ein fotografisches Papier bekannt mit einem Latex, der ein Alkyldiphenylethersulfonat enthält und/oder ein Formalin-Kondensationsprodukt des Naphtalinsulfonats und kolloidale Kieselsäure und Alkalialuminat auf der Rückseite des von beiden Seiten mit Polyolefin beschichteten Papieres. Jedoch enthält diese Anleitung keinerlei Mengenangaben und außerdem ist eine derartige Beschichtung offensichtlich nur beschreibbar und antistatisch.Japanese patent application JP-A-60 76744 discloses a photographic paper with a latex which contains an alkyl diphenyl ether sulfonate and / or a formalin condensation product of the naphthalene sulfonate and colloidal silica and alkali aluminate on the back of the paper coated with polyolefin on both sides. However, these instructions do not contain any quantities and, in addition, such a coating is obviously only writable and antistatic.

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 tape adhesion, are difficult to print 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 the 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 wahrend 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, as little dirt pick-up as possible, 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 ein fotografisches Trägermaterial für lichtempfindliche Schichten in Form eines kunststoffbeschichteten Papiers oder einer Kunststoffolie mit einer beschreibbaren, antistatischen Rückseitenbeschichtung die eine Styrol-Butadien-Methacrylat-Copolymer, Kieselsäure und Aluminiumverbindungen enthält, dadurch gekennzeichnet, daß die wäßrige Mischung, die den Rückseitenstrich ergibt, folgende Zusammensetzung hat: a) Ein Terpolymer-Latex aus Styrol-Butadien-Methacrylat frei von Carboxyl- und Hydroxylgruppen mit einem Festkörpergehalt zwischen 30 - 55 Gew.-%, 10 - 30 Gew.-% b) Kieselsäure (SiO₂) mit einer Teilchengröße von 3 - 6 µm 0,1 - 3,0 Gew.-% c) Ein aluminiummodifiziertes kolloïdales Kieselsäuresol mit einer mittleren Teilchengröße von 10 - 15 nm, 30 Gew.-% in Wasser 8 - 30 Gew.-% d) Eine wäßrige Lösung eines Alkali-polystyrolsulfonats, 30%ig in Wasser 0,5 - 5 Gew.-% Rest entsalztes Wasser in einer Menge, die eine gute, streichfähige Konsistenz ergibt. This is achieved by means of a 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 which contains a styrene-butadiene-methacrylate copolymer, silica and aluminum compounds, characterized in that the aqueous mixture comprising the back coating results in the following composition: a) a terpolymer latex made from styrene-butadiene methacrylate free of carboxyl and hydroxyl groups and having a solids content of between 30 and 55% by weight, 10 - 30% by weight b) silica (SiO₂) with a particle size of 3 - 6 microns 0.1 - 3.0% by weight c) An aluminum-modified colloidal silica sol with an average particle size of 10-15 nm, 30% by weight in water 8 - 30% by weight d) An aqueous solution of an alkali polystyrene sulfonate, 30% in water 0.5 - 5% by weight Remainder of demineralized water in an amount that gives a good, spreadable consistency.

Die Beschichtung gewährleistet, 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.The coating ensures 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, das frei von Carboxyl- und Hydroxylgruppen ist, besteht aus Styrol-Butadien-Methacrylat in wäßriger Suspension mit einem Festkörpergehalt von 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 wichtigste 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 gewählt, 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, which is free of carboxyl and hydroxyl groups, consists of styrene-butadiene-methacrylate in an aqueous suspension with a solids content of 30 to 55% by weight. It is a latex that specifically fulfills optimal printability, adhesive tape adhesion and minimal contamination ( Tar Stain) of the backstroke of the base paper. It is the most 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 backside stroke is chosen so that the stroke still its strength and invulnerability in the 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 (SiO₂) mit einer Teilchengröße von 3 bis 6 µm ist zuständig für die Beschreibbarkeit mit Bleistift. 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 zwischen 0,1 und 3,0 Gew.-% Festkörpergehalt, bezogen auf die Gesamtmischung.The silica (SiO₂) with a particle size of 3 to 6 µm is responsible for being writable with a pencil. 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 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, the latex is weakened, so that the effect is no longer entirely satisfactory.

Das aluminiummodifizierte kolloidale Kieselsäuresol in Wasser mit einer Teilchengröße von 10 bis 15 nm enthält 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 8 und 30 Gew.-%.The aluminum-modified colloidal silica sol in water with a particle size of 10 to 15 nm contains 30% by weight solids and is self-binding on drying 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 8 and 30% by weight.

Der Bestandteil d), nämlich die wäßrige Lösung des Alkalisalzes einer organischen Polysäure ist eine Substanz, die die eigentlich antistatische Wirkung hervorruft, vorzugsweise werden Alkalisalze organischer Polysulfonsäuren verwendet.The component d), namely the aqueous solution of the alkali salt of an organic polyacid is a substance which produces the actually antistatic effect, alkali salts of organic polysulfonic acids are preferably used.

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.In combination 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: Terpolymer-Latex aus Styrol-Butadien-Methacrylat in entsalztem Wasser frei von Carboxyl- und Hydroxylgruppen mit einem Festkörpergehalt von 50 Gew.-%, zwischen 10 - 30 Gew.-% Kieselsäure, 10%ig in Wasser, Teilchengröße 3 - 6 µm 0,1 - 3 Gew.-% aluminiummodifiziertes Kieselsäurehydrosol, 30%ig in Wasser mit einer Teilchengröße 10 - 15 nm 8 - 30 Gew.-% Natriumpolystyrolsulfonsäure, 30%ige wäßrige Lösung 0,5 - 5 Gew.-% und entsalztes Wasser in einer Menge, die eine gute streichfähige Konsistenz ergibt. The attached table shows a comparison with various other backside coatings A-E on the market, the coating according to the invention according to the following recipe in the last vertical column. A universally applicable mixture can be composed as follows: Terpolymer latex made of styrene-butadiene methacrylate in demineralized water free of carboxyl and hydroxyl groups with a solids content of 50% by weight, between 10 - 30% by weight Silicic acid, 10% in water, particle size 3 - 6 µm 0.1 - 3% by weight Aluminum modified silicic acid hydrosol, 30% in water with a particle size of 10 - 15 nm 8 - 30% by weight Sodium polystyrene sulfonic acid, 30% aqueous solution 0.5 - 5% by weight and demineralized water in an amount that gives a good spreadable consistency.

Eine bevorzugte Mischung hat folgende Zusammensetzung: Entsalztes Wasser 67,0 Gew.-% Terpolymer-Latex aus Styrol-Butadien-Methacrylat in wäßriger Form mit 50 Gew.-% Festkörpergehalt und frei von Carboxyl- und Hydroxylgruppen 20,0 Gew.-% Kieselsäure, Teilchengröße 3 - 6 µm, 1,0 Gew.-% aluminiummodifiziertes kolloidales Kieselsäuresol, 30%ig 10,0 Gew.-% Natriumsalz einer Polystyrolsulfonsäure MG 20 000, 30%ige wäßrige Lösung 2,0 Gew.-% 100 Gew.-%

Figure imgb0001
A preferred mixture has the following composition: Desalinated water 67.0% by weight Terpolymer latex made from styrene-butadiene methacrylate in aqueous form with 50% by weight solids content and free of carboxyl and hydroxyl groups 20.0% by weight Silica, particle size 3 - 6 µm, 1.0% by weight aluminum-modified colloidal silica sol, 30% 10.0% by weight Sodium salt of a polystyrene sulfonic acid MG 20,000, 30% aqueous solution 2.0% by weight 100% by weight
Figure imgb0001

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 soiling (tar stain) on the back.

Die 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 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 adhesive tape adhesion was tested on samples using 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 (3)

  1. Photographic support material for photosensitive layers in the form of a plastics-coated paper or a plastics sheet having a writable, antistatic reverse side coating which contains a styrene-butadiene-methacrylate copolymer, silica and aluminium compounds, characterized in that the aqueous mixture which yields the reverse side coating has the following composition: a) a terpolymer latex of styrene-butadiene-methacrylate free from carboxy and hydroxy groups having a solids content between 30 and 55% by wt. 10 - 30% by wt. b) silica (SiO₂) having a particle size of 3 - 6 µm 0.1 - 3.0% by wt. c) an aluminium-modified colloidal silica sol having a mean particle size of 10 - 15 nm, 30% by wt. in water 8 - 30% by wt. d) an aqueous solution of an alkali polystyrene sulphonate, 30% in water 0.5 - 5% by wt. remainder, desalted water in a quantity which yields a good, brushable consistency.
  2. Photographic support material according to Claim 1, characterized in that the aqueous mixture which yields the reverse side coating has the following composition: desalted water 67.0% by wt. terpolymer latex of styrene-butadiene-methacrylate in water having a solids content of 50% by wt. (free from carboxy and hydroxy groups) 20.0% by wt. silica (SiO₂), particle size 3 - 6 µm 1.0% by wt. aluminium-modified colloidal silica sol, 30% in water, mean particle size 10 - 15 nm 10.0% by wt. sodium salt of a polystyrene sulphonic acid, molecular weight 20,000, 30% aqueous solution 2.0% by wt. 100.0% by wt.
  3. Support material according to Claims 1 and 2, characterized in that the monomer ratio in the terpolymer lies within the following ranges: 50 - 70% by wt. styrene 25 - 40% by wt. butadiene and 5 - 15% by wt. methacrylate.
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
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.
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.
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
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 EP0312638A1 (en) 1989-04-26
EP0312638B1 true EP0312638B1 (en) 1993-01-20

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EP (1) EP0312638B1 (en)
AT (1) ATE84885T1 (en)
DE (1) DE3783768D1 (en)
ES (1) ES2037056T3 (en)
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Publication number Priority date Publication date Assignee Title
DE3735871A1 (en) * 1987-10-23 1989-05-03 Schoeller F Jun Gmbh Co Kg PHOTOGRAPHIC SUPPORT MATERIAL FOR LIGHT-SENSITIVE LAYERS IN THE FORM OF A PLASTIC-COATED PAPER OR A PLASTIC SOLVE WITH A BACK COATING
JP2704311B2 (en) * 1989-10-03 1998-01-26 富士写真フイルム株式会社 Photographic paper support
US5075164A (en) * 1989-12-05 1991-12-24 Eastman Kodak Company Print retaining coatings
US5221555A (en) * 1991-12-12 1993-06-22 Felix Schoeller, Jr. Gmbh & Co. Kg 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
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

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Publication number Priority date Publication date Assignee Title
US3769020A (en) * 1971-02-11 1973-10-30 Agfa Gevaert Ag Photographic material with improved properties

Non-Patent Citations (1)

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Title
englische Übersetzung des japanischen Dokumentes JP-A-6 076 744 *

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ATE84885T1 (en) 1993-02-15
GR3007455T3 (en) 1993-07-30
EP0312638A1 (en) 1989-04-26
ES2037056T3 (en) 1993-06-16
GR920300114T1 (en) 1993-02-17
DE3783768D1 (en) 1993-03-04

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