EP0114973B1 - Water-proof photographic paper - Google Patents

Water-proof photographic paper Download PDF

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Publication number
EP0114973B1
EP0114973B1 EP83111927A EP83111927A EP0114973B1 EP 0114973 B1 EP0114973 B1 EP 0114973B1 EP 83111927 A EP83111927 A EP 83111927A EP 83111927 A EP83111927 A EP 83111927A EP 0114973 B1 EP0114973 B1 EP 0114973B1
Authority
EP
European Patent Office
Prior art keywords
barrier layer
layer
paper
hardened
gew
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83111927A
Other languages
German (de)
French (fr)
Other versions
EP0114973A2 (en
EP0114973A3 (en
Inventor
Reiner Chem.-Ing. Anthonsen
Wieland Dr. Dipl.-Phys. Sack
Heinz Trentmann
Hans-Georg Wöllmer
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.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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 AT83111927T priority Critical patent/ATE42838T1/en
Publication of EP0114973A2 publication Critical patent/EP0114973A2/en
Publication of EP0114973A3 publication Critical patent/EP0114973A3/en
Application granted granted Critical
Publication of EP0114973B1 publication Critical patent/EP0114973B1/en
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D21H19/822—Paper comprising more than one coating superposed two superposed coatings, both being pigmented
    • 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
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper

Definitions

  • the invention relates to a multi-layer, waterproof photographic paper support with a particularly high surface flatness and good photographic properties, and to a method for the production thereof.
  • DE-AS 1 447 815 describes a paper support for photosensitive layers coated on both sides with polyolefin resin.
  • DE-OS 3 022 451 describes a paper support which is coated on both sides with lacquer layers hardened by electron beams.
  • DE-OS 3 022 709 finally describes a paper carrier coated with curable mixtures, in which a coating is cured in contact with a shaping surface, and which is consequently distinguished by high flatness of the surface.
  • the new waterproof lacquer coatings hardened by electron beams described in DE-OS 3 022 451 and DE-OS 3 022 709 are above all more scratch-resistant than the bis-. long common polyolefin coatings according to DE-AS 1 447 815.
  • the layer hardened by electron beams according to DE-OS 3 046 130 was covered with an additional polyolefin layer.
  • an additional polyolefin layer As a result, it was possible to ensure a storage stability of several months while almost maintaining the good surface characteristics of the support and to obtain a product that could be used under normal conditions.
  • a reduction in sharpness due to the polyolefin coverage had to be accepted.
  • the scratch sensitivity of the polyolefin surface is again disadvantageous in this embodiment.
  • the durability of the photographic material is limited by the polyolefin, which, in terms of its aging resistance, lags far behind the classic photo supports with baryta layers.
  • the paper backing consists of a fully glued base paper, which is coated with a radiation-hardened lacquer layer. At least one barrier layer is arranged between the paper and the lacquer layer.
  • the base paper preferably consists of fiber pulp or synthetic fibers or other constituents, also in a mixture, it is hydrophobized and equipped with other customary glues and strengthening agents.
  • the barrier layer which is described in detail below, lies on the base paper.
  • the permeability of the barrier layer for acrylate monomer is such that when testing with the Hercules sizing tester more than 100 seconds are required until the remission has dropped to 70%.
  • the permeability for an acrylate monomer does not fall below the stated value of 100 seconds and that the layer contains only minimal amounts of free wetting agent, preferably no free wetting agent.
  • the barrier layer consists of a polyolefin film which has been applied by extrusion coating.
  • the thickness of the layer in this case is 5-30 11 m, preferably 7-20 11 m.
  • the polyolefin is, for example, polypropylene or polyethylene or an ionomer resin or another ethylene copolymer resin.
  • the barrier layer can also consist of a mixture of the thermoplastic resins mentioned with one another or with other thermoplastic resins.
  • the front side barrier layer preferably contains pigments.
  • the barrier layer is applied as an aqueous solution of a water-soluble film-forming polymer and dried.
  • Suitable water-soluble polymers are, for example, polyvinyl alcohols, film-forming starch derivatives, film-forming cellulose derivatives, copolymers of acrylic acid with other vinyl monomers, alginates, casein, polyacrylamide, polystyrene sulfonate or mixtures of these polymers with one another or with other substances dissolved or dispersed in water.
  • the fat The dried barrier layer is between 4 and 30 pm, depending on the type of polymer.
  • the barrier layer is produced from the aqueous dispersion of a water-insoluble polymer or from a mixture of such a polymer dispersion with a water-soluble binder dissolved in water.
  • Suitable polymer dispersions are dispersions with ethylene polymers and copolymers, acrylate or methacrylate polymers and copolymers, vinyl acetate copolymers and mixtures of such polymer dispersions with one another which are film-forming at the drying temperatures customary in the paper machine or in the coating machine.
  • the thickness of the dried barrier layer is between 4 and 30 ⁇ m when it is produced from an aqueous dispersion.
  • the barrier layer can contain all the usual additives and auxiliaries such as pigments, dyes. Brighteners, plasticizers, electrolytes etc. contain. The only exception is the use of larger amounts of free wetting agents. Specifically, this means that the surface tension of an aqueous coating mixture should preferably not be less than 55 mN / m. In particular, non-ionic wetting agents in the barrier layer should be avoided as far as possible.
  • a mixture curable by electron beams is applied to the water-free barrier layer either directly or after carrying out an adhesion-improving pretreatment and solidified by the action of electron beams.
  • Conventional photographic layers based on photocatalytic redox systems, for example silver salts, are applied to this layer hardened by means of electron beams, optionally also after applying an adhesive layer.
  • the coating consolidated by means of electron beams preferably contains pigments and optionally small amounts of dyes and / or other additives in addition to the binder.
  • a coating has a basis weight of about 10 to 60 g / m 2 (preferably 15 to 40 g / m 2 ).
  • the curable mixture is applied using one of the known coating processes, leveled and, after being covered with a protective gas, cured by means of electron beams.
  • a protective gas cured by means of electron beams.
  • DE-OS 3 022 709 it can also be pressed against a shaping surface after application and then solidified by means of electron beams through paper and barrier layers without the use of a protective gas.
  • the two-sided layers according to DE-OS 3 022 709 can also be applied in one operation and solidified at the same time.
  • pigments in a layer to be hardened by means of electron beams are white pigments, e.g. Titanium oxide, zirconium oxide, zinc oxide, zinc sulfide, antimony oxide, barium sulfate, calcium carbonate. Color pigments, carbon black or soluble dyes can also be contained in the layer for special purposes or for taste considerations. However, the layer can also be transparent.
  • the back of the paper of the multi-layer carrier material produced according to the invention is also coated with a barrier layer and a hardenable layer and optionally further layers.
  • the single-sided multilayer structure according to the invention is sufficient for simple applications.
  • One or more photographic layers based on silver salt emulsions for black / white or color photographs are arranged over the front-side layer hardened by electron beams, optionally after application of a further intermediate layer.
  • FIGS. 1-3 For a better understanding of the structure of the carrier material according to the invention, different embodiments are shown in cross section in FIGS. 1-3.
  • 1 denotes the photographic layer, which in turn can consist of several layers.
  • 2 denotes an optionally present adhesion-promoting intermediate layer
  • 3 denotes the front layer which is solidified by means of electron beams and preferably contains pigment
  • 4 denotes the front barrier layer
  • 5 denotes the photographic base paper with a hydrophobizing inner sizing and / or optionally a surface sizing
  • 6 denotes the rear barrier layer
  • 7 denotes another layer hardened by electron beams
  • 8 denotes another functional back layer.
  • a photographic base paper weighing approx. 80 g / m 2 which is glued on the inside with alkyl ketene dimer and polyamide epichlorohydrin resin and which has been given a surface sizing made from anionic starch with NaCl, is coated on both sides by means of extrusion coating with approx. 12 g / m 2 of a polyethylene mixture.
  • the polyethylene mixture contains approx. 10% by weight of titanium dioxide and 0.2% by weight of cobalt violet pigment.
  • Polyethylene represents all extrudable thermoplastic polymers.
  • Parts of the thus pre-coated paper are then respectively by corona treatment of the poly äthylenoberfest on both sides according to the method described in DE-OS 3,022,709 with 25 g / m 2 coated with radiation-curable mixtures, and this is solidified by means of electron beams.
  • the coating on one side is solidified through the paper in contact with a high-gloss cylinder, and the coating on the opposite side is solidified under nitrogen as a protective gas after equalization.
  • the solidification takes place by means of electron beams with an energy dose of 40 J / g.
  • the dried barrier coating has a weight per unit area of approximately 15 g / m 2 . It is smoothed with the aid of a calendering device and, according to example 1, recipe F, is coated on both sides with 20 g / m 2 of a layer hardened by electron beams.
  • the layer is solidified under nitrogen by means of electron beams with an energy dose of 30 J / g and forms the back of the photographic support.
  • the weight per unit area of the barrier layer is approx. 25 g / m 2 .
  • the precoated paper is smoothed and, according to Example 1, recipe F, coated on one side with about 15 g / m 2 of a curable mixture. The mixture is pressed against a high-gloss cylinder and solidified from the back by means of electron beams at 50 J / g.
  • a comparative example 13 was taken from a photographic carrier paper coated on both sides with polyethylene, which according to comparative example A from DOS 3 022 451 was coated on the front with a 15/85 titanium dioxide / polyethylene mixture and on the back with a non-pigmented polyethylene layer.
  • barrier layers were determined with the Hercules sizing tester using hexanediol diacrylate (HDDA) as test equipment. The device and its function are described in the leaflet "Hercules - degree of performance tester " from Hercules NV. The Hague (Holland). These tests were carried out before the hardenable coating was applied to the papers.
  • HDDA hexanediol diacrylate
  • Papers coated on both sides with water resistance are generally only coated on the side with a barrier layer and an electron beam hardened layer which is intended for coating with light-sensitive layers.
  • the opposite side can be coated in any waterproof manner according to one of the methods described in the literature. All known types of surface design that are required by the use of the papers, i.e. Roughness, writeability, antistatic properties and rolling behavior of the papers are preferably controlled via the back coating.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Packages (AREA)

Abstract

A multilayer, waterproof photographic paper support includes a paper which is coated with a layer of radiation hardened varnish or varnish color and a barrier layer is positioned between the paper and varnish layer. The barrier layer comprises a polymer, film-forming material, produced either by extrusion coating, a coating of an aqueous solution or dispersion.

Description

Die Erfindung betrifft einen mehrschichtigen wasserfesten fotografischen Papierträger mit besonders hoher Oberflächenebenheit und guten fotografischen Eigenschaften sowie ein Verfahren zu dessen Herstellung.The invention relates to a multi-layer, waterproof photographic paper support with a particularly high surface flatness and good photographic properties, and to a method for the production thereof.

Wasserfest beschichtete fotografische Papierträger sind in verschiedenen Ausführungsformen bekannt. Die DE-AS 1 447 815 beschreibt einen beidseitig mit Polyolefinharz beschichteten Papierträger für lichtempfindliche Schichten. In der DE-OS 3 022 451 wird ein Papierträger beschrieben, der beidseitig mit durch Elektronenstrahlen gehärteten Lackschichten überzogen ist. Die DE-OS 3 022 709 beschreibt schließlich einen mit härtbaren Mischungen überzogenen Papierträger, bei dem ein Überzug in Kontakt mit einer formgebenden Oberfläche ausgehärtet wird, und der infolgedessen durch hohe Ebenheit der Oberfläche ausgezeichnet ist. Die neuen in der DE-OS 3 022 451 und DE-OS 3 022 709 beschriebenen durch Elektronenstrahlen gehärteten wasserfesten Lack- überzüge sind vor allem kratzfester als die bis- . lang üblichen Polyolefinberzüge gemäß DE-AS 1 447 815. Darüber hinaus ist die Möglichkeit zu höherer Pigmentierung gegeben, die eine bessere Bildschärfe bei Aufsichtsbildern zur Folge hat, und die Verbesserung der Oberflächenstruktur gemäß DE-OS 3 022 709 trägt entscheiden dazu bei, daß dünnere fotografische Schichten gleichmäßig aufgezogen werden können. Auch dies hat eine Verbesserung der Bildqualität zur Folge.Water-proof coated photographic paper supports are known in various embodiments. DE-AS 1 447 815 describes a paper support for photosensitive layers coated on both sides with polyolefin resin. DE-OS 3 022 451 describes a paper support which is coated on both sides with lacquer layers hardened by electron beams. DE-OS 3 022 709 finally describes a paper carrier coated with curable mixtures, in which a coating is cured in contact with a shaping surface, and which is consequently distinguished by high flatness of the surface. The new waterproof lacquer coatings hardened by electron beams described in DE-OS 3 022 451 and DE-OS 3 022 709 are above all more scratch-resistant than the bis-. long common polyolefin coatings according to DE-AS 1 447 815. In addition, there is the possibility of higher pigmentation, which results in better image sharpness in the case of top-view images, and the improvement in the surface structure according to DE-OS 3 022 709 contributes to the fact that thinner photographic layers can be drawn up evenly. This also results in an improvement in the image quality.

Nachteilig an Trägermaterialien mit strahlengehärteten Überzügen ist bislang, daß bei normaler Lagerung der fotografischen Produkte eine geringfügige Verschiebung der Empfindlichkeit der fotografischen Schichten und bei längeren Lagerzeiten ein meßbarer Schleier auftritt. Dieser Nachteil macht sich nach einigen Monaten Lagerung bemerkbar.A disadvantage of support materials with radiation-hardened coatings has hitherto been that, with normal storage of the photographic products, there is a slight shift in the sensitivity of the photographic layers and a measurable haze occurs during longer storage times. This disadvantage becomes noticeable after a few months of storage.

Bislang ist unklar, warum die Lagerstabilität nicht gewährleistet ist, denn die Ausgangsmaterialien haben keinen meßbaren Einfluß auf die fotografischen Schichten. Es wird angenommen, daß ein fotochemisch aktives niedermolekulares Monomer oder Verunreinigung durch Diffusion in die fotografischen Schichten gelangt und dort zur Reaktion gelangt, nachdem es durch die Strahlung erst fotochemisch aktiv wurde. Solche niedermolekulare Monomere sind in der härtbaren, bzw. noch ungehärteten Schicht enthalten.So far it is unclear why the storage stability is not guaranteed, because the starting materials have no measurable influence on the photographic layers. It is assumed that a photochemically active low molecular monomer or impurity by diffusion gets into the photographic layers and reacts there after it has only become photochemically active due to the radiation. Such low molecular weight monomers are contained in the curable or still uncured layer.

Um diesem Nachteil zu begegnen, wurde die durch Elektronenstrahlen gehärtete Schicht gemäß DE-OS 3 046 130 mit einer zusätzlichen Polyolefinschicht überdeckt. Dadurch gelang es, unter annäherndem Erhalt der guten Oberflächencharakteristik des Trägers eine Lagerstabilität von mehreren Monaten sicherzustellen und ein unter Normalbedingungen gebrauchsfähiges Produkt zu erhalten. Als Nachteil mußte eine durch die Polyolefinüberdeckung bedingte Verringerung der Bildschärfe in Kauf genommen werden. Auch die Kratzempfindlichkeit der Polyolefinoberfläche ist bei dieser Ausführungsform wieder nachteilig zu vermerken. Außerdem wird die Haltbarkeit des fotografischen Materials durch das Polyolefin begrenzt, das hinsichtlich seiner Alterungsbeständigkeit deutlich hinter den klassischen Fototrägern mit Barytschichten zurückbleibt.In order to counter this disadvantage, the layer hardened by electron beams according to DE-OS 3 046 130 was covered with an additional polyolefin layer. As a result, it was possible to ensure a storage stability of several months while almost maintaining the good surface characteristics of the support and to obtain a product that could be used under normal conditions. As a disadvantage, a reduction in sharpness due to the polyolefin coverage had to be accepted. The scratch sensitivity of the polyolefin surface is again disadvantageous in this embodiment. In addition, the durability of the photographic material is limited by the polyolefin, which, in terms of its aging resistance, lags far behind the classic photo supports with baryta layers.

Es ist demzufolge Aufgabe der vorliegenden Erfindung, ein wasserfestes und kratzfestes fotografisches Trägerelement mit hoher Haltbarkeit zu schaffen, das nicht nur eine stabile, gleichbleibend ebene Oberfläche besitzt, sondern auch nach längeren Lagerungszeiten keinen Einfluß auf die Empfindlichkeit aufliegender fotografischer Schichten hat und keinen störenden Schleier in den fotografischen Schichten verursacht.It is therefore an object of the present invention to provide a waterproof and scratch-resistant photographic support element with high durability, which not only has a stable, consistently flat surface, but also has no influence on the sensitivity of overlying photographic layers after long periods of storage and has no disturbing haze in the photographic layers.

Diese Aufgabe wird gelöst, durch die in den Ansprüchen gekennzeichneten Merkmale.This object is achieved by the features characterized in the claims.

Der Papierträger besteht aus einem voll geleimten Basispapier, welches mit einer strahlengehärteten Lackschicht überzogen ist. Zwischen Papier und Lackschicht ist mindestens eine Sperrschicht angeordnet. Das Basispapier besteht vorzugsweise aus Faserzellstoff oder aus synthetischen Fasern oder sonstigen Bestandteilen auch in Mischung, es ist hydrophobiert und mit sonstigen üblichen Leim- und Verfestigungsmitteln ausgerüstet. Auf dem Basispapier liegt die Sperrschicht, die unten ausführlich beschrieben ist.The paper backing consists of a fully glued base paper, which is coated with a radiation-hardened lacquer layer. At least one barrier layer is arranged between the paper and the lacquer layer. The base paper preferably consists of fiber pulp or synthetic fibers or other constituents, also in a mixture, it is hydrophobized and equipped with other customary glues and strengthening agents. The barrier layer, which is described in detail below, lies on the base paper.

Die Durchlässigkeit der Sperrschicht für Acrylatmonomer ist so, daß bei Prüfung mit dem Hercules-Sizing-Tester mehr als 100 Sekunden benötigt werden bis die Remission auf 70% abgefallen ist.The permeability of the barrier layer for acrylate monomer is such that when testing with the Hercules sizing tester more than 100 seconds are required until the remission has dropped to 70%.

Die Sperrschicht kann erfindungsgemäß auf unterschiedliche Weise aus unterschiedlichen Stoffen hergestellt werden.According to the invention, the barrier layer can be produced in different ways from different substances.

Zu beachten ist lediglich, daß die Durchlässigkeit für ein Acrylatmonomer den genannten Wert von 100 Sekunden nicht unterschreitet, und daß die Schicht nur minimale Mengen an freiem Netzmittel, vorzugsweise kein freies Netzmittel enthält.It should only be noted that the permeability for an acrylate monomer does not fall below the stated value of 100 seconds and that the layer contains only minimal amounts of free wetting agent, preferably no free wetting agent.

In einer besonderen Ausführungsform besteht die Sperrschicht aus einem Polyolefinfilm, der durch Extrusionsbeschichtung aufgebracht wurde. Die Dicke der Schicht beträgt in diesem Falle 5-30 11m, vorzugsweise 7-20 11m. Das Polyolefin ist beispielsweise Polypropylen oder Polyäthylen oder ein lonomerharz oder ein anderes Äthylencopolymerharz. Die Sperrschicht kann aber auch aus einer Mischung der genannten thermoplastischen Harze untereinander oder mit anderen thermoplastischen Harzen bestehen. Vorzugsweise enthält die Sperrschicht der Vorderseite Pigmente.In a particular embodiment, the barrier layer consists of a polyolefin film which has been applied by extrusion coating. The thickness of the layer in this case is 5-30 11 m, preferably 7-20 11 m. The polyolefin is, for example, polypropylene or polyethylene or an ionomer resin or another ethylene copolymer resin. However, the barrier layer can also consist of a mixture of the thermoplastic resins mentioned with one another or with other thermoplastic resins. The front side barrier layer preferably contains pigments.

In einer weiteren Ausführungsform wird die Sperrschicht als wässrige Lösung eines wasserlöslichen filmbildenden Polymers aufgetragen und getrocknet. Geeignete wasserlösliche Polymere sind beispielsweise Polyvinylalkohole, filmbildende Stärkederivate, filmbildende Cellulosederivate, Copolymere der Acrylsäure mit anderen Vinylmonomeren, Alginate, Kasein, Polyacrylamid, Polystyrolsulfonat oder Mischungen dieser Polymere untereinander oder mit anderen in Wasser gelösterroder dispergierten Stoffen. Die Dicke der getrockneten Sperrschicht beträgt je nach Art des Polymers zwischen 4 und 30 pm.In a further embodiment, the barrier layer is applied as an aqueous solution of a water-soluble film-forming polymer and dried. Suitable water-soluble polymers are, for example, polyvinyl alcohols, film-forming starch derivatives, film-forming cellulose derivatives, copolymers of acrylic acid with other vinyl monomers, alginates, casein, polyacrylamide, polystyrene sulfonate or mixtures of these polymers with one another or with other substances dissolved or dispersed in water. The fat The dried barrier layer is between 4 and 30 pm, depending on the type of polymer.

In einer dritten Ausführungsform wird die Sperrschicht aus der wässrigen Dispersion eines in Wasser unlöslichen Polymerisates oder aus einer Mischung einer solchen Polymerisatdispersion mit einem in Wasser gelösten wasserlöslichen Bindemittel hergestellt. Geeignete Polymerisatdispersionen sind Dispersionen mit Äthylen-Polymeren und -Copolymeren, Acrylat- oder Methacrylat-Polymeren und -Copolymeren, Vinylacetat-Copolymeren sowie Mischungen solcher Polymerisatdispersionen untereinander, die bei den in der Papiermaschine oder in der Streichmaschine üblichen Trocknungstemperaturen filmbildend sind. Die Dicke der getrockneten Sperrschicht beträgt bei Herstellung aus wässriger Dispersion zwischen 4 und 30 µm.In a third embodiment, the barrier layer is produced from the aqueous dispersion of a water-insoluble polymer or from a mixture of such a polymer dispersion with a water-soluble binder dissolved in water. Suitable polymer dispersions are dispersions with ethylene polymers and copolymers, acrylate or methacrylate polymers and copolymers, vinyl acetate copolymers and mixtures of such polymer dispersions with one another which are film-forming at the drying temperatures customary in the paper machine or in the coating machine. The thickness of the dried barrier layer is between 4 and 30 μm when it is produced from an aqueous dispersion.

Grundsätzlich kann die Sperrschicht alle üblichen Zusätze und Hilfsmittel wie Pigmente, Farbstoffe. Aufheller, Weichmacher, Elektrolyte u.a. enthalten. Ausgenommen ist lediglich die Verwendung von größeren Mengen an freien Netzmitteln. Konkret bedeutet dies, daß die Oberflächenspannung einer wässrigen Streichmischung vorzugsweise nicht kleiner als 55 mN/m sein sollte. Insbesondere sind nichtionische Netzmittel in der Sperrschicht möglichst zu vermeiden.In principle, the barrier layer can contain all the usual additives and auxiliaries such as pigments, dyes. Brighteners, plasticizers, electrolytes etc. contain. The only exception is the use of larger amounts of free wetting agents. Specifically, this means that the surface tension of an aqueous coating mixture should preferably not be less than 55 mN / m. In particular, non-ionic wetting agents in the barrier layer should be avoided as far as possible.

Auf die wasserfreie Sperrschicht wird entweder direkt oder nach Vornahme einer haftungsverbessernden Vorbehandlung eine durch Elektronenstrahlen härtbare Mischung aufgezogen und durch Einwirkung von Elektronenstrahlen verfestigt. Auf diese mittels Elektronenstrahlen gehärtete Schicht werden, gegebenenfalls auch nach Anbringung einer Haftschicht, übliche fotografische Schichten auf der Basis von fotokatalytischen Redoxsystemen, beispielsweise Silbersalzen, aufgetragen.A mixture curable by electron beams is applied to the water-free barrier layer either directly or after carrying out an adhesion-improving pretreatment and solidified by the action of electron beams. Conventional photographic layers based on photocatalytic redox systems, for example silver salts, are applied to this layer hardened by means of electron beams, optionally also after applying an adhesive layer.

Der mittels Elektronenstrahlen verfestigte Überzug enthält neben dem Bindemittel vorzugsweise Pigmente und gegebenenfalls kleine Mengen an Farbstoffen und/oder anderen Zusatzstoffen. Ein Überzug hat ein Flächengewicht von etwa 10 bis 60 g/m2 (vorzugsweise 15 bis 40 g/m2).The coating consolidated by means of electron beams preferably contains pigments and optionally small amounts of dyes and / or other additives in addition to the binder. A coating has a basis weight of about 10 to 60 g / m 2 (preferably 15 to 40 g / m 2 ).

Die härtbare Mischung wird unter Verwendung eines der bekannten Beschichtungsverfahren aufgetragen, egalisiert und nach Abdeckung mit einem Schutzgas mittels Elektronenstahlen ausgehärtet. Sie kann aber auch gemäß der DE-OS 3 022 709 nach Auftragung gegen eine formgebende Oberfläche gedrückt werden und dann ohne Anwendung eines Schutzgases durch Papier- und Sperrschichten hindurch mittels Elektronenstrahlen verfestigt werden. Schlieslich können die beidseitigen Schichten gemäß der DE-OS 3 022 709 auch in einem Arbeitsgang aufgetragen und gleichzeitig verfestigt werden.The curable mixture is applied using one of the known coating processes, leveled and, after being covered with a protective gas, cured by means of electron beams. However, according to DE-OS 3 022 709, it can also be pressed against a shaping surface after application and then solidified by means of electron beams through paper and barrier layers without the use of a protective gas. Finally, the two-sided layers according to DE-OS 3 022 709 can also be applied in one operation and solidified at the same time.

Das Bindemittel der durch Elektronenstrahlen härtbaren Schicht besteht im wesentlichen aus solchen Stoffen, die vor der Härtung c = c Doppelbindungen, z.B. in Form von Acrylat- oder Methacrylatgruppen enthalten.The binder of the layer curable by electron beams essentially consists of such substances that c = c double bonds, e.g. contained in the form of acrylate or methacrylate groups.

Es kann auch kleinere Anteile an nicht härtbaren polymeren, oligomeren oder niedermolekularen Substanzen enthalten, soweit solche Zusätze zur Verbesserung bestimmter Eigenschaften sinnvoll sind und den Charakter einer durch Elektronenstrahlen härtbaren Mischung nicht grundsätzlich verändern. Bevorzugte Pigmente in einer mittels Elektronenstrahlen zu härtenden Schicht sind Weißpigmente, z.B. Titanoxid, Zirkonoxid, Zinkoxid, Zinksulfid, Antimonoxid, Bariumsulaft, Calciumcarbonat. Für spezielle Anwendungszwecke oder aus geschmacklichen Erwägungen können auch Farbpigmente, Ruß oder lösliche Farbstoffe in der Schicht enthalten sein. Die Schicht kann aber auch transparent sein.It can also contain smaller proportions of non-curable polymeric, oligomeric or low molecular weight substances, as long as such additives are useful for improving certain properties and do not fundamentally change the character of a mixture curable by electron beams. Preferred pigments in a layer to be hardened by means of electron beams are white pigments, e.g. Titanium oxide, zirconium oxide, zinc oxide, zinc sulfide, antimony oxide, barium sulfate, calcium carbonate. Color pigments, carbon black or soluble dyes can also be contained in the layer for special purposes or for taste considerations. However, the layer can also be transparent.

Im allgemeinen wird die Papierrückseite des erfindungsgemäß hergestellten mehrschichtigen Trägermaterials gleichfalls mit Sperrschicht und härtbarer Schicht sowie gegebenenfalls weiteren Schichten überzogen. Für einfache Anwendungen ist jedoch der einseitige Mehrschichtaufbau gemäß der Erfindung ausreichend.In general, the back of the paper of the multi-layer carrier material produced according to the invention is also coated with a barrier layer and a hardenable layer and optionally further layers. However, the single-sided multilayer structure according to the invention is sufficient for simple applications.

Über der vorderseitigen durch Elektronenstrahlen gehärteten Schicht werden, gegebenenfalls nach Aufbringung einer weiteren Zwischenschicht, eine oder mehrere fotografische Schichten auf der Basis von Silbersalzemulsionen für Schwarz/Weiß- oder Farbfotografien angeordnet.One or more photographic layers based on silver salt emulsions for black / white or color photographs are arranged over the front-side layer hardened by electron beams, optionally after application of a further intermediate layer.

Zum besseren Verständnis des Aufbaus des erfindungsgemäßen Trägermaterials sind in den Abbildungen 1-3 verschiedene Ausführungsformen im Querschnitt dargestellt.For a better understanding of the structure of the carrier material according to the invention, different embodiments are shown in cross section in FIGS. 1-3.

In den Zeichnungen ist jeweils mit 1 die fotografische Schicht bezeichnet, die ihrerseits aus mehreren Schichten bestehen kann. 2 bezeichnet eine gegebenenfalls vorhandene haftungsvermittelnde Zwischenschicht, 3 bezeichnet die vorderseitige mittels Elektronenstrahlen verfestigte und vorzugsweise Pigment enthaltende Schicht, 4 bezeichnet die vorderseitige Sperrschicht, 5 bezeichnet das fotografische Basispapier mit einer hydrophobierenden Innenleimung und/oder gegebenenfalls einer Oberflächenleimung, 6 bezeichnet die rückseitige Sperrschicht, 7 bezeichnet eine weitere durch Elektronenstrahlen gehärtete Schicht und 8 bezeichnet eine weitere funktionelle Rückseitenschicht.In the drawings, 1 denotes the photographic layer, which in turn can consist of several layers. 2 denotes an optionally present adhesion-promoting intermediate layer, 3 denotes the front layer which is solidified by means of electron beams and preferably contains pigment, 4 denotes the front barrier layer, 5 denotes the photographic base paper with a hydrophobizing inner sizing and / or optionally a surface sizing, 6 denotes the rear barrier layer, 7 denotes another layer hardened by electron beams and 8 denotes another functional back layer.

Die Erfindung wird nun anhand der nachfolgenden Beispiele näher erläutert.The invention will now be explained in more detail with reference to the following examples.

Beispiel 1example 1

Ein ca. 80 g/m2 schweres fotografisches Basispapier, das innen mit Alkylketendimer und Polyamidepichlorhydrin-Harz geleimt ist und eine Oberflächenleimung aus anionischer Stärke mit NaCI erhalten hat, wird beidseitig mittels Extrusionsbeschichtung mit ca. 12 g/m2 einer Polyäthylenmischung beschichtet. Die Polyäthylenmischung enthält ca. 10 Gew.-% Titandioxid und 0,2 Gew.-% Kobaltviolett-Pigment.A photographic base paper weighing approx. 80 g / m 2 , which is glued on the inside with alkyl ketene dimer and polyamide epichlorohydrin resin and which has been given a surface sizing made from anionic starch with NaCl, is coated on both sides by means of extrusion coating with approx. 12 g / m 2 of a polyethylene mixture. The polyethylene mixture contains approx. 10% by weight of titanium dioxide and 0.2% by weight of cobalt violet pigment.

Es hat sich gezeigt, daß die Art, die Dicke oder das Molekulargewicht oder eventuelle Abmischungen mit anderen thermoplastischen Stoffen keinen Einfluß auf die Sperrwirkung haben. Polyäthylen steht stellvertretend für alle extrudierbaren thermoplastischen Polymere.It has been shown that the type, the thickness or the molecular weight or any blends with other thermoplastic substances have no influence on the barrier effect. Polyethylene represents all extrudable thermoplastic polymers.

Teile des so vorbeschichteten Papieres werden dann jeweils nach Coronabehandlung der Poly- äthylenoberflächen auf beiden Seiten gemäß dem in der DE-OS 3 022 709 beschriebenen Verfahren mit je 25 g/m2 von strahlenhärtbaren Mischungen überzogen und diese mittels Elektronenstrahlen verfestigt. Dabei wird der Überzug der einen Seite jeweils in Kontakt mit einem Hochglanzzylinder durch das Papier hindurch und der Überzug der entgegengesetzten Seite nach Egalisierung jeweils unter Stickstoff als Schutzgas verfestigt. Die Verfestigung geschieht mittels Elektronenstrahlen mit einer Energiedosis von 40 J/g.Parts of the thus pre-coated paper are then respectively by corona treatment of the poly äthylenoberflächen on both sides according to the method described in DE-OS 3,022,709 with 25 g / m 2 coated with radiation-curable mixtures, and this is solidified by means of electron beams. The coating on one side is solidified through the paper in contact with a high-gloss cylinder, and the coating on the opposite side is solidified under nitrogen as a protective gas after equalization. The solidification takes place by means of electron beams with an energy dose of 40 J / g.

Die verwendeten härtbaren Mischungen bei den verschiedenen Proben des Beispiels waren wie folgt zusammengesetzt:

  • A) 51,60 Gew.-% Polyesteracrylat (M = ca. 1000 mit 4 Acrylgruppen je MG)
    • 13,00 Gew.-% Hexandioldiacrylat
    • 19,00 Gew.-% Oligotriacrylat (MG = 480)
    • 16,00 Gew.-% Titandioxid (Rutiltype mit organischer Oberflächenbehandlung)
    • 0,35 Gew.-% Celluloseacetobutyrat
    • 0,05 Gew.-% Zinkrizinoleat
  • B) 18,00 Gew.-% Polyesteracrylat (M = ca. 1000 mit 4 Acrylatgruppen je MG)
    • 18,00 Gew.-% Epoxiharzacrylat (M = ca. 2400 mit 2 Acrylatgruppen je MG)
    • 4,00 Gew.-% 2-hydroxiäthylacrylat
    • 8,00 Gew.-% Tripropylenglykoldiacrylat 20,00 Gew.-% Hexandioldiacrylat
    • 20,00 Gew.-% Titandioxid, Rutil (mittl. 0 0,32 µm mit AI + Si stabilisiert)
    • 10,00 Gew.-% Calciumcarbonat (oberflächenveredelt mit Ca-resinat)
    • 0,0025 Gew.-% Tetrachlor-Thioindigo
    • 0,0025 Gew.-% Phthalocyaninblau-Pigment 1,995 Gew.-% Perfluoralkylester FC 430
  • C) 25 Gew.-% Polyesteracrylat (M = ca. 1000 mit 4 Acrylatgruppen je MG)
    • 12 Gew.-% Hexandioldiacrylat
    • 8 Gew.-% N-Vinylpyrrolidon
    • 10 Gew.-% Polyesterweichmacher aus
    • Phthalsäure und Äthylenglykol 5 Gew.-% Xylylenglykoldiacrylat 40 Gew.-% Titandioxid, Anatas (mittl. Teilchendurchmesser ca. 0,35 µm).
  • D) 27 Gew.-% aliphatisches Polyurethanacrylat (M = ca. 4000 mit 3 Acrylatgruppen je MG)
    • 16 Gew.-% Hexandioldiacrylat
    • 3 Gew.-% Trimethylolpropantriacrylat
    • 4 Gew.-% Äthylenglykolmonoacrylat
    • 5 Gew.-% Aziridin
    • 15 Gew.-% Titandioxid, Anatas
    • 20 Gew.-% Bariumsulfat (mittl. Teilchendurchmesser ca. 0,8 um).
  • E) 5 Gew.-% Polystyrolharz (M = ca. 325)
    • 10 Gew.-% Vinylacetatcopolymer mit Vinylstearat
    • 5 Gew.-% Polyesterweichmacher aus Phthalsäure und Glykol
    • 20 Gew.-% Tripropylenglykoldiacrylat
    • 30 Gew.-% Hexandioldiacrylat
    • 10 Gew.-% Trimethylolpropantriacrylat
    • 4 Gew.-% Äthylenglykolmonoacrylat
    • 16 Gew.-% Titandioxid, Rutil
  • F) 29 Gew.-% Polyesteracrylat (M = ca. 1000 mit 4 Acrylgruppen je MG)
    • 9 Gew.-% Oligotriacrylat
    • 6 Gew.-% Hexandioldiacrylat
    • 6 Gew.-% N-Vinylpyrrolidon
    • 50 Gew.-% Titandioxid, Rutil
  • G) 40 Gew.-% Epoxiharzdiacrylat
    • 10 Gew.-% Pentaerythritoltriacrylat
    • 12 Gew.-% Hexandioldiacrylat
    • 7,8 Gew.-% Cyclohexylacrylat
    • 0,2 Gew.-% Ethyltriphenylphosphoran
    • 30 Gew.-% Titandioxid, Anatas
The curable mixtures used in the different samples of the example were composed as follows:
  • A) 51.60% by weight polyester acrylate (M = approx. 1000 with 4 acrylic groups per MG)
    • 13.00 wt% hexanediol diacrylate
    • 19.00% by weight of oligotria acrylate (MW = 480)
    • 16.00% by weight titanium dioxide (rutile type with organic surface treatment)
    • 0.35% by weight cellulose acetobutyrate
    • 0.05% by weight zinc ricinoleate
  • B) 18.00% by weight polyester acrylate (M = approx. 1000 with 4 acrylate groups per MG)
    • 18.00% by weight epoxy resin acrylate (M = approx. 2400 with 2 acrylate groups per MG)
    • 4.00% by weight of 2-hydroxyethyl acrylate
    • 8.00% by weight tripropylene glycol diacrylate 20.00% by weight hexanediol diacrylate
    • 20.00% by weight titanium dioxide, rutile (average 0 0.32 µm stabilized with Al + Si)
    • 10.00% by weight calcium carbonate (surface refined with Ca resinate)
    • 0.0025 wt% tetrachloro-thioindigo
    • 0.0025% by weight phthalocyanine blue pigment 1.995% by weight perfluoroalkyl ester FC 430
  • C) 25% by weight polyester acrylate (M = approx. 1000 with 4 acrylate groups per MG)
    • 12% by weight hexanediol diacrylate
    • 8% by weight N-vinyl pyrrolidone
    • 10 wt .-% polyester plasticizer
    • Phthalic acid and ethylene glycol 5% by weight xylylene glycol diacrylate 40% by weight titanium dioxide, anatase (average particle diameter approx. 0.35 µm).
  • D) 27% by weight of aliphatic polyurethane acrylate (M = approx. 4000 with 3 acrylate groups per MG)
    • 16% by weight hexanediol diacrylate
    • 3% by weight trimethylolpropane triacrylate
    • 4% by weight of ethylene glycol monoacrylate
    • 5% by weight aziridine
    • 15% by weight titanium dioxide, anatase
    • 20% by weight of barium sulfate (average particle diameter approx. 0.8 μm).
  • E) 5% by weight polystyrene resin (M = approx. 325)
    • 10% by weight vinyl acetate copolymer with vinyl stearate
    • 5% by weight polyester plasticizer made from phthalic acid and glycol
    • 20% by weight tripropylene glycol diacrylate
    • 30% by weight hexanediol diacrylate
    • 10% by weight trimethylolpropane triacrylate
    • 4% by weight of ethylene glycol monoacrylate
    • 16% by weight titanium dioxide, rutile
  • F) 29% by weight polyester acrylate (M = approx. 1000 with 4 acrylic groups per MG)
    • 9% by weight oligotria acrylate
    • 6% by weight hexanediol diacrylate
    • 6% by weight of N-vinyl pyrrolidone
    • 50% by weight titanium dioxide, rutile
  • G) 40% by weight epoxy resin diacrylate
    • 10% by weight pentaerythritol triacrylate
    • 12% by weight hexanediol diacrylate
    • 7.8% by weight of cyclohexyl acrylate
    • 0.2% by weight of ethyl triphenylphosphorane
    • 30% by weight titanium dioxide, anatase

Beispiel 2Example 2

Ein ca. 110 g/m2 schweres und wie im Beispiel 1 geleimtes fotografisches Basispapier wird beidseitig mittels Rakel mit einer Mischung der folgenden Zusammensetzung überzogen und getrocknet:

  • 60 Gew.-% 50%ige Polymerisatdispersion von Äthylacrylat/Vinylacetat/Acrylsäure-Copolymer
  • 10 Gew.-% Natriumpolystyrolsulfonat (M = 40.000)
  • 1 Gew.-% Natriumpolyacrylat (M = ca. 5000)
  • 0,5 Gew.-% konz. NHa-Lösung
  • 18 Gew.-% Wasser
  • 10 Gew.-% Titandioxid, Anatas
  • 0,5 Gew.-% Papierblaufarbstoff (Papierblau S der Firma Bayer).
A photographic base paper weighing approximately 110 g / m 2 and sized as in Example 1 is coated on both sides with a doctor blade with a mixture of the following composition and dried:
  • 60% by weight 50% polymer dispersion of ethyl acrylate / vinyl acetate / acrylic acid copolymer
  • 10% by weight sodium polystyrene sulfonate (M = 40,000)
  • 1% by weight sodium polyacrylate (M = approx. 5000)
  • 0.5 wt .-% conc. NH a solution
  • 18% by weight water
  • 10% by weight titanium dioxide, anatase
  • 0.5% by weight of paper blue dye (Paper Blue S from Bayer).

Der getrocknete Sperrschicht-Überzug hat ein Flächengewicht von ca. 15 g/m2 je Seite. Er wird mit Hilfe einer Kalandriervorrichtung geglättet und gemäß Beispiel 1, Rezeptur F, beidseitig mit je 20 g/m2 einer durch Elektronenstrahlen gehärteten Schicht überzogen.The dried barrier coating has a weight per unit area of approximately 15 g / m 2 . It is smoothed with the aid of a calendering device and, according to example 1, recipe F, is coated on both sides with 20 g / m 2 of a layer hardened by electron beams.

Beispiel 3Example 3

Ein ca. 100 g/m2 schweres und wie im Beispiel 1 geleimtes fotografisches Basispapier wird innerhalb einer Papiermaschine beidseitig mit Hilfe einer Twinblade-Streicheinrichtung mit einer Lösung der folgenden Zusammensetzung überzogen:

  • 14 Gew.-% Hydroxipropylstärkeäther (Solfarex A 115 der Firma Scholten's Chemische Fabrieken)
  • 5 Gew.-% Natriumsalz eines 1 :1 1 Styrol/ Maleinsäureanhydrit-Copolymers
  • 0,1 Gew.-% Remastrahlblau FFRL 80,9 Gew.-% Wasser. Der nach Trocknung und Glättung erhaltene Sperrschicht-Überzug hat ein Flächengewicht von ca. 7 g/m2 je Seite. Das so vorbeschichtete Papier wird anschließend gemäß Beispiel 1, Rezeptur F, beidseitig mit je 30 g/m2 einer durch Elektronenstrahlen gehärteten Schicht überzogen.
An approx. 100 g / m 2 heavy photographic base paper as sized in Example 1 is coated on both sides in a paper machine with the aid of a Twinblade coating device with a solution of the following composition:
  • 14% by weight of hydroxypropyl starch ether (Solfarex A 115 from Scholten's Chemische Fabrieken)
  • 5% by weight sodium salt of a 1: 1 1 styrene / maleic anhydrite copolymer
  • 0.1% by weight of Remastrahlblau FFRL 80.9% by weight of water. The barrier coating obtained after drying and smoothing has a weight per unit area of approximately 7 g / m 2 . The paper precoated in this way is then coated on both sides with 30 g / m 2 of a layer hardened by electron beams in accordance with Example 1, recipe F.

Beispiel 4Example 4

Ein ca. 100 g/m2 schweres und wie im Beispiel 1 geleimtes fotografisches Basispapier wird einseitig mit einer Mischung der folgenden Zusammensetzung überzogen:

  • 20 Gew.-% Äthylen/Vinylacetat-(30/70)-Copolymer-Dispersion (50%ig)
  • 8 Gew.-% Polyvinylalkohol, mittelviskos
  • 2 Gew.-% Natriumalginat, mittelviskos
  • 10 Gew.-% Titandioxid, Anatas
  • 60 Gew.-% Wasser.
A photographic base paper weighing approximately 100 g / m 2 and sized as in Example 1 is coated on one side with a mixture of the following composition:
  • 20% by weight ethylene / vinyl acetate (30/70) copolymer dispersion (50%)
  • 8% by weight polyvinyl alcohol, medium viscosity
  • 2% by weight sodium alginate, medium viscosity
  • 10% by weight titanium dioxide, anatase
  • 60% by weight water.

Nach Trocknung beträgt der Schichtauftrag ca. 10 g/m2. Die getrocknete Schicht wird mittels eines erwärmten Kalanders geglättet und mit ca. 20 g/m2 einer härtbaren Mischung gemäß Rezeptur F aus Beispiel 1 überzogen, gegen einen Hochglanzzylinder gedrückt und von der unbeschichteten Papierseite her mittels Elektronenstrahlen mit einer Energiedosis von 40 J/g verfestigt.After drying, the layer application is approx. 10 g / m 2 . The dried layer is smoothed using a heated calender and coated with about 20 g / m 2 of a curable mixture according to recipe F from Example 1, pressed against a high-gloss cylinder and solidified from the uncoated paper side by means of electron beams with an energy dose of 40 J / g .

Beispiel 5Example 5

Ein ca. 70 g/m2 schweres fotografisches Basispapier, das mit epoxidiertem Difettsäureamid (R = C14 oder größer), Stärke/Polyacrylamid und Aluminiumstearat geleimt ist, wird in der Leimpresse der Papiermaschine beidseitig mit einer Mischung der folgenden Zusammensetzung überzogen:

  • 20 Gew.-% Polyesterharz-Dispersion, 30%ig
  • 5 Gew.-% Natriumcellulosesulfat (Substitutionsgrad ca. 1,5)
  • 10 Gew.-% Titandioxid, Anatas
  • 65 Gew.-% Wasser.
A photographic base paper weighing approx. 70 g / m 2 , which is sized with epoxidized difatty acid amide (R = C14 or larger), starch / polyacrylamide and aluminum stearate, is coated on both sides in the size press of the paper machine with a mixture of the following composition:
  • 20% by weight polyester resin dispersion, 30%
  • 5% by weight sodium cellulose sulfate (degree of substitution approx. 1.5)
  • 10% by weight titanium dioxide, anatase
  • 65% by weight water.

Nach Trocknung und Glättung beträgt der Schichtauftrag ca. 6 g/m2 je Seite. Das vorbeschichtete Papier wird einseitig mit ca. 25 g/m2 einer härtbaren Mischung entsprechend Rezeptur F aus Beispiel 1 überzogen, die ungehärtete Mischung gegen einen Hochglanzzylinder gedrückt und von der unbeschichteten Papierseite her mittels Elektronenstrahlen mit 40 J/g verfestigt. Dann wird die Gegenseite mit ca. 25 g/ m2 einer härtbaren Mischung überzogen, die folgende Zusammensetzung hat:

  • 40 Gew.-% Polyesteracrylat (M = ca. 1000 mit 4 Acrylgruppen je MG)
  • 12 Gew.-% Hexandioldiacrylat
  • 13 Gew.-% Oligotriacrylat
  • 10 Gew.-% Titandioxid, Rutil
  • 25 Gew.-% Gasruß.
After drying and smoothing, the layer application is approximately 6 g / m 2 per side. The precoated paper is coated on one side with approx. 25 g / m 2 of a curable mixture according to formula F from Example 1, the uncured mixture is pressed against a high-gloss cylinder and solidified from the uncoated paper side by means of electron beams at 40 J / g. Then the opposite side is coated with about 25 g / m 2 of a curable mixture, which has the following composition:
  • 40% by weight polyester acrylate (M = approx. 1000 with 4 acrylic groups per MG)
  • 12% by weight hexanediol diacrylate
  • 13% by weight oligotria acrylate
  • 10% by weight titanium dioxide, rutile
  • 25% by weight of soot.

Die Schicht wird unter Stickstoff mittels Elektronenstrahlen mit einer Energiedosis von 30 J/g verfestigt und bildet die Rückseite des fotografischen Trägers.The layer is solidified under nitrogen by means of electron beams with an energy dose of 30 J / g and forms the back of the photographic support.

Beispiel 6Example 6

Ein ca. 170 g/m2 schweres fotografisches Basispapier, das mit Alkylketendimer, Aluminiumstearat, Gelatine und Polyamidepichlorhydrinharz geleimt ist, wird beidseitig mit einer Streichmischung überzogen, die folgende Zusammensetzung hat:

  • 30 Gew.-% 40%iger Dispersion eines Copolymerisates aus Styrol/Äthylacrylat/Acrylamid (40 : 55: 5)
  • 8 Gew.-% Gelatine
  • 1 Gew.-% Polyacrylamid
  • 20 Gew.-% Kaolin
  • 41 Gew.-% Bariumsulfat.
A photographic base paper weighing approx. 170 g / m 2 and sized with alkyl ketene dimer, aluminum stearate, gelatin and polyamide epichlorohydrin resin is coated on both sides with a coating mixture which has the following composition:
  • 30% by weight 40% dispersion of a copolymer of styrene / ethyl acrylate / acrylamide (40: 55: 5)
  • 8% by weight gelatin
  • 1% by weight polyacrylamide
  • 20% by weight kaolin
  • 41% by weight barium sulfate.

Nach Trocknung beträgt das Flächengewicht der Sperrschicht ca. 25 g/m2 je Seite. Das vorbeschichtete Papier wird geglättet und gemäß Beispiel 1, Rezeptur F, einseitig mit ca. 15 g/m2 einer härtbaren Mischung überzogen. Die Mischung wird gegen einen Hochglanzzylinder gedrückt und von der Rückseite mittels Elektronenstrahlen mit 50 J/g verfestigt.After drying, the weight per unit area of the barrier layer is approx. 25 g / m 2 . The precoated paper is smoothed and, according to Example 1, recipe F, coated on one side with about 15 g / m 2 of a curable mixture. The mixture is pressed against a high-gloss cylinder and solidified from the back by means of electron beams at 50 J / g.

VergleichsbeispieleComparative examples

Als Vergleiche 7-12 wurden jeweils die in den Beispielen 1-6 benutzten Rohpapiere ohne vorherige Aufbringung der Sperrschichten direkt mit den in den Beispielen angegebenen strahlenhärtbaren Mischungen überzogen. Dabei wurde das Überzugsgewicht jeweils um den Betrag erhöht, den die halbe Sperrschicht ausmacht. Die Überzüge wurden wie in den zugehörigen Beispielen mittels Elektronenstrahlen mit der in den Beispielen angegebenen Energiedosis verfestigt.As comparisons 7-12, the base papers used in Examples 1-6 were coated directly with the radiation-curable mixtures specified in the examples without prior application of the barrier layers. The coating weight was increased by the amount that makes up half the barrier layer. As in the associated examples, the coatings were solidified by means of electron beams with the energy dose given in the examples.

Als Vergleichsbeispiel 13 wurde ein standardgemäß beidseitig mit Polyäthylen überzogenes fotografisches Trägerpapier genommen, das gemäß Vergleichsbeispiel A aus DOS 3 022 451 vorderseitig mit einer 15/85-Titandioxid/Polyäthylen- mischung und rückseitig mit einer nicht pigmentierten Polyäthylenschicht überzogen war.A comparative example 13 was taken from a photographic carrier paper coated on both sides with polyethylene, which according to comparative example A from DOS 3 022 451 was coated on the front with a 15/85 titanium dioxide / polyethylene mixture and on the back with a non-pigmented polyethylene layer.

Prüfung der TrägermaterialienExamination of the carrier materials

Der Effekt der Sperrschichten wurde mit dem Hercules-Leimungsprüfgerät unter Verwendung von Hexandioldiacrylat (HDDA) als Prüfmittel bestimmt. Das Gerät und seine Funktion sind beschrieben in dem Merkblatt «Hercules - Lei- mungsgradprüfer" der Hercules NV. Den Haag (Holland). Diese Prüfungen wurden jeweils vor Aufbringung des härtbaren Überzugs an den Papieren durchgeführt.The effect of the barrier layers was determined with the Hercules sizing tester using hexanediol diacrylate (HDDA) as test equipment. The device and its function are described in the leaflet "Hercules - degree of performance tester " from Hercules NV. The Hague (Holland). These tests were carried out before the hardenable coating was applied to the papers.

Die Wirkung der Sperrschichten auf Schleier und Empfindlichkeit der fotografischen Schichten wurde auf zweierlei Art ermittelt. Zunächst wurden Muster der mit strahlengehärteten Schichten überzogenen Beispiele und Vergleichsbeispiele sowie Muster der zugehörigen Basispapiere je zwischen zwei Blatt handelsüblichen fotografischen Bromsilberpapiers gelegt und so im Dunkeln vier Tage bei 60°C und 80% relativer Luftfeuchte gelagert. Bei dieser Kontaktlagerprüfung waren die Blätter einer Druckbelastung von etwa 2.9 Pa ausgesetzt. Nach Ablauf der 4-Tage-Kontaktprüfung wurden die Prüflinge entnommen und die mit den Prüflingen in Kontakt gewesenen fotografischen Papiere zu einem mittleren Grauton belichtet und entwickelt und die jeweils mit den Prüflingen in Kontakt gewesenen Flächen mit den umgebenden Flächen verglichen. Eine eventuell vorhandene Abweichung im Grauton wurde bewertet und in einer 6er Skala benotet. Dabei bedeutet:

  • 1 - keine Abweichung
  • 2 - kaum sichtbare Abweichung
  • 3 - sichtbare Abweichung
  • 4 - deutliche Abweichung
  • 5 - starke Abweichung
  • 6 - extreme Abweichung
The effect of the barrier layers on fog and sensitivity of the photographic layers was determined in two ways. First, samples of the examples and comparative examples coated with radiation-hardened layers and samples of the associated base papers were each placed between two sheets of commercially available photographic bromine silver paper and thus stored in the dark for four days at 60 ° C. and 80% relative atmospheric humidity. In this contact bearing test, the blades were exposed to a pressure load of approximately 2.9 Pa. After the 4-day contact test, the test specimens were removed and the photographic papers that had been in contact with the test specimens were exposed and developed to a medium shade of gray, and each with the surfaces in contact with the test objects compared with the surrounding surfaces. A possible deviation in the gray tone was assessed and graded on a 6-point scale. Here means:
  • 1 - no deviation
  • 2 - barely visible deviation
  • 3 - visible deviation
  • 4 - significant deviation
  • 5 - large deviation
  • 6 - extreme deviation

Eine Abweichung vom Vergleichsgrauton zeigte sich immer als Sensibilisierung (= dunkler).A deviation from the comparison gray tone always showed itself as sensitization (= darker).

Bei der zweiten fotografischen Prüfung wurden die mit strahlengehärteten Schichten überzogenen Papiere nach Coronabehandlung der Oberfläche mit einer üblichen feinkörnigen Schwarzweiß-Silberhalogenidemulsionsschicht mit hohem Auflösungsvermögen überzogen.In the second photographic test, after the corona treatment of the surface, the papers coated with radiation-hardened layers were coated with a conventional fine-grained black and white silver halide emulsion layer with high resolution.

Teile der so hergestellten lichtempfindlichen Papiere wurden lichtdicht verpackt und ein Jahr bei Zimmertemperatur gelagert. Dann wurden sie standardmäßig entwickelt und der jeweils entstandene Schleier wurde mit dem Densitometer ausgemessen. Die erhaltenen Meßwerte sind mit den anderen Prüfdaten in Tabelle 1 zusammengestellt.Parts of the light-sensitive papers produced in this way were packed light-tight and stored for one year at room temperature. Then they were developed as standard and the respective veil was measured with the densitometer. The measured values obtained are summarized in Table 1 with the other test data.

Andere Teile der wie beschrieben hergestellten lichtempfindlichen Papiere wurden durch ein Testnegativ bildmäßig belichtet und in üblicher Weise entwickelt und fixiert.Other parts of the photosensitive papers prepared as described were imagewise exposed through a test negative and developed and fixed in a conventional manner.

Das verwendete Testnegativ war ein Linienraster, das in Form eines Verlaufkeiles hergestellt war. Aus dem unterschiedlichen Verlauf der optischen Dichte über den Verlaufkeil ermöglicht das aufkopierte Linienraster eine vergleichende Aussage über die Schärfeleistung der verschiedenen Proben. Die relativen Bildschärfezahlen sind ebenfalls in Tabelle 1 zusammengestellt. Dabei sind alle Werte auf die Probe mit der relativ höchsten Schärfeleistung bezogen. (d.i. Beispiel 1 F = 100%).

Figure imgb0001
The test negative used was a line grid, which was made in the form of a gradient wedge. From the different course of the optical density over the course wedge, the copied line grid enables a comparative statement about the sharpness performance of the different samples. The relative sharpness figures are also shown in Table 1. All values are based on the sample with the relatively highest sharpness. (di example 1 F = 100%).
Figure imgb0001

Es sind weitere Ausgestaltungen der Erfindung möglich. In einer Variante kann der mittels Elektronenstrahlen härtbaren Mischung zur Erhöhung der Weiße neben Weißpigment und gegebenenfalls Farbpigment ein optischer Aufheller, z.B. vom Aminocumarintyp, wie er von der Firma ACC unter der Bezeichnung «Calcofluor White RW» in den Handel gebracht wird, zugefügt sein. Es ist ferner möglich, das Basispapier einzufärben und es kann eine Seite des Papieres mit einer Ruß enthaltenden Schicht überzogen werden, während die andere mit einer weißen Schicht überzogen wird.Further refinements of the invention are possible. In a variant, the mixture curable by means of electron beams can be used to increase the whiteness in addition to white pigment and optionally color pigment, an optical brightener, e.g. of the aminocoumarin type, as marketed by the ACC company under the name "Calcofluor White RW". It is also possible to color the base paper and to coat one side of the paper with a layer containing carbon black while the other is coated with a white layer.

In einer speziellen Ausführungsform ist es auch möglich, eine wässrige Sperrschicht aufzutragen und diese ohne Zwischentrocknung mit der strahlenhärtbaren Mischung zu überziehen. Überraschenderweise kann die härtbare Mischung auch dann ohne nachteilige Begleiterscheinung gehärtet werden, während das Wasser zunächst vom Basispapier aufgenommen und über die Rückseite entfernt wird, nachdem die Härtung vollzogen ist.In a special embodiment, it is also possible to apply an aqueous barrier layer and to coat it with the radiation-curable mixture without intermediate drying. Surprisingly, the curable mixture can also be cured without adverse side effects, while the water is first absorbed by the base paper and removed via the back after the curing has been carried out.

Beidseitig wasserfest überzogene Papiere sind in der Regel nur auf der Seite mit Sperrschicht und Elektronenstrahlen gehärteter Schicht überzogen, die für die Beschichtung mit lichtempfindlichen Schichten vorgesehen ist. Die Gegenseite kann beliebig wasserfest überzogen sein gemäß eines der in der Literatur beschriebenen Verfahren. Dabei können alle bekannten Arten der Ausgestaltung der Oberfläche praktiziert werden, die durch die Anwendung der Papiere erforderlich werden, d.h. Rauhigkeit, Beschreibbarkeit, antistatische Eigenschaften und Rollverhalten der Papiere werden vorzugsweise über die Rückseitenbeschichtung gesteuert.Papers coated on both sides with water resistance are generally only coated on the side with a barrier layer and an electron beam hardened layer which is intended for coating with light-sensitive layers. The opposite side can be coated in any waterproof manner according to one of the methods described in the literature. All known types of surface design that are required by the use of the papers, i.e. Roughness, writeability, antistatic properties and rolling behavior of the papers are preferably controlled via the back coating.

Claims (23)

1. Water-resistant photographic paper support comprising several layers, the paper support being coated with a layer of a radiation-hardened lacquer, characterized in that between the base paper and the lacquer layer at least one barrier .layer is disposed, the thickness of which is 4 to 30 pm and the permeability of which to acrylate monomers, measured with the Hercules sizing tester, is not less than the value of 100 seconds.
2. Paper support according to Claim 1, characterized in that the barrier layer is of a polymeric film-forming material and possibly contains further additives.
3. Paper support according to Claims 1 to 2, characterized in that the barrier layer contains pigments, dyes, brighteners, plasticizers, electrolytes and other known admixtures.
4. Paper support according to Claim 3, characterized in that the barrier layer contains white pigments such as titanium dioxide, zirconium oxide, zinc oxide, zinc sulphide, antimony oxide, barium sulphate and calcium carbonate.
5. Paper support according to Claims 1 to 4, characterized in that the barrier layer is of a polyolefin or polyolefin copolymer.
6. Paper support according to Claims 1 to 5, characterized in that the barrier layer is of a (meth)acrylate polymer or copolymer.
7. Paper support according to Claims 1 to 6, characterized in that the barrier layer is of a film-forming starch derivative having a content of a synthetic film-forming polymer.
8. Paper support according to Claims 1 to 7, characterized in that the barrier layer is of polyvinyl alcohol or a combination with other watersoluble polymers or polymers which can be dispersed in water.
9. Paper support according to Claim 1, characterized in that the base paper is sized.
10. Paper support according to Claim 1, characterized in that the base paper is sized and surface- sized.
11. A method of making a multi-layer photographic support material on a paper basis, according to Claims 1 to 10, characterized by the combination of the following process steps:
a) application of a barrier layer having a thickness of 4 to 30 um, its permeability to acrylate monomers being not less than the value of 100 s, measured with the Hercules sizing tester, onto at least one surface of a base paper.
b) coating of the barrier layer with a flowable mixture which can be hardened by means of electron radiation and
c) hardening of the flowable mixture layer disposed over the barrier layer by means of electron radiation.
12. A method according to Claim 11, characterized by the combination of the following process steps:
a) application of a barrier layer having a thickness of 4 to 30 um, its permeability to acrylate monomers being not less than the value of 100 s, measured with the Hercules sizing tester, onto at least one surface of a base paper,
b) pretreatment of the surface of the barrier layer for the purpose of improving the bond of the hardenable coating to be applied subsequently,
c) coating of the pretreated surface of the barrier layer with a flowable mixture which can be hardened by means of electron radiation and
d) hardening of the hardenable mixture layer disposed over the barrier layer by means of electron radiation.
13. A method according to Claim 11 or 12, characterized in that the barrier layer is produced from a thermoplastics resin by means of an extrusion coating process.
14. A method according to Claim 11 or 12, characterized in that the barrier layer is formed by application of an aqueous dispersion of a film-forming substance or substance mixture with subsequent drying.
15. A method according to Claim 11 or 12, characterized in that the barrier layer is formed by application of an aqueous solution of a film-forming substance or substance mixture.
16. A method according to Claims 12 to 15, characterized in that the pretreatment of the surface of the barrier layer is a pretreatment having an oxidizing action.
17. A method according to Claim 16, characterized in that the oxidizing pretreatment is a corona discharge treatment.
18. A method according to Claims 12 to 15, characterized in that the pretreatment of the surface of the barrier layer is a separate bonding coating.
19. A method according to Claim 11 or 12, characterized in that the layer which can be hardened by means of electron radiation is hardened with an energy dose of 5-60 Joule/g (preferably 10 to 50 J/g).
20. A method according to Claims 11 to 19, characterized in that the surface of the layer hardened by means of electron radiation is subjected to a bond-improving pretreatment before the application of a photographic layer.
21. A method of making a multi-layer photographic support material on a paper base, according to Claims 11 to 20, characterized by the combination of the following process steps:
a) application of a coating consisting substantially of polyolefin onto both surfaces of a base paper,
b) oxidizing pretreatment of one of the two polyolefin surfaces,
c) coating of the pretreated polyolefin surface with a flowable mixture which can be hardened by means of electron radiation,
d) hardening of the hardenable layer by means of electron radiation.
22. A method according to Claims 11 to 21, characterized in that the layer which can be hardened by means of electron radiation is brought into contact with a shaping surface, is then hardened by means of electron radiation through the paper and thereafter is separated from the shaping surface.
23. A method according to Claims 11 to 21, characterized in that the layer which can be hardened by means of electron radiation is brought into contact with a shaping surface, is then hardened by means of electron radiation through the shaping material and thereafter is separated from the shaping surface.
EP83111927A 1983-01-03 1983-11-29 Water-proof photographic paper Expired EP0114973B1 (en)

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