EP0219615B1 - Water-proof paper support for photographic purposes - Google Patents

Water-proof paper support for photographic purposes Download PDF

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Publication number
EP0219615B1
EP0219615B1 EP86109856A EP86109856A EP0219615B1 EP 0219615 B1 EP0219615 B1 EP 0219615B1 EP 86109856 A EP86109856 A EP 86109856A EP 86109856 A EP86109856 A EP 86109856A EP 0219615 B1 EP0219615 B1 EP 0219615B1
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EP
European Patent Office
Prior art keywords
coating
weight
water
acid
phosphoric acid
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
EP86109856A
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German (de)
French (fr)
Other versions
EP0219615A1 (en
Inventor
Reiner Anthonsen
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
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Application filed by Felix Schoeller Jr Foto und Spezialpapiere GmbH, Felex Schoeller Jr and GmbH and Co KG filed Critical Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority to AT86109856T priority Critical patent/ATE40481T1/en
Publication of EP0219615A1 publication Critical patent/EP0219615A1/en
Application granted granted Critical
Publication of EP0219615B1 publication Critical patent/EP0219615B1/en
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—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
    • D21H19/46—Non-macromolecular organic compounds
    • D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Definitions

  • the invention relates to a waterproof paper support for photographic purposes, which contains at least one side of a coating hardened by means of electron beams.
  • Water-resistant coated paper supports for photographic purposes are known in various embodiments. Papers provided with extruded polyolefin layers have found wide application.
  • DE-A-3 022 451, DE-A-3 022 709 and DE-A-3 410 797 which have become known in recent times, describe paper supports whose base paper is provided with at least one coating produced in situ with the aid of electron beam curing.
  • Electron beam cured coatings have improved properties, such as: B. the increase in scratch resistance, the increase in pigment absorption or smoother surfaces. Like polyolefin coatings, they are resistant to photographic process solutions and therefore also protect the paper carrier underneath from the penetration of these solutions.
  • the coatings hardened with electron beams are produced according to DE-A-3 022 451 or DE-A-3 022 709 by applying a flowable mixture to the surface of the paper, distributing it evenly there and then solidifying it with high-energy electron beams under a protective gas or other covering .
  • the mixtures contain as a crucial component at least one substance with ethylenically unsaturated double bonds, which have the ability to polymerize with each other when initiated by radiation.
  • Suitable substances with ethylenically unsaturated double bonds are all vinyl or vinylidene compounds. Those substances which contain acrylate or methacrylate groups are preferably used. Esters of maleic acid, fumaric acid, mesaconic acid, citraconic acid or itaconic acid, other derivatives of these acids, allyl compounds and linear and cyclic dienes or trienes can also be used as reactive mixture components.
  • hexanediol acrylate, trimethylolpropane triacrylate, polyester acrylates, polyurethane acrylates, polyether acrylates, polyepoxy acrylates or alkyd resin acrylates are particularly suitable.
  • the mixture should preferably contain at least one substance which contains two or more double bonds.
  • the flow properties of curable mixtures are adjusted by mixing components of higher molecular weight with low molecular weight substances.
  • non-reactive substances without double bonds can also be contained in a mixture to a limited extent.
  • mixtures for the coatings curable by means of electron beams can contain pigments, dyes, optical brighteners, image stabilizers, antioxidants or other additives, insofar as this is desirable or necessary in view of the desired properties of an overlying photographic image.
  • the photographic layers are applied to the surface of the coating hardened by electron beams either directly or after prior application of an adhesion-promoting intermediate layer.
  • These photographic layers are preferably layers which are known under the term "silver salt photography" and are used to produce black / white or color images.
  • An advantage over polyolefin coatings is e.g. B. the increased pigment absorption capacity of the coatings hardened by means of electron beams.
  • the highest possible content of white pigment e.g. B. titanium oxide, desirable.
  • the hardened layer becomes so brittle in large quantities that stress cracks soon occur or that the layer adheres poorly to the substrate.
  • the discoloration does not occur on polyolefin surfaces, nor can it be observed on classic baryta papers.
  • EP-A-0 159 493 describes a way of obtaining coatings with reduced staining by means of the special composition of the curable components of a coating mixture. That there The method described is based on the fact that unsaturated hydroxyl-functional compounds are contained in the coating mixtures in a molar concentration of 2 or more than 2.
  • EP-A-0 176 656 describes the use of a special titanium dioxide as a white pigment to reduce the coloration of the electron beam-hardened coating in photographic color developers.
  • the special titanium dioxide used has a surface coating that makes up at least 2% by weight of the total pigment.
  • the surface covering is an inorganic oxide or hydrated oxide and can be an aluminum oxide, silica, zinc oxide, magnesium oxide, tin oxide, zirconium oxide, antimony oxide or one of the alkaline earth metal oxides or mixtures of such compounds.
  • acrylated or methacrylated phosphoric acid with average molecular weights of 400 to 600 or monomeric itaconic acid are used.
  • the number of reactive, unsaturated groups determines the degree of crosslinking of the substances according to the invention with one another after curing by means of electron beams.
  • the degree of crosslinking is important for anchoring the substances according to the invention in the radiation-hardened layer during exposure to the photographic baths.
  • the effect according to the invention results in particular from the use of substances which, in addition to free acid groups, also contain reactive, unsaturated groups which can be crosslinked by radiation.
  • the acrylated or methacrylated phosphoric acids used according to the invention have a ratio of reactive, unsaturated groups to polar acid groups of 1: 2 to 2: 1, ie. H. per molecule are on average z. B. 1.5 free acid groups and 1.5 acrylate or methacrylate groups.
  • Monomeric itaconic acid has a ratio of unsaturated to polar groups of 1: 2 and is also suitable.
  • the substances according to the invention can be added in amounts of 1-15% by weight, but preferably 4-10% by weight, based on the coating mixture.
  • color pigments of any type and dispersion aids, dyes and other substances which have a favorable effect on the image quality to the coating mixtures, without adversely affecting the effect according to the invention.
  • the coatings according to the invention can be produced and solidified in any manner according to one of the known processes and have different surface structures (e.g. according to DE-C-2 515 261, DE-A-3 022 709 or EP-A-0 159 493.
  • the base paper is also waterproof coated on the opposite side.
  • This coating can also consist of a mixture according to the invention, but also of polyolefin. Several identical or different coatings can also be placed on top of each other.
  • the substances according to the invention are used in the mixtures for radiation-curable coatings, the discoloration in the color developer baths is avoided.
  • the hardened layer is scratch-resistant, and even with a high pigment content it has sufficient elasticity to prevent stress cracks and to ensure that the layer adheres sufficiently to the base paper.
  • the amount of layers applied was approximately 20 g / m 2 .
  • the coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.
  • the amount of layers applied was approximately 20 g / m 2 .
  • the coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.
  • the amount of layers applied was approximately 20 g / m 2 .
  • the coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.
  • the amount of layers applied was approximately 20 g / m 2 .
  • the coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.
  • the amount of layers applied was approximately 20 g / m 2 .
  • the coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.
  • the amount of layers applied was approximately 20 g / m 2 .
  • the coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.
  • the amount of layers applied was approximately 20 g / m 2 .
  • the coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.
  • the folding causes only a part of the pattern to come into contact with the developer solution, so that a direct comparison between the treated and the untreated area on the same pattern is possible.
  • the sample After treatment with the color developer, the sample is watered for 2 hours, mechanically dried and then stored for four days at room temperature under the influence of daylight.
  • the extent of the yellowing is determined densiometrically in accordance with DIN 4512.

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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)

Abstract

There is described a water-resistant paper support for photographic purposes with at least one coating which is hardened by electron beams, wherein the resin layer forming the coating contains acrylated or methacrylated phosphoric acid with a ratio of acrylate or methacrylate groups to acid groups of 1:2 to 2:1, or itaconic acid, and wherein this acrylated or methacrylated phosphoric acid or the itaconic acid in the resin mixture forming the coating amounts to 1 to 15 weight %, and preferably 4 to 10 weight %, relative to the entire mixture, and the acrylated or methacrylated phosphoric acid possesses an average molecular weight of 400 to 600.

Description

Die Erfindung betrifft einen wasserfesten Papierträger für fotografische Zwecke, der zumindest einseitig einen mittels Elektronenstrahlen gehärteten Überzug enthält.The invention relates to a waterproof paper support for photographic purposes, which contains at least one side of a coating hardened by means of electron beams.

Wasserfest beschichtete Papierträger für fotografische Zwecke sind in verschiedenen Ausführungsformen bekannt. Eine breite Anwendung haben besonders mit extrudierten Polyolefinschichten versehene Papiere gefunden.Water-resistant coated paper supports for photographic purposes are known in various embodiments. Papers provided with extruded polyolefin layers have found wide application.

Die in neuerer Zeit bekannt gewordenen DE-A-3 022 451, DE-A-3 022 709 sowie DE-A-3 410 797 beschreiben Papierträger, deren Basispapier mit mindestens einem in situ mit Hilfe von Elektronenstrahlhärtung hergestellten Überzug versehen ist.DE-A-3 022 451, DE-A-3 022 709 and DE-A-3 410 797, which have become known in recent times, describe paper supports whose base paper is provided with at least one coating produced in situ with the aid of electron beam curing.

Durch Elektronenstrahlen gehärtete Überzüge besitzen im Vergleich zu den Polyolefinüberzügen verbesserte Eigenschaften, wie z. B. die Erhöhung der Kratzfestigkeit, die Erhöhung des Pigmentaufnahmevermögens oder glattere Oberflächen. Sie sind wie Polyolefinüberzüge beständig gegen fotografische Prozeßlösungen und schützen daher den darunter befindlichen Papierträger ebenfalls vor dem Eindringen dieser Lösungen.Electron beam cured coatings have improved properties, such as: B. the increase in scratch resistance, the increase in pigment absorption or smoother surfaces. Like polyolefin coatings, they are resistant to photographic process solutions and therefore also protect the paper carrier underneath from the penetration of these solutions.

Die Prozeßdauer und insbesondere der Waschvorgang werden dadurch entscheidend verkürzt.The process time and especially the washing process are shortened significantly.

Die mit Elektronenstrahlen gehärteten Überzüge werden gemäß DE-A-3 022 451 oder DE-A-3 022 709 hergestellt, indem eine fließfähige Mischung auf die Oberfläche des Papieres aufgetragen, dort gleichmäßig verteilt und anschließend unter Schutzgas oder sonstiger Abdeckung mit energiereichen Elektronenstrahlen verfestigt wird.The coatings hardened with electron beams are produced according to DE-A-3 022 451 or DE-A-3 022 709 by applying a flowable mixture to the surface of the paper, distributing it evenly there and then solidifying it with high-energy electron beams under a protective gas or other covering .

Die Mischungen enthalten als entscheidenden Bestandteil zumindest eine Substanz mit ethylenisch ungesättigten Doppelbindungen, die die Fähigkeit zur polymerisierenden Reaktion miteinander haben, wenn diese durch Bestrahlung initiiert wird.The mixtures contain as a crucial component at least one substance with ethylenically unsaturated double bonds, which have the ability to polymerize with each other when initiated by radiation.

Geeignete Stoffe mit ethylenisch ungesättigten Doppelbindungen sind alle Vinyl- oder Vinylidenverbindungen. Bevorzugt werden solche Stoffe benutzt, die Acrylat- oder Methacrylatgruppen enthalten. Auch Ester von Maleinsäure, Fumarsäure, Mesaconsäure, Citraconsäure oder Itaconsäure, andere Derivate dieser Säuren, Allylverbindungen sowie lineare und cyclische Diene bzw. Triene können als reaktive Mischungskomponenten verwendet werden. Die Ester der genannten Säuren, die sich von mehrwertigen Alkoholen ableiten, z. B. Hexandiolacrylat, Trimethylolpropantriacrylat, Polyesteracrylate, Polyurethanacrylate, Polyetheracrylate, Polyepoxidacrylate oder Alkydharzacrylate, sind besonders geeignet. Vorzugsweise soll die Mischung jedoch zumindest einen Stoff enthalten, der zwei oder mehr Doppelbindungen enthält.Suitable substances with ethylenically unsaturated double bonds are all vinyl or vinylidene compounds. Those substances which contain acrylate or methacrylate groups are preferably used. Esters of maleic acid, fumaric acid, mesaconic acid, citraconic acid or itaconic acid, other derivatives of these acids, allyl compounds and linear and cyclic dienes or trienes can also be used as reactive mixture components. The esters of the acids mentioned, which are derived from polyhydric alcohols, for. B. hexanediol acrylate, trimethylolpropane triacrylate, polyester acrylates, polyurethane acrylates, polyether acrylates, polyepoxy acrylates or alkyd resin acrylates are particularly suitable. However, the mixture should preferably contain at least one substance which contains two or more double bonds.

Die Fließeigenschaften härtbarer Mischungen werden eingestellt, indem Bestandteile von höherem Molekulargewicht mit niedermolekularen Stoffen gemischt werden.The flow properties of curable mixtures are adjusted by mixing components of higher molecular weight with low molecular weight substances.

Neben den reaktiven Komponenten können in begrenztem Umfang auch nicht reagierende Stoffe ohne Doppelbindungen in einer Mischung enthalten sein.In addition to the reactive components, non-reactive substances without double bonds can also be contained in a mixture to a limited extent.

Darüber hinaus können die Mischungen für die mittels Elektronenstrahlen härtbaren Überzüge Pigmente, Farbstoffe, optische Aufheller, Bildstabilisatoren, Antioxidantien oder andere Zusatzstoffe enthalten, soweit dies im Hinblick auf die angestrebten Eigenschaften eines aufliegenden fotografischen Bildes wünschenswert oder notwendig ist.In addition, the mixtures for the coatings curable by means of electron beams can contain pigments, dyes, optical brighteners, image stabilizers, antioxidants or other additives, insofar as this is desirable or necessary in view of the desired properties of an overlying photographic image.

Die fotografischen Schichten werden nach geeigneter Vorbehandlung des mittels Elektronenstrahlen gehärteten Überzugs entweder direkt oder nach vorheriger Aufbringung einer Haftung vermittelnden Zwischenschicht auf die Oberfläche des mittels Elektronenstrahlen gehärteten Überzugs gebracht. Bei diesen fotografischen Schichten handelt es sich vorzugsweise um solche Schichten, die unter dem Begriff "Silbersalzfotographie" bekannt sind und zur Erzeugung von Schwarz/Weiß- oder von Farbbildern dienen. Obwohl die mittels Elektronenstrahlen gehärteten Überzüge gegenüber Polyolefinüberzügen etliche Vorteile aufweisen, sind sie jedoch bislang auch noch mit Nachteilen behaftet.After suitable pretreatment of the coating hardened by means of electron beams, the photographic layers are applied to the surface of the coating hardened by electron beams either directly or after prior application of an adhesion-promoting intermediate layer. These photographic layers are preferably layers which are known under the term "silver salt photography" and are used to produce black / white or color images. Although the coatings which have been hardened by means of electron beams have a number of advantages over polyolefin coatings, they still have disadvantages to date.

Vorteilhaft gegenüber Polyolefinüberzügen ist z. B. das erhöhte Pigmentaufnahmevermögen der mittels Elektronenstrahlen gehärteten Überzüge. Zur Verbesserung des Weißegrades bzw. zur Verbesserung der Auflösung oder der Bildschärfe nach Applikation einer fotografischen Emulsion ist ein möglichst hoher Gehalt an Weißpigment, z. B. Titanoxid, wünschenswert.An advantage over polyolefin coatings is e.g. B. the increased pigment absorption capacity of the coatings hardened by means of electron beams. To improve the degree of whiteness or to improve the resolution or image sharpness after application of a photographic emulsion, the highest possible content of white pigment, e.g. B. titanium oxide, desirable.

Zwar kann einer Harzmischung für mittels Elektronenstrahlen härtbare Überzüge bis zu 70 Gew.-% Weißpigment zugesetzt werden, jedoch wird bei großen Mengen die gehärtete Schicht so spröde, daß bald Spannungsrisse auftreten oder daß die Schicht nur noch schlecht an der Unterlage haftet.Although up to 70% by weight of white pigment can be added to a resin mixture for electron-curable coatings, the hardened layer becomes so brittle in large quantities that stress cracks soon occur or that the layer adheres poorly to the substrate.

Nachteilig ist außerdem, daß die mit Elektronenstrahlen gehärteten Überzüge sich gegenüber verschiedenen fotografischen Prozeßlösungen unterschliedlich verhalten. So wurde festgestellt, daß bei der Verwendung solcher handelsüblicher fotografischer Colorentwickler, die aromatischen Aminderivate. z. B. Derivate von Phenylendiamin, Toluidin u. a., enthalten, eine gelbliche Verfärbung der Oberfläche des strahlengehärteten Überzugs eintritt.Another disadvantage is that the coatings hardened with electron beams behave differently from different photographic process solutions. It was found that when using such commercially available photographic color developers, the aromatic amine derivatives. e.g. B. derivatives of phenylenediamine, toluidine and. a., contains a yellowish discoloration of the surface of the radiation-hardened coating occurs.

Diese Verfärbung ist zwar gering, aber deutlich sichtbar und kann weder durch das Stoppbad, noch durch gründliches Waschen verhindert werden.This discoloration is slight, but clearly visible and can neither be prevented by the stop bath, nor by thorough washing.

Sie zeigt sich sowohl bei pigmentfreien, als auch bei mit Weißpigment pigmentierten Überzügen, wobei in der Regel die Verfärbung bei pigmenthaltigen Überzügen stärker ist als bei pigmentfreien Überzügen.It is evident both in the case of pigment-free and in the case of coatings pigmented with white pigment, with the discoloration generally being stronger in the case of pigment-containing coatings than in the case of pigment-free coatings.

Die Verfärbung tritt weder bei Polyolefinoberflächen auf, noch ist sie an den klassischen Barytpapieren zu beobachten.The discoloration does not occur on polyolefin surfaces, nor can it be observed on classic baryta papers.

In der EP-A-0 159 493 wurde ein Weg beschrieben, um durch spezielle Zusammensetzung der härtbaren Komponenten einer Überzugsmischung Überzüge mit verringerter Anfärbung zu erhalten. Das dort beschriebene Verfahren basiert darauf, daß ungesättigte hydroxi-funktionelle Verbindungen in einer molalen Konzentration von 2 oder mehr als 2 in den Überzugsmischungen enthalten sind.EP-A-0 159 493 describes a way of obtaining coatings with reduced staining by means of the special composition of the curable components of a coating mixture. That there The method described is based on the fact that unsaturated hydroxyl-functional compounds are contained in the coating mixtures in a molar concentration of 2 or more than 2.

Die EP-A-0 176 656 beschreibt die Verwendung eines speziellen Titandioxids als Weißpigment zur Verringerung der Anfärbung des Elektronenstrahlen gehärteten Überzugs in fotorgafischen Colorentwicklern. Das verwendete, spezielle Titandioxid trägt eine Oberflächenbelegung, die wenigstens 2 Gew.-% des Gesamtpigmentes ausmacht. Die Oberflächenbelegung ist ein anorganisches Oxid oder Oxidhydrat und kann ein Aluminiumoxid, Kieselsäure, Zinkoxid, Magnesiumoxid, Zinnoxid, Zirkonoxid, Antimonoxid oder eines der Erdalkalimetalloxide oder Mischungen solcher Verbindungen sein.EP-A-0 176 656 describes the use of a special titanium dioxide as a white pigment to reduce the coloration of the electron beam-hardened coating in photographic color developers. The special titanium dioxide used has a surface coating that makes up at least 2% by weight of the total pigment. The surface covering is an inorganic oxide or hydrated oxide and can be an aluminum oxide, silica, zinc oxide, magnesium oxide, tin oxide, zirconium oxide, antimony oxide or one of the alkaline earth metal oxides or mixtures of such compounds.

Beide beschriebenen Wege führen zwar zu einer Verringerung der Gelbfärbung des strahlengehärteten Überzugs bei der Verwendung von Colorentwicklern, nachteilig an den gegebenen Lösungen ist jedoch die starke Beschränkung in der Auswahl der Mischungskomponenten gemäß EP-A-0 159 493 bzw. in der Verwendung des Weißpigmentes gemäß EP-A-0 176 656, sowie die sich bei höheren Pigmentgehalten einstellende Sprödigkeit des Überzugs.Both of the described ways lead to a reduction in the yellowing of the radiation-hardened coating when using color developers, but a disadvantage of the given solutions is the severe limitation in the selection of the mixture components according to EP-A-0 159 493 or in the use of the white pigment EP-A-0 176 656, and the brittleness of the coating which occurs at higher pigment contents.

Es ist daher die Aufgabe der vorliegenden Erfindung, einen mit mindestens einem mittels Elektronenstrahlen gehärteten Überzug versehenen, wasserfesten Papierträger für fotografische Zwecke zu schaffen, der die beschriebenen Nachteile nicht aufweist und der speziell nach Behandlung mit fotografischen Entwicklerlösungen beliebiger Art keine sichtbare Tendenz zur Gelbfärbung zeigt.It is therefore the object of the present invention to provide a waterproof paper support for photographic purposes provided with at least one electron-hardened coating, which does not have the disadvantages described and which shows no visible tendency to yellow, especially after treatment with photographic developer solutions of any kind.

Dabei wird als nicht mehr sichtbare Tendenz zur Gelbfärbung bezeichnet, wenn die Bestimmung der optischen Dichte nach DIN 4512, mit Gelbfilter über weißem Untergrund gemessen, Veränderungen aufweist, die kleiner als 0,03 sind.The trend towards yellowing is no longer visible if the determination of the optical density according to DIN 4512, measured with a yellow filter over a white background, shows changes that are smaller than 0.03.

Gelöst wird die vorstehend aufgezeigte Aufgabe durch die in den Patentansprüchen gekennzeichnete Erfindung.The above-stated object is achieved by the invention characterized in the patent claims.

Es war festgestellt worden, daß speziell die strahlengehärteten Überzüge, die als ungesättigte Verbindungen Acrylate, Methacrylate oder Allylverbindungen aufweisen, besonders stark zur Anfärbung mit Colorentwickler neigen. Für die Entstehung der Anfärbung wurde daher der Binderanteil, der ungesättigte Gruppen enthält, verantwortlich gemacht.It had been found that especially the radiation-hardened coatings, which have acrylates, methacrylates or allyl compounds as unsaturated compounds, have a particularly strong tendency to stain with color developers. The proportion of binder that contains unsaturated groups was therefore made responsible for the development of the staining.

Es ist daher überraschend, daß die erfindungsgemäß verwendeten Substanzen, die ebenfalls ungesättigte Gruppen enthalten, die Verfärbung in Colorentwicklerbädern verhindern.It is therefore surprising that the substances used according to the invention, which also contain unsaturated groups, prevent discoloration in color developer baths.

Erfindungsgemäß werden acrylierte oder methacrylierte Phosphorsäure mit mittleren Molekulargewichten von 400 bis 600 oder monomere Itaconsäure verwendet.According to the invention, acrylated or methacrylated phosphoric acid with average molecular weights of 400 to 600 or monomeric itaconic acid are used.

Die Anzahl der reaktiven, ungesättigten Gruppen bestimmt das Ausmaß der Vernetzung der erfindungsgemäßen Substanzen untereinander nach der Härtung mittels Elektronenstrahlen. Das Ausmaß der Vernetzung ist wichtig für die Verankerung der erfindungsgemäßen Substanzen in der strahlengehärteten Schicht während der Einwirkung durch die fotografischen Bäder.The number of reactive, unsaturated groups determines the degree of crosslinking of the substances according to the invention with one another after curing by means of electron beams. The degree of crosslinking is important for anchoring the substances according to the invention in the radiation-hardened layer during exposure to the photographic baths.

Der erfindungsgemäße Effekt ergibt sich besondes bei der Verwendung solcher Substanzen, in denen neben freien Säuregruppen auch reaktive, ungesättigte, durch Strahlung vernetzbare Gruppen enthalten sind.The effect according to the invention results in particular from the use of substances which, in addition to free acid groups, also contain reactive, unsaturated groups which can be crosslinked by radiation.

Die erfindungsgemäß verwendeten acrylierten bzw. methacrylierten Phosphoräsuren besitzen ein Verhältnis von reaktiven, ungesättigten Gruppen zu polaren Säuregruppen von 1 : 2 bis 2 : 1, d. h. pro Molekül liegen im Mittel z. B. 1,5 freie Säuregruppen und 1,5 Acrylat- bzw. Methacrylatgruppen vor.The acrylated or methacrylated phosphoric acids used according to the invention have a ratio of reactive, unsaturated groups to polar acid groups of 1: 2 to 2: 1, ie. H. per molecule are on average z. B. 1.5 free acid groups and 1.5 acrylate or methacrylate groups.

Monomere Itaconsäure weist ein Verhältnis von ungesättigten zu polaren Gruppen von 1 : 2 auf und ist ebenfalls geeignet.Monomeric itaconic acid has a ratio of unsaturated to polar groups of 1: 2 and is also suitable.

Die erfindungsgemäßen Substanzen können in Mengen von 1 - 15 Gew.-%, vorzugsweise jedoch 4 - 10 Gew.- %, bezogen auf die Überzugsmischung, zugesetzt werden.The substances according to the invention can be added in amounts of 1-15% by weight, but preferably 4-10% by weight, based on the coating mixture.

Im Rahmen der Erfindung ist es unerheblich, ob die mit Elektronenstrahlen gehärteten Überzüge noch weitere Zusätze enthalten wie sie in derartigen fotografischen Trägern gebräuchlich sind.In the context of the invention it is immaterial whether the coatings hardened with electron beams contain further additives as are customary in such photographic supports.

Vielmehr ist z. B. die Wahl der Art und Menge des Weißpigmentes unter den bekannten oder anderen denkbaren Weißpigmenten, mit oder ohne Oberflächenbelegung, völlig frei, ohne daß der erfindungsgemäße Effekt nachteilig beeinflußt wird.Rather, z. B. the choice of the type and amount of white pigment among the known or other conceivable white pigments, with or without surface coverage, completely free, without the effect of the invention is adversely affected.

Ebenso ist die Auswahl der verschiedenen Komponenten für die Herstellung strahlenhärtbarer Überzugsmischungen unter den bekannten, für die Herstellung dieser Mischungen bereits beschriebenen Substanzen (z. B. gemäß DE-A-3 022 451 oder DE-A-3 022 709) sowie anderer, denkbarer, geeigneter Substanzen völlig frei.Likewise, the selection of the various components for the production of radiation-curable coating mixtures from the known substances already described for the production of these mixtures (for example according to DE-A-3 022 451 or DE-A-3 022 709) and others is more conceivable , suitable substances completely free.

Desgleichen können neben dem Weißpigment noch Farbpigmente jeder Art sowie Dispergierhilfsmittel, Farbstoffe und andere die Bildqualität günstig beeinflussende Stoffe den Überzugsmischungen zugesetzt werden, ohne den erfindungsgemäßen Effekt negativ zu beeinflussen.In addition to the white pigment, it is also possible to add color pigments of any type and dispersion aids, dyes and other substances which have a favorable effect on the image quality to the coating mixtures, without adversely affecting the effect according to the invention.

Die erfindungsgemäßen Überzüge können in beliebiger Weise gemäß einem der bekannten Verfahren hergestellt und verfestigt werden und verschiedene Oberflächenstrukturen haben (z. B. gemäß DE-C-2 515 261, DE-A-3 022 709 oder EP-A-0 159 493.The coatings according to the invention can be produced and solidified in any manner according to one of the known processes and have different surface structures (e.g. according to DE-C-2 515 261, DE-A-3 022 709 or EP-A-0 159 493.

In der Regel wird das Basispapier auch auf der Gegenseite wasserfest überzogen. Dieser Überzug kann ebenfalls aus einer erfindungsgemäßen Mischung, aber auch aus Polyolefin bestehen. Auch mehrere gleichartige oder verschiedene Überzüge können übereinander gelegt werden.As a rule, the base paper is also waterproof coated on the opposite side. This coating can also consist of a mixture according to the invention, but also of polyolefin. Several identical or different coatings can also be placed on top of each other.

Entscheidend ist, daß bei der Verwendung der erfindungsgemäßen Substanzen in den Mischungen für strahlenhärtbare Überzüge die Verfärbung in den Colorentwicklerbädern vermieden wird. Darüber hinaus ist die ausgehärtete Schicht kratzfest, sie weist außerdem selbst bei hohem Pigmentgehalt genügend Elastizität aus, damit Spannungsrisse vermieden werden und eine genügende Haftfestigkeit der Schicht am Basispapier erreicht wird.It is crucial that when the substances according to the invention are used in the mixtures for radiation-curable coatings, the discoloration in the color developer baths is avoided. In addition, the hardened layer is scratch-resistant, and even with a high pigment content it has sufficient elasticity to prevent stress cracks and to ensure that the layer adheres sufficiently to the base paper.

Der erfindungsgemäße Gedanke wird an den nachfolgenden Beispielen verdeutlicht.The idea according to the invention is illustrated in the examples below.

Beispiel 1example 1

Eine Grundmischung aus

  • 50 Gew.-% Polyestertetraacrylat (M ca. 1000)
  • 30 Gew.-% Glyceroltriacrylat
  • 20 Gew.-% Hexandioldiacrylat
wurde in gleiche Teile geteilt und mit acrylierter Phosphorsäure des Molekulargewichts 500 und im Mittel 1,5 Acrylat- sowie 1,5 freien Säuregruppen pro Molekül folgender Mengen versetzt:A basic mix of
  • 50% by weight polyester tetraacrylate (M approx. 1000)
  • 30% by weight glycerol triacrylate
  • 20% by weight hexanediol diacrylate
was divided into equal parts and mixed with acrylated phosphoric acid with a molecular weight of 500 and an average of 1.5 acrylate and 1.5 free acid groups per molecule of the following amounts:

Figure imgb0001
Figure imgb0001

Ein ca. 150 g/m2 schweres mittels Alkylketendimer im neutralen pH-Bereich hydrophobiertes Basispapier wurde mit jeweils einer der Überzugsmischungen 1a bis 1 überzogen.An approximately 150 g / m 2 heavy base paper hydrophobized by means of alkyl ketene dimer in the neutral pH range was coated with one of the coating mixtures 1a to 1 in each case.

Die aufgebrachte Schichtmenge betrug ca. 20 g/m2.The amount of layers applied was approximately 20 g / m 2 .

Der Überzug wurde unter Stickstoff mittels Elektronenstrahlen bei Anwendung einer Energiedosis von 4 Mrad ausgehärtet.The coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.

Beispiel 2Example 2

Eine Grundmischung aus

  • 50 Gew.-% Polyestertetraacrylat (M ca. 1000)
  • 30 Gew.-% Glyceroltriacrylat
  • 20 Gew.-% Hexandioldiacrylat
wurde in gleiche Teile geteilt und mit methacrylierter Phosphorsäure des ungefähren Molekulargewichts 500 und im Mittel 1,5 Methacrylat- sowie 1,5 freien Säuregruppen pro Molekül folgender Mengen versetzt:A basic mix of
  • 50% by weight polyester tetraacrylate (M approx. 1000)
  • 30% by weight glycerol triacrylate
  • 20% by weight hexanediol diacrylate
was divided into equal parts and mixed with methacrylated phosphoric acid with an approximate molecular weight of 500 and an average of 1.5 methacrylate and 1.5 free acid groups per molecule of the following amounts:

Figure imgb0002
Figure imgb0002

Ein ca. 150 g/m2 schweres mittels Alkylketendimer im neutralen pH-Bereich hydrophobiertes Basispapier wurde mit jeweils einer der Überzugsmischungen 2a bis 2i überzogen.An approximately 150 g / m 2 heavy base paper hydrophobized by means of alkyl ketene dimer in the neutral pH range was coated with one of the coating mixtures 2a to 2i in each case.

Die aufgebrachte Schichtmenge betrug ca. 20 g/m2.The amount of layers applied was approximately 20 g / m 2 .

Der Überzug wurde unter Stickstoff mittels Elektronenstrahlen bei Anwendung einer Energiedosis von 4 Mrad ausgehärtet.The coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.

Beispiel 3Example 3

Eine Grundmischung aus

  • 50 Gew.-% Polyestertetraacrylat (M ca. 1000)
  • 30 Gew.-% Glyceroltriacrylat
  • 20 Gew.-% Hexandioldiacrylat
wurde in gleiche Teile geteilt und mit monomerer Itaconsäure folgender Mengen versetzt:A basic mix of
  • 50% by weight polyester tetraacrylate (M approx. 1000)
  • 30% by weight glycerol triacrylate
  • 20% by weight hexanediol diacrylate
was divided into equal parts and the following amounts were added with monomeric itaconic acid:

Figure imgb0003
Figure imgb0003

Ein ca. 150 g/m2 schweres mittels Alkylketendimer im neutralen pH-Bereich hydrophobiertes Basispapier wurde mit jeweils einer der Überzugsmischungen 3a bis 3i überzogen.An approximately 150 g / m 2 heavy base paper hydrophobized by means of alkyl ketene dimer in the neutral pH range was coated with one of the coating mixtures 3a to 3i.

Die aufgebrachte Schichtmenge betrug ca. 20 g/m2.The amount of layers applied was approximately 20 g / m 2 .

Der Überzug wurde unter Stickstoff mittels Elektronenstrahlen bei Anwendung einer Energiedosis von 4 Mrad ausgehärtet.The coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.

Beispiel 4Example 4

Eine Grundmischung aus

  • 62 Gew.-% Polyestertetraacrylat (M ca. 1000)
  • 23 Gew.-% Glyceroltriacrylat
  • 15 Gew.-% Hexandioldiacrylat
wurde in gleiche Teile geteilt und mit den erfindungsgemäßen Substanzen folgender Mengen versetzt:A basic mix of
  • 62% by weight polyester tetraacrylate (M approx. 1000)
  • 23% by weight glycerol triacrylate
  • 15% by weight hexanediol diacrylate
was divided into equal parts and the following amounts were added to the substances according to the invention:

Figure imgb0004
Figure imgb0004

Ein ca. 150 g/m2 schweres mittels Alkylketendimer im neutralen pH-Bereich hydrophobiertes Basispapier wurde mit jeweils einer der Überzugsmischungen 4a bis 4c überzogen.An approximately 150 g / m2 heavy base paper hydrophobized by means of alkyl ketene dimer in the neutral pH range was coated with one of the coating mixtures 4a to 4c.

Die aufgebrachte Schichtmenge betrug ca. 20 g/m2.The amount of layers applied was approximately 20 g / m 2 .

Der Überzug wurde unter Stickstoff mittels Elektronenstrahlen bei Anwendung einer Energiedosis von 4 Mrad ausgehärtet.The coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.

Beispiel 5Example 5

Eine Grundmischung aus

  • 70 Gew.-% Triethylenglykoldiacrylat
  • und
  • 30 Gew.-% Pentaerythritoltriacrylat
wurde in gleiche Teile geteilt und mit den erfindungsgemäßen Substanzen folgender Mengen versetzt:A basic mix of
  • 70% by weight of triethylene glycol diacrylate
  • and
  • 30% by weight pentaerythritol triacrylate
was divided into equal parts and the following amounts were added to the substances according to the invention:

Figure imgb0005
Ein ca. 120 g/m2 schweres unter Verwendung von Fettsäureseifen hydrophobiertes Basispapier wurde mit jeweils einer der Überzugsmischungen 5a bis 5c überzogen.
Figure imgb0005
 An approximately 120 g / m 2 heavy base paper hydrophobicized using fatty acid soaps was coated with one of the coating mixtures 5a to 5c.

Die aufgebrachte Schichtmenge betrug ca. 20 g/m2.The amount of layers applied was approximately 20 g / m 2 .

Der Überzug wurde unter Stickstoff mittels Elektronenstrahlen bei Anwendung einer Energiedosis von 4 Mrad ausgehärtet.The coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.

Beispiel 6Example 6

Eine Grundmischung aus

  • 40 Gew.-% Polyestertetraacrylat (M ca. 1000)
  • 30 Gew.-% Trimethylolpropantriethoxytriacrylat
  • 20 Gew.-% Hexandioldiacrylat
  • 10 Gew.-% Polyethylenglykoldiacrylat (MW des Polyethylenglykols ca. 400)
wurde in gleiche Teile geteilt und mit erfindungsgemäß verwendeter Phosphorsäure folgender Mengen versetzt:A basic mix of
  • 40% by weight polyester tetraacrylate (M approx. 1000)
  • 30% by weight trimethylolpropane triethoxy triacrylate
  • 20% by weight hexanediol diacrylate
  • 10% by weight of polyethylene glycol diacrylate (MW of the polyethylene glycol approx. 400)
was divided into equal parts and the following amounts were added with phosphoric acid used according to the invention:

Figure imgb0006
Figure imgb0006

Ein ca. 150 g/m2 schweres mittels Alkylketendimer im neutralen pH-Bereich hydrophobiertes Basispapier wurde mit jeweils einer der Überzugsmischungen 6a und 6b überzogen.An approximately 150 g / m 2 heavy base paper hydrophobicized with alkyl ketene dimer in the neutral pH range was coated with one of the coating mixtures 6a and 6b.

Die aufgebrachte Schichtmenge betrug ca. 20 g/m2.The amount of layers applied was approximately 20 g / m 2 .

Der Überzug wurde unter Stickstoff mittels Elektronenstrahlen bei Anwendung einer Energiedosis von 4 Mrad ausgehärtet.The coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.

Beispiel 7Example 7

Eine Grundmischung aus

  • 28 Gew.-% Polyestertetraacrylat (M ca. 1000)
  • 21 Gew.-% Trimethylolpropantriethoxytriacrylat
  • 14 Gew.-% Hexandioldiacrylat
  • 7 Gew.-% Polyethylenglykoldiacrylat
  • 30 Gew.-% Ti02 ohne Oberflächenbehandlung, Rutil-Typ
wurde in gleiche Teile geteilt und mit erfindungsgemäß verwendeter Phosphorsäure folgender Mengen versetzt:A basic mix of
  • 28% by weight polyester tetraacrylate (M approx. 1000)
  • 21% by weight trimethylolpropane triethoxy triacrylate
  • 14% by weight hexanediol diacrylate
  • 7% by weight of polyethylene glycol diacrylate
  • 30% by weight Ti0 2 without surface treatment, rutile type
was divided into equal parts and the following amounts were added with phosphoric acid used according to the invention:

Figure imgb0007
Figure imgb0007

Ein ca. 120 g/m2 schweres unter Verwendung von Fettsäureseifen hydrophobiertes Basispapier wurde mit jeweils einer der beiden Überzugsmischungen 7a und 7b überzogen.An approximately 120 g / m 2 heavy base paper hydrophobized using fatty acid soaps was coated with one of the two coating mixtures 7a and 7b.

Die aufgebrachte Schichtmenge betrug ca. 20 g/m2.The amount of layers applied was approximately 20 g / m 2 .

Der Überzug wurde unter Stickstoff mittels Elektronenstrahlen bei Anwendung einer Energiedosis von 4 Mrad ausgehärtet.The coating was cured under nitrogen using electron beams using an energy dose of 4 Mrad.

Prüfung der TrägermaterialienExamination of the carrier materials

Zur Prüfung der mit den Überzugsmischungen aus Beispiel 1 - 6 beschichteten Papierträger wird jeweils ein Muster in Form eines Schiffchens gefaltet und für 15 Minuten bei 30°C auf handelsübliche Colorentwickler gesetzt.To test the paper supports coated with the coating mixtures from Examples 1-6, a pattern is folded in the form of a boat and placed on commercially available color developers for 15 minutes at 30 ° C.

Die Faltung bewirkt, daß nur ein Teil des Musters mit der Entwicklerlösung in Kontakt kommt, so daß ein direkter Vergleich zwischen der behandelten und der unbehandelten Fläche an dem gleichem Muster möglich ist.The folding causes only a part of the pattern to come into contact with the developer solution, so that a direct comparison between the treated and the untreated area on the same pattern is possible.

Nach der Behandlung mit dem Colorentwickler wird das Muster 2 Stunden gewässert, mechanisch abgetrocknet und anschließend vier Tage bei Raumtemperatur unter Tageslichteinwirkung gelagert.After treatment with the color developer, the sample is watered for 2 hours, mechanically dried and then stored for four days at room temperature under the influence of daylight.

Nach Ablauf der Lagerungszeit wird das Ausmaß der Gelbfärbung densiometrisch nach DIN 4512 bestimmt.After the storage time has elapsed, the extent of the yellowing is determined densiometrically in accordance with DIN 4512.

Densitometriscne PrüfergebnisseDensitometric test results

Figure imgb0008
Figure imgb0008

Claims (5)

1. Water-resistant paper carrier for photographic emulsions, with at least one resin coating which is hardened by electron beams, characterised in that the still non-hardened mixture of the resin for the coating contains monomeric itaconic acid or acrylated or methacrylated phosphoric acid, the ratio of acrylate or methylacrylate groups to acid groups in the derivatised phosphoric acid has a value of 1 : 2 to 2 : 1.
2. Water-resistant paper carrier according to Claim 1, characterised in that the acrylated or methyacrylated phosphoric acid or the itaconic acid in the coating mixture which can be hardened by electron beams is present at the rate of 1 to 15 % by weight and preferably 4 to 10 % by weight in relation to the total quantity of mixture.
3. Water-resistant paper carrier according to Claim 1 and 2, characterised in that the acrylated or methacrylated phosphoric acid has a mean molecular weight of 400 to 600.
4. Water-resistant paper carrier according to Claim 1, characterised in that the acrylated or methacrylated phosphoric acid contains on average 1.5 acrylate or methylacrylate groups and 1.5 acid groups per molecule.
5. Water-resistant paper carrier according to Claim 1 and 2, characterised in that the resin mixture for the coating contains a white pigment.
EP86109856A 1985-10-09 1986-07-17 Water-proof paper support for photographic purposes Expired EP0219615B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86109856T ATE40481T1 (en) 1985-10-09 1986-07-17 WATERPROOF PAPER SUPPORT FOR PHOTOGRAPHIC PURPOSES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3535954A DE3535954C2 (en) 1985-10-09 1985-10-09 Waterproof paper carrier for photographic recording materials
DE3535954 1985-10-09

Publications (2)

Publication Number Publication Date
EP0219615A1 EP0219615A1 (en) 1987-04-29
EP0219615B1 true EP0219615B1 (en) 1989-01-25

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Country Status (7)

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US (1) US4731285A (en)
EP (1) EP0219615B1 (en)
JP (1) JPH061352B2 (en)
AT (1) ATE40481T1 (en)
DE (2) DE3535954C2 (en)
ES (1) ES2001715A6 (en)
GR (1) GR862521B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5374508A (en) * 1990-12-21 1994-12-20 New Oji Paper Co., Ltd. Support sheet for photographic printing sheet
DE69127432T2 (en) * 1990-12-21 1998-04-09 Oji Paper Co Supports for photographic prints
US5783043A (en) * 1996-01-11 1998-07-21 Christensen; Leif Paper coating apparatus
US6545283B1 (en) 2000-05-17 2003-04-08 Playtex Products, Inc. Process of improving the whitening of a polymeric tampon applicator
US20070218254A1 (en) * 2006-03-15 2007-09-20 Xiaoqi Zhou Photographic printing paper and method of making same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2808931A1 (en) * 1977-03-04 1978-09-07 Dynachem Corp PROCESS FOR COATING OR PRINTING A SUBSTRATE
DE3022451A1 (en) * 1980-06-14 1982-01-07 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück WATERPROOF PHOTOGRAPHIC PAPER
DE3022709A1 (en) * 1980-06-18 1982-01-07 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück WATERPROOF PHOTOGRAPHIC PAPER AND METHOD FOR THE PRODUCTION THEREOF
DE3300025A1 (en) * 1983-01-03 1984-07-05 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück WATERPROOF PHOTOGRAPHIC PAPER CARRIER
US4554175A (en) * 1983-03-28 1985-11-19 Konishiroku Photo Industry Co., Ltd. Method of producing support for photographic paper
JPS60100144A (en) * 1983-11-07 1985-06-04 Fuji Photo Film Co Ltd Photographic printing paper support

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DE3535954A1 (en) 1987-04-09
DE3535954C2 (en) 1994-05-26
DE3661974D1 (en) 1989-03-02
JPS6289043A (en) 1987-04-23
GR862521B (en) 1986-10-10
EP0219615A1 (en) 1987-04-29
ES2001715A6 (en) 1988-06-01
US4731285A (en) 1988-03-15
ATE40481T1 (en) 1989-02-15

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