EP0176656A2 - Support material for black and white and colour photography - Google Patents

Support material for black and white and colour photography Download PDF

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Publication number
EP0176656A2
EP0176656A2 EP85103457A EP85103457A EP0176656A2 EP 0176656 A2 EP0176656 A2 EP 0176656A2 EP 85103457 A EP85103457 A EP 85103457A EP 85103457 A EP85103457 A EP 85103457A EP 0176656 A2 EP0176656 A2 EP 0176656A2
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EP
European Patent Office
Prior art keywords
oxide
support material
material according
pigment
white
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.)
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Application number
EP85103457A
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German (de)
French (fr)
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EP0176656A3 (en
EP0176656B1 (en
Inventor
Wieland Dr. Dipl.-Phys. Sack
Reiner Anthonsen
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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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Priority to AT85103457T priority Critical patent/ATE57773T1/en
Publication of EP0176656A2 publication Critical patent/EP0176656A2/en
Publication of EP0176656A3 publication Critical patent/EP0176656A3/en
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Publication of EP0176656B1 publication Critical patent/EP0176656B1/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
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/136—Coating process making radiation sensitive element
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/143—Electron beam
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • 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]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179—Next to cellulosic

Definitions

  • the invention relates to a carrier material for black / white and color photographic layers, which contains at least one cover layer hardened by means of electron beams.
  • a large number of substrates for photographic layers are known.
  • the most common media include film materials and papers. Papers are usually additionally coated. Waterproof papers coated in particular with synthetic resin layers have found wide use as supports for photographic layers. Resin films and laminates coated with special layers are also known. Papers coated on both sides with polyolefin resin and film materials coated with pigmented layers (DAS 14 47 815, US 38 33 380, US 36 30 742, US 39 28 037) were most widespread. However, such coatings only have a limited pigment absorption, are not scratch-resistant and are unsuitable for thermal image development.
  • DOS 30 22 451 and DOS 30 22 709 which consist of base paper with at least one top layer produced in situ with the aid of electron beam curing.
  • the advantages of an upper layer hardened with electron beams are its scratch resistance, the high pigment absorption capacity and the higher smoothness of the surface in comparison to polyolefin coatings.
  • Resin coatings are not only resistant to water, but also to acidic and alkaline photographic process solutions and thus prevent these solutions from penetrating into any paper carrier underneath.
  • All resin coatings 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.
  • pigments and dyes are of the greatest importance for the visual impression of a photographic image on the coating. They determine the color character of color images and are decisive for the sharpness of the photographic images.
  • the photographic layers are applied to the surface of the resin layer either directly or after previously applying an adhesion-promoting intermediate layer.
  • These photographic layers are preferably layers which are known under the term silver salt photography and which are used either for producing black / white or color images.
  • Resin coatings hardened with electron beams in accordance with DOS 30 22 451 or DOS 30 22 709 are produced by applying a flowable mixture to the surface of a paper or other base support, distributing it uniformly there and then solidifying it under inert gas or other covering with high-energy electron beams.
  • the mixtures contain at least one substance with an ethylenically unsaturated double as a crucial constituent bonds that have the ability to polymerize with one another when initiated by radiation.
  • the layers hardened with electron beams now have many advantages compared to polyolefin layers, but so far they have also had disadvantages.
  • Despite the wide range of variations in the composition of radiation-hardened layers it was not possible to create a layer that showed equally good behavior in all photographic process solutions. Rather, it was found that the layers hardened with electron beams behave differently towards different process solutions.
  • There are commercially available color developer preparations which, in combination with subsequent exposure to oxygen, lead to a yellowish discoloration of the surface of the radiation-hardened layer. This discoloration is slight, but clearly visible and can neither be prevented by the stop bath, nor by thorough washing. It occurs especially when using such photographic developer solutions that contain an aromatic amine derivative (e.g.
  • the discoloration of radiation-hardened coatings with color developers is evident both with pigment-free coatings and with coatings that contain white pigment. As a rule, the discoloration is even stronger with pigment-containing coatings than with pigment-free coatings, as shown in Table 1 below.
  • the binder used here consisted of 62% by weight of polyester tetraacrylate, 22.5% by weight of glycerol propoxitriacrylate and 15.5% by weight of hexanediol diacrylate).
  • German patent application P 34 15 215 has already shown a way to obtain layers with reduced staining by means of a special composition of the curable components of a coating mixture.
  • the process described there 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.
  • the technical teaching from P 34 15 215 is basically applicable to both pigment-free and pigmented coating mixtures.
  • pigment-containing coating mixtures usually stain somewhat more strongly than pigment-free coatings. Therefore, the OH concentration in pigmented coatings should generally be a little higher than in comparable pigment-free coatings.
  • This object is achieved in that a titanium dioxide is used as the white pigment which bears an inorganic surface coating which makes up at least 2% by weight of the total pigment.
  • Titanium dioxide pigments used in coating layers can be untreated like the Ti0 2 (rutile 2) contained in Table 1. In many cases, however, they are surface-treated, ie coated, to improve the dispersibility with inorganic oxides (Al Z 0 3 , AlO (OH), SiO 2 , ZnO etc.). Oxides in the broader sense also mean oxide hydrates. Such surface-coated types are, for example, the TiO 2 (anatase) and Ti0 2 (rutile 1) contained in Table 1, which are coated with 0.6 and 1.0% by weight Al oxide, and like the other white pigments in Table 1 lead to increased discoloration with color developers.
  • inorganic oxides Al Z 0 3 , AlO (OH), SiO 2 , ZnO etc.
  • Oxides in the broader sense also mean oxide hydrates.
  • Such surface-coated types are, for example, the TiO 2 (anatase) and Ti0 2 (rutile 1) contained in Table 1, which are coated with 0.6 and 1.0% by weight
  • the discoloration with color developer is significantly less if a titanium dioxide is used which is surface-coated with 2% by weight or more than 2% by weight of an inorganic oxide or hydrated oxide.
  • the inorganic oxide or hydrated oxide can be an aluminum oxide or silica or zinc oxide or magnesium oxide or tin oxide or zirconium oxide or antimony oxide or one of the alkaline earth metal oxides or mixtures of such compounds. Due to the surface coverage, the titanium dioxide particles are provided with a more or less closed coating of foreign oxide or oxide hydrate.
  • the coating can consist of one or more layers and contain other oxides in addition to those mentioned, provided that these are not coloring.
  • Titanium dioxide pigments coated in this way can be produced by any process. They can also exist as mixed oxides with another white oxide under the surface coverage, and they can additionally be treated in any way with organic compounds. It is crucial that the pigment particles contain a sufficiently strong coating of an inorganic oxide or hydrated oxide other than Ti0 2 .
  • titanium dioxide pigments coated with 2 or more% by weight of any white oxides or hydrated oxides in radiation-hardened coating mixtures have a particularly advantageous effect on the coloring of the hardened coating layer with a photographic color developer. This is all the more surprising since the corresponding oxides and hydrated oxides lead to increased discoloration even when used alone in radiation-hardened layers (see Table 1).
  • titanium dioxide pigments with 2 or more% by weight of other oxide or oxide hydrate coatings in radiation-hardened layers are evident both in layers which are hardened by means of electron beams and in layers of unsaturated starting components hardened in another way.
  • the coating layers can be on paper, film, metal foil, paper laminate or any other support and contain known other additives.
  • titanium dioxide pigment is used, the surface covering of which consists largely or even predominantly of silica.
  • a small proportion of an aluminum oxide and / or zinc oxide and / or antimony oxide and / or zirconium oxide and / or alkaline earth oxide can be present. It is of minor importance whether the coating of the TiO is more or less closed. The key is open obviously the degree of occupancy.
  • An additional organic surface covering e.g. with polyhydric alcohol, (poly) siloxane, organic titanates, organophosphates, lactone, amino compounds etc.
  • Substances which generally serve to improve the dispersibility are possible and also have their known advantages in the case of the titanium dioxide pigments coated with inorganic oxides.
  • Titanium dioxide pigment in the sense of the invention is not only to be understood to mean the known Ti0 2 modifications rutile and anatase, but also other pure or mixed titanium oxides and white pigment-like titanates.
  • titanium dioxide surface-coated with at least 2% by weight of foreign oxide is used in a hardenable mixture which contains hydroxyl-functional unsaturated substances.
  • the particular advantage of this combination is that the molar concentration of the OH groups in the mixture can also be less than 2, and nonetheless layers are obtained which show no visible coloring with color developer.
  • the invention has a particularly advantageous effect if the substances curable by electron beams are mixtures which contain at least one substance which contains two or more double bonds.
  • non-reactive substances without double bonds can also be contained in a mixture to a limited extent.
  • Substances that contain acrylate or methacrylate groups are primarily used as reactive components contain. However, 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 are also suitable as reactive mixture components. Those esters of the acids mentioned which are derived from polyhydric alcohols are preferred. Examples are hexanediol diacrylate, trimethylolpropane triacrylate, polyester acrylates, polyurethane acrylates, polyether acrylates, polyepoxy diacrylates, alkyd resin acrylates or the methacrylates corresponding to the acrylates mentioned.
  • the flow properties of such curable mixtures are adjusted according to the invention by mixing constituents of higher molecular weight with low molecular weight substances.
  • the hardness and flexibility of the hardened layers is determined by the ratio of double bonds to the molecular size in the starting material and can be varied widely by mixing different substances.
  • Support materials according to the invention are suitable as supports for all known photographic layers containing at least one silver compound. In particular, they are suitable for all wet development processes as well as for thermal image development processes.
  • the hardened coating had a thickness of approx. 20 g m.
  • the layer coatings were then treated with commercially available photographic developer for color paper, washed and the samples were stored for four days at room temperature with access to air.
  • the discoloration of the layer surface that occurred during storage was determined according to DIN 4512 as a change in the optical density compared to the initial value and is shown in Table 2.
  • a B a mixture of 50 wt .-% of tripropylene glycol diacrylate, 45 wt .-% trimethylolpropane triacrylate and 5 wt .-% glycidyl methacrylate was brought on the one hand without added pigment (2a) and on the other hand with the addition of 30 wt .-% titanium oxide pigment (2b) on a photographic base paper , leveled with the aid of a doctor rod to a thickness of approx. 35 ⁇ m and hardened in a known manner by means of electron beams.
  • a basic mixture of 45% by weight of pentaerythritol triacrylate, 50% by weight of triethylene glycol diacrylate and 5% by weight of hydroxyethyl acrylate was uniformly applied to a polyethylene on the one hand without pigment addition and on the other hand with the addition of 40% by weight of different titanium oxide pigments / Paper laminate brought and cured by means of electron beams.
  • the cured coating each had a thickness of approximately 20 microns.

Abstract

Beschrieben wird ein fotografisches Trägermaterial für schwarz/weiß- und farbfotografische Schichten, das zumindest einseitig mit einer Weißpigment enthaltenden Schicht überzogen ist, deren Binderkomponente überwiegend aus ungesättigten, organischen Verbindungen besteht und mittels energieliefernder Strahlung gehärtet ist, wobei das weißpigment, welches vorzugsweise ein Titanoxid oder -mischoxid ist, eine anorganische Oberflächenbelegung trägt, die aus Oxiden oder Oxidhydraten besteht, welche wenigstens 2 Gew.-% des Gesamtpigments ausmacht. Bei den Oxiden und Oxidhydraten handelt es sich um solche des Aluminiums, des Siliziums, des Zinks, des Magnesiums, des Zinns, des Zirkons, des Antimons oder der Erdalkalimetalle.A photographic support material for black / white and color photographic layers is described, which is coated on at least one side with a layer containing white pigment, the binder component of which consists predominantly of unsaturated, organic compounds and is hardened by means of energy-providing radiation, the white pigment, which is preferably a titanium oxide or -mixed oxide, carries an inorganic surface coating, which consists of oxides or oxide hydrates, which makes up at least 2 wt .-% of the total pigment. The oxides and hydrated oxides are those of aluminum, silicon, zinc, magnesium, tin, zirconium, antimony or alkaline earth metals.

Description

Die Erfindung betrifft ein Trägermaterial für schwarz/weiß- und farbfotografische Schichten, das zumindest einen mittels Elektronenstrahlen gehärteten Oberzug enthält.The invention relates to a carrier material for black / white and color photographic layers, which contains at least one cover layer hardened by means of electron beams.

Es Ist eine Vielzahl von Trägermaterialien für fotografische Schichten bekannt. Zu den verbreitetsten Trägern gehören Filmmaterialien und Papiere. Papiere sind in der Regel zusätzlich beschichtet. Insbesondere mit Kunstharzschichten überzogene wasserfeste Papiere haben eine breite Anwendung als Träger für fotografische Schichten gefunden. Aber auch mit speziellen Schichten überzogene Kunstharzfilme und Laminate sind bekannt. Die weiteste Verbreitung fanden beidseitig mit Polyolefinharz überzogene Papiere und mit pigmentierten Schichten überzogene Filmmaterialien (DAS 14 47 815, US 38 33 380, US 36 30 742, US 39 28 037). Solche Oberzüge haben jedoch nur eine begrenzte Pigmentaufnahme, sind nicht kratzfest und sind ungeeignet für thermische Bildentwicklung.A large number of substrates for photographic layers are known. The most common media include film materials and papers. Papers are usually additionally coated. Waterproof papers coated in particular with synthetic resin layers have found wide use as supports for photographic layers. Resin films and laminates coated with special layers are also known. Papers coated on both sides with polyolefin resin and film materials coated with pigmented layers (DAS 14 47 815, US 38 33 380, US 36 30 742, US 39 28 037) were most widespread. However, such coatings only have a limited pigment absorption, are not scratch-resistant and are unsuitable for thermal image development.

In neuerer Zeit wurden in DOS 30 22 451 und DOS 30 22 709 besonders fortschrittliche Papierträger beschrieben, die aus Basispapier mit mindestens einem in situ mit Hilfe einer Elektronenstrahlenhärtung hergestellten Oberzug bestehen. Die Vorteile eines mit Elektronenstrahlen gehärteten Oberzuges sind seine Kratzfestigkeit, das hohe Pigmentaufnahmevermögen und die im Vergleich zu Polyolefinüberzügen höhere Glätte der Oberfläche.Recently, particularly advanced paper supports have been described in DOS 30 22 451 and DOS 30 22 709, which consist of base paper with at least one top layer produced in situ with the aid of electron beam curing. The advantages of an upper layer hardened with electron beams are its scratch resistance, the high pigment absorption capacity and the higher smoothness of the surface in comparison to polyolefin coatings.

Kunstharzüberzüge sind nicht nur gegen Wasser, sondern auch gegen saure und alkalische fotografische Prozeßlösungen beständig und verhindern dadurch ein Eindringen dieser Lösungen in eventuell darunter liegende Papierträger.Resin coatings are not only resistant to water, but also to acidic and alkaline photographic process solutions and thus prevent these solutions from penetrating into any paper carrier underneath.

Infolgedessen ist bei Papier oder Vliesbasis der zeitraubende Waschvorgang entscheidend verkürzt.As a result, the time-consuming washing process for paper or nonwoven base is significantly shortened.

Alle Harzüberzüge, seien sie auf Papier oder auf Film, können 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. Von den möglichen Zusätzen haben Pigmente und Farbstoffe die größte Bedeutung für den visuellen Eindruck eines auf dem Uberzug befindlichen fotografischen Bildes. Sie bestimmen bei Farbbildern den Farbcharakter und sind entscheidend für die Bildschärfe der fotografischen Abbildungen.All resin coatings, whether on paper or on film, 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. Of the possible additives, pigments and dyes are of the greatest importance for the visual impression of a photographic image on the coating. They determine the color character of color images and are decisive for the sharpness of the photographic images.

Die fotografischen Schichten werden nach geeigneter Vorbehandlung der Harzoberfläche entweder direkt oder nach vorheriger Aufbringung einer Haftung vermittelnden Zwischenschicht auf die Oberfläche der Harzschicht gebracht. Bei diesen fotografischen Schichten handelt es sich vorzugsweise um solche Schichten, die unter dem Begriff der Silbersalzfotografie bekannt sind und entweder zur Erzeugung von Schwarz/Weiß- oder von Farbbildern dienen.After suitable pretreatment of the resin surface, the photographic layers are applied to the surface of the resin layer either directly or after previously applying an adhesion-promoting intermediate layer. These photographic layers are preferably layers which are known under the term silver salt photography and which are used either for producing black / white or color images.

Gemäß DOS 30 22 451 oder DOS 30 22 709 mit Elektronenstrahlen gehärtete Harzüberzüge werden hergestellt, indem eine fließfähige Mischung auf die Oberfläche eines Papieres oder anderen Basisträgers aufgetragen, dort gleichmäßig verteilt und anschließend unter Schutzgas oder sonstiger Abdekkung mit energiereichen Elektronenstrahlen verfestigt wird. Die Mischungen enthalten als entscheidenden Bestandteil zumindest eine Substanz mit äthylenisch ungesättigten Doppelbindungen, die die Fähigkeit zur polymerisierenden Reaktion miteinander haben, wenn diese durch Bestrahlung initiiert wird.Resin coatings hardened with electron beams in accordance with DOS 30 22 451 or DOS 30 22 709 are produced by applying a flowable mixture to the surface of a paper or other base support, distributing it uniformly there and then solidifying it under inert gas or other covering with high-energy electron beams. The mixtures contain at least one substance with an ethylenically unsaturated double as a crucial constituent bonds that have the ability to polymerize with one another when initiated by radiation.

Die mit Elektronenstrahlen gehärteten Schichten haben nun zwar im Vergleich zu Polyolefinschichten viele Vorteile, sind aber bislang auch noch mit Nachteilen behaftet. So gelang es trotz der großen Variationsbreite in der Zusammensetzung strahlengehärteter Schichten nicht, eine Schicht zu erzeugen, die in allen fotografischen Prozeßlösungen ein gleichermaßen gutes Verhalten zeigt. Vielmehr wurde festgestellt, daß die mit Elektronenstrahlen gehärteten Schichten sich gegenüber verschiedenen Prozeßlösungen unterschiedlich verhalten. Es gibt handelsübliche Colorentwicklerpräparate, die in Verbindung mit einer nachfolgenden Sauerstoffeinwirkung zu einer gelblichen Verfärbung der Oberfläche der strahlengehärteten Schicht führen. Diese Verfärbung ist zwar gering, aber deutlich sichtbar und kann weder durch das Stoppbad, noch durch gründliches Waschen verhindert werden. Sie tritt vor allem bei Anwendung solcher fotografischer Entwicklerlösungen auf, die ein aromatisches Aminderivat enthalten (z.B. Derivate von Phenylendiamin, Toluidin u.a.). Die Verwendung von Papieren mit strahlengehärtetem Uberzug ist infolgedessen bislang beschränkt auf solche Prozesse, in denen andere Chemikalien zur Bildentwicklung benutzt werden, wie z. B. Hydrochinon.The layers hardened with electron beams now have many advantages compared to polyolefin layers, but so far they have also had disadvantages. Despite the wide range of variations in the composition of radiation-hardened layers, it was not possible to create a layer that showed equally good behavior in all photographic process solutions. Rather, it was found that the layers hardened with electron beams behave differently towards different process solutions. There are commercially available color developer preparations which, in combination with subsequent exposure to oxygen, lead to a yellowish discoloration of the surface of the radiation-hardened layer. This discoloration is slight, but clearly visible and can neither be prevented by the stop bath, nor by thorough washing. It occurs especially when using such photographic developer solutions that contain an aromatic amine derivative (e.g. derivatives of phenylenediamine, toluidine, etc.). As a result, the use of papers with a radiation-hardened coating has hitherto been restricted to processes in which other chemicals are used for image development, such as, for example. B. Hydroquinone.

Diese Gelbfärbung durch Colorentwickler tritt weder bei Polyolefinoberflächen auf, die Rutil oder Anatas oder ein anderes Weißpigment enthalten, noch ist sie an den klassischen Barytpapieren zu beobachten, die wenigstens einen im wesentlichen aus Bariumsulfat und Gelatine bestehenden Uberzug tragen. Auch andere aus verschiedenen Kunstharzen und Weißpigment bestehenden Uberzüge zeigen diese Anfärbung nicht, während bisher beschriebene strahlengehärtete Überzüge auf der Basis von Acrylaten, Methacrylaten oder Allylverbindungen mit Colorentwickler immer sichtbar angefärbt werden. Entscheidend für die Verfärbung mit Entwickler scheint demnach der Binderanteil, insbesondere eine mögliche Anwesenheit ungesättigter organischer Verbindungen zu sein.This yellowing by color developers does not occur with polyolefin surfaces which contain rutile or anatase or another white pigment, nor is it observed on classic baryta papers which have at least one coating consisting essentially of barium sulfate and gelatin. Also other coatings consisting of different synthetic resins and white pigment do not show this staining, whereas previously described radiation-hardened coatings based on acrylates, methacrylates or allyl compounds are always visibly colored with color developers. Decisive for the discoloration with developer therefore seems to be the proportion of binder, especially a possible presence of unsaturated organic compounds.

Die Verfärbung von strahlengehärteten Überzügen mit Colorentwickler zeigt sich sowohl bei pigmentfreien Überzügen als auch bei Überzügen, die Weißpigment enthalten. In der Regel ist die Verfärbung bei pigmenthaltigen Überzügen sogar stärker als bei pigmentfreien Überzügen wie die nachstehende Tabelle 1 zeigt. (Der hier verwendete Binder bestand aus 62 Gew.-% Polyestertetraacrylat, 22,5 Gew.-% Glycerinpropoxitriacrylat und 15,5 Gew.-% Hexandioldiacrylat).

Figure imgb0001
Figure imgb0002
 The discoloration of radiation-hardened coatings with color developers is evident both with pigment-free coatings and with coatings that contain white pigment. As a rule, the discoloration is even stronger with pigment-containing coatings than with pigment-free coatings, as shown in Table 1 below. (The binder used here consisted of 62% by weight of polyester tetraacrylate, 22.5% by weight of glycerol propoxitriacrylate and 15.5% by weight of hexanediol diacrylate).
Figure imgb0001
Figure imgb0002

In der deutschen Patentanmeldung P 34 15 215 wurde bereits ein Weg aufgezeigt, um durch spezielle Zusammensetzung der härtbaren Komponenten einer Uberzugsmischung Schichten mit verringerter Anfärbung zu erhalten. Das dort beschriebene Verfahren basiert darauf, daß ungesättigte hydroxifunktionelle Verbindungen in einer molalen Konzentration von 2 oder mehr als 2 in den Uberzugsmischungen enthalten sind.German patent application P 34 15 215 has already shown a way to obtain layers with reduced staining by means of a special composition of the curable components of a coating mixture. The process described there 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 technische Lehre aus P 34 15 215 ist grundsätzlich sowohl auf pigmentfreie wie auf pigmentierte Überzugsmischungen anwendbar. Allerdings färben sich pigmenthaltige Uberzugsmischungen in der Regel etwas stärker an als pigmentfreie Überzüge. Deshalb sollte die OH-Konzentration in pigmentierten Überzügen im allgemeinen ein wenig höher sein als in vergleichbaren pigmentfreien Überzügen.The technical teaching from P 34 15 215 is basically applicable to both pigment-free and pigmented coating mixtures. However, pigment-containing coating mixtures usually stain somewhat more strongly than pigment-free coatings. Therefore, the OH concentration in pigmented coatings should generally be a little higher than in comparable pigment-free coatings.

Nachteilig an dieser mit der Patentanmeldung P 34 15 215 gegebenen Lösung ist jedoch die starke Beschränkung in der Auswahl der verwendbaren Mischungskomponenten. Dieser Nachteil machtsich besonders bei höher pigmentierten Schichten bemerkbar, die zur Vermeidung einer unerwünschten Sprödigkeit mit steigendem Pigmentgehalt eine steigende Menge an flexibilisierenden Zusätzen benötigen.A disadvantage of this solution given by patent application P 34 15 215, however, is the strong limitation in the selection of the mixture components that can be used. This disadvantage is particularly noticeable in the case of highly pigmented layers, which are used to avoid an undesirable brittle with increasing pigment content need an increasing amount of flexibilizing additives.

Es ist daher Aufgabe der vorliegenden Erfindung, eine strahlengehärtete Oberzugsschicht zu schaffen, die eine möglichst vielseitige Verwendung des überzogenen Trägers ermöglicht und insbesondere auch nach üblicher Behandlung mit handelsüblichen Colorentwicklern nur eine geringe oder keine Anfärbung zeigt.It is therefore an object of the present invention to provide a radiation-hardened top layer which enables the coated backing to be used in as many different ways as possible and in particular shows little or no staining even after customary treatment with commercially available color developers.

Diese Aufgabe wird dadurch gelöst, daß als Weißpigment ein Titandioxid verwendet wird, das eine anorganische Oberflächenbelegung trägt, die wenigstens 2 Gew.-% des Gesamtpigments ausmacht.This object is achieved in that a titanium dioxide is used as the white pigment which bears an inorganic surface coating which makes up at least 2% by weight of the total pigment.

In Oberzugsschichten verwendete Titandioxidpigmente können un - behandelt sein wie das in Tabelle 1 enthaltene Ti02 (Rutil 2). Vielfach sind sie aber zwecks Verbesserung der Dispergierbarkeit mit anorganischen Oxiden (AIZ03, AIO (OH), SiO2, ZnO u. a.) oberflächlich nachbehandelt, d. h. belegt. Dabei sind unter Oxiden im weiteren Sinne auch Oxidhydrate zu verstehen. Solche oberflächenbelegten Typen sind beispielsweise die in Tabelle 1 enthaltenen TiO2 (Anatas) und Ti02 (Rutil 1), die mit 0,6 bzw. 1,0 Gew.-% AI-Oxid belegt sind und wie die übrigen Weißpigmente der Tabelle 1 zu einer verstärkten Verfärbung mit Colorentwickler führen.Titanium dioxide pigments used in coating layers can be untreated like the Ti0 2 (rutile 2) contained in Table 1. In many cases, however, they are surface-treated, ie coated, to improve the dispersibility with inorganic oxides (Al Z 0 3 , AlO (OH), SiO 2 , ZnO etc.). Oxides in the broader sense also mean oxide hydrates. Such surface-coated types are, for example, the TiO 2 (anatase) and Ti0 2 (rutile 1) contained in Table 1, which are coated with 0.6 and 1.0% by weight Al oxide, and like the other white pigments in Table 1 lead to increased discoloration with color developers.

Auch die Verwendung solcher Titandioxide, die allein oder zusätzlich zur anorganischen Oberflächenbelegung mit organischen Stoffen behandelt sind, führt nicht zu einer Verringerung der Anfärbung mit Colorentwickler, außer wenn gleichzeitig OH-haltige Verbindungen gemäß P 34 15 215.6 anwesend sind.The use of such titanium dioxides, which are treated alone or in addition to the inorganic surface covering with organic substances, does not lead to a reduction in the coloration with color developer, unless OH-containing compounds according to P 34 1 5 215.6 are present at the same time.

Uberraschenderweise ist die Verfärbung mit Colorentwickler jedoch deutlich geringer, wenn ein Titandioxid verwendet wird, das mit 2-Gew.-% oder mehr als 2 Gew.-% eines anorganischen Oxides oder Oxidhydrates oberflächenbelegt ist. Das anorganische Oxid oder Oxidhydrat kann ein Aluminiumoxid oder Kieselsäure oder Zinkoxid oder Magnesiumoxid oder Zinnoxid oder Zirkonoxid oder Antimonoxid oder eines der Erdalkalimetalloxide oder Mischungen solcher Verbindungen sein. Aufgrund der Oberflächenbelegung sind die Titandioxidteilchen mit einem mehr oder weniger geschlossenen Uberzug von Fremdoxid oder -oxidhydrat versehen. Die Belegung kann aus einer oder aus mehreren Schichten bestehen und neben den genannten noch andere Oxide enthalten, sofern diese nicht färbend sind.Surprisingly, however, the discoloration with color developer is significantly less if a titanium dioxide is used which is surface-coated with 2% by weight or more than 2% by weight of an inorganic oxide or hydrated oxide. The inorganic oxide or hydrated oxide can be an aluminum oxide or silica or zinc oxide or magnesium oxide or tin oxide or zirconium oxide or antimony oxide or one of the alkaline earth metal oxides or mixtures of such compounds. Due to the surface coverage, the titanium dioxide particles are provided with a more or less closed coating of foreign oxide or oxide hydrate. The coating can consist of one or more layers and contain other oxides in addition to those mentioned, provided that these are not coloring.

Derart belegte Titandioxidpigmente können nach einem beliebigen Verfahren hergestellt sein. Sie können ferner unter der Oberflächenbelegung als gemischte Oxide mit einem anderen weißen Oxid vorliegen, und sie können zusätzlich in beliebiger Weise mit organischen Verbindungen behandelt sein. Entscheidend ist, daß die Pigmentteilchen eine ausreichend starke Belegung aus einem anderen anorganischen Oxid oder Oxidhydrat enthalten als Ti02.Titanium dioxide pigments coated in this way can be produced by any process. They can also exist as mixed oxides with another white oxide under the surface coverage, and they can additionally be treated in any way with organic compounds. It is crucial that the pigment particles contain a sufficiently strong coating of an inorganic oxide or hydrated oxide other than Ti0 2 .

Oberflächenbelegungen mit Titandioxidpigment mit verschiedenen anorganischen Überzügen sind in "Titanium" von J. Barksdale (New York, 1966) sowie in verschiedenen Patenten und Patentanmeldungen beschrieben. Es ist aus der japanischen Offenlegungsschrift 57-108849/1982 auch bekannt, mit 0,2 bis 1,2 Gew.-% Aluminumoxidhydrat nachbehandeltes Titandioxid in Polyolefinüberzügen auf fotografischen Papieren zu verwenden.Surface coatings with titanium dioxide pigment with various inorganic coatings are described in "Titanium" by J. Barksdale (New York, 1966) and in various patents and patent applications. It is also known from Japanese Patent Application Laid-Open No. 57-108849 / 1982 titanium dioxide aftertreated with 0.2 to 1.2% by weight of aluminum oxide hydrate in polyolefin coatings on photographic papers.

Es ist jedoch überraschend, daß Titandioxid-Pigmente, die mit 2 oder mehr Gew.-% beliebiger weißer Oxide oder Oxidhydrate belegt sind, in strahlengehärteten Uberzugsmischungen eine besonders vorteilhafte Wirkung auf die Anfärbung der gehärteten Uberzugsschicht mit fotografischem Colorentwickler haben. Dies ist umso überraschender als die entsprechenden Oxide und Oxidhydrate selbst bei alleiniger Anwendung in strahlengehärteten Schichten zu einer verstärkten Verfärbung führen (vergl. Tabelle 1).It is surprising, however, that titanium dioxide pigments coated with 2 or more% by weight of any white oxides or hydrated oxides in radiation-hardened coating mixtures have a particularly advantageous effect on the coloring of the hardened coating layer with a photographic color developer. This is all the more surprising since the corresponding oxides and hydrated oxides lead to increased discoloration even when used alone in radiation-hardened layers (see Table 1).

Die Vorteile einer erfindungsgemäßen Verwendung von Titandioxidpigmenten mit 2 oder mehr Gew.-% anderer Oxid-oder Oxidhydratüberzüge in strahlengehärteten Schichten zeigen sich sowohl in Schichten, die mittels Elektronenstrahlen gehärtet werden, als auch in auf andere Weise gehärteten Schichten aus ungesättigten Ausgangskomponenten. Die Uberzugsschichten können sich auf Papier, Film, Metallfolie, Papierlaminat oder einem beliebigen anderen Träger befinden und bekannte andere Zusätze enthalten.The advantages of using titanium dioxide pigments with 2 or more% by weight of other oxide or oxide hydrate coatings in radiation-hardened layers are evident both in layers which are hardened by means of electron beams and in layers of unsaturated starting components hardened in another way. The coating layers can be on paper, film, metal foil, paper laminate or any other support and contain known other additives.

In einer besonderen Ausführungsform der Erfindung wird Titandioxidpigment verwendet, dessen Oberflächenbelegung großenteils oder gar überwiegend aus Kieselsäure besteht. Daneben kann ein kleiner Anteil eines Aluminiumoxids und/oder Zinkoxids und/oder Antimonoxids und/oder Zirkonoxids und/oder Erdalkalioxids vorhanden sein. Es ist dabei von untergeordneter Bedeutung, ob die Umhüllung des TiO, mehr oder weniger geschlossen ist. Entscheidend ist offensichtlich der Belegungsgrad.In a special embodiment of the invention, titanium dioxide pigment is used, the surface covering of which consists largely or even predominantly of silica. In addition, a small proportion of an aluminum oxide and / or zinc oxide and / or antimony oxide and / or zirconium oxide and / or alkaline earth oxide can be present. It is of minor importance whether the coating of the TiO is more or less closed. The key is open obviously the degree of occupancy.

Eine zusätzliche organische Oberflächenbelegung z.B. mit mehrwertigem Alkohol, (Poly)Siloxan, organischen Titanaten, Organophosphaten, Lacton, Aminoverbindungen u.a. Stoffen, die im allgemeinen der Verbesserung der Dispergierbarkeit dient, ist möglich und entfaltet ihre bekannten Vorteile auch bei den mit anorganischen Oxiden belegten Titandioxid-Pigmenten.An additional organic surface covering e.g. with polyhydric alcohol, (poly) siloxane, organic titanates, organophosphates, lactone, amino compounds etc. Substances which generally serve to improve the dispersibility are possible and also have their known advantages in the case of the titanium dioxide pigments coated with inorganic oxides.

Unter Titandioxid-Pigment im Sinne der Erfindung sind nicht nur die bekannten Ti02- Modifikationen Rutil und Anatas zu verstehen, sondern auch andere reine oder gemischte Titanoxide sowie weiße pigmentartige Titanate.Titanium dioxide pigment in the sense of the invention is not only to be understood to mean the known Ti0 2 modifications rutile and anatase, but also other pure or mixed titanium oxides and white pigment-like titanates.

Besonders vorteilhaft kann es sein, wenn mit wenigstens 2 Gew.-% Fremdoxid oberflächenbelegtes Titandioxid in einer härtbaren Mischung angewandt wird, die hydroxifunktionelle ungesättigte Substanzen enthält. Der besondere Vorteil dieser Kombination liegt darin, daß die molale Konzentration der OH-Gruppen in der Mischung durchaus auch kleiner als 2 sein kann und trotzdem Schichten erhalten werden, die keine sichtbare Anfärbung mit Colorentwickler zeigen.It can be particularly advantageous if titanium dioxide surface-coated with at least 2% by weight of foreign oxide is used in a hardenable mixture which contains hydroxyl-functional unsaturated substances. The particular advantage of this combination is that the molar concentration of the OH groups in the mixture can also be less than 2, and nonetheless layers are obtained which show no visible coloring with color developer.

Besonders vorteilhaft wirkt sich die Erfindung aus, wenn die durch Elektronenstrahlen härtbaren Stoffe Mischungen sind, die zumindest einen Stoff enthalten, der zwei oder mehr Doppelbindungen enthält. Daneben können in begrenztem Umfang aber auch nicht reagierende Stoffe ohne Doppelbindungen in einer Mischung enthalten sein.The invention has a particularly advantageous effect if the substances curable by electron beams are mixtures which contain at least one substance which contains two or more double bonds. In addition, non-reactive substances without double bonds can also be contained in a mixture to a limited extent.

Als reaktionsfähige Komponenten werden vor allem solche Stoffe benutzt, die Acrylat- oder Methacrylatgruppen enthalten. Aber auch Ester von Maleinsäure, Fumarsäure, Mesaconsäure, Citraconsäure oder Itaconsäure, andere Derivate dieser Säuren, Allylverbindungen sowie lineare und cyclische Diene bzw. Triene eignen sich als reaktive Mischungskomponenten. Bevorzugt sind solche Ester der genannten Säuren, die sich von mehrwertigen Alkoholen ableiten. Beispiele sind Hexandioldiacrylat, Trimethylolpropantriacrylat, Polyesteracrylate, Polyurethanacrylate, Polyätheracrylate, Polyepoxydiacrylate, Alkydharzacrylate bzw, die den genannten Acrylaten entsprechenden Methacrylate.Substances that contain acrylate or methacrylate groups are primarily used as reactive components contain. However, 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 are also suitable as reactive mixture components. Those esters of the acids mentioned which are derived from polyhydric alcohols are preferred. Examples are hexanediol diacrylate, trimethylolpropane triacrylate, polyester acrylates, polyurethane acrylates, polyether acrylates, polyepoxy diacrylates, alkyd resin acrylates or the methacrylates corresponding to the acrylates mentioned.

Die Fließeigenschaften solcher härtbarer Mischungen werden erfindungsgemäß eingestellt, indem Bestandteile von höherem Molekulargewicht mit niedermolekularen Stoffen gemischt werden. Die Härte und Flexibilität der gehärteten Schichten wird bestimmt durch das im Ausgangsmaterial vorhandene Verhältnis von Doppelbindungen zur Molekülgröße und kann in weitem Rahmen durch Mischung verschiedener Stoffe miteinander variiert werden.The flow properties of such curable mixtures are adjusted according to the invention by mixing constituents of higher molecular weight with low molecular weight substances. The hardness and flexibility of the hardened layers is determined by the ratio of double bonds to the molecular size in the starting material and can be varied widely by mixing different substances.

Erfindungsgemäße Trägermaterialien eignen sich als Träger für alle bekannten wenigstens eine Silberverbindung enthaltenden fotografischen Schichten. Insbesondere eignen sie sich sowohl für alle Verfahren der Naßentwicklung als auch für thermische Bildentwicklungsverfahren.Support materials according to the invention are suitable as supports for all known photographic layers containing at least one silver compound. In particular, they are suitable for all wet development processes as well as for thermal image development processes.

Mit den nachfolgenden Beispielen wird der Erfindungsgedanke näher erläutert.The concept of the invention is explained in more detail with the following examples.

Beispiel 1example 1

Eine Mischung aus 62 Gew.-% Polyestertetraacrylat (M = ca. 1000), 22, Gew.-% Glycerinpropoxitriacrylat und 15,5 Gew.-% Hexandioldiacrylat wurde einerseits ohne Pigmentzusatz und andererseits mit Zusatz von 20 Gew.-% Titandioxidpigment mit 2 oder mehr Gew.-% anorganischer Oberflächenbelegung gleichmäßig auf ein Polyethylen/Papier-Laminat gebracht und mittels Elektronenstrahlen ausgehärtet. Der gehärtete überzug hatte jeweils die Dicke von ca. 20 gm.A mixture of 62% by weight of polyester tetraacrylate (M = approx. 1000), 22% by weight of glycerol propoxitriacrylate and 15.5% by weight of hexanediol diacrylate was added on the one hand without pigment addition and on the other hand with the addition of 20% by weight of titanium dioxide pigment with 2 or more% by weight of inorganic surface coverage evenly placed on a polyethylene / paper laminate and cured by means of electron beams. The hardened coating had a thickness of approx. 20 g m.

Die Schichtüberzüge wurden anschließend mit handelsüblichem fotografischem Entwickler für Colorpapier behandelt, gewaschen und die Proben vier Tage bei Zimmertemperatur unter Luftzutritt gelagert. Die sich währen der Lagerung einstellende Verfärbung der Schichtoberfläche wurde nach DIN 4512 als Veränderung der optischen Dichte gegenüber dem Ausgangswert bestimmt und ist in Tabelle 2 aufgeführt.

Figure imgb0003
The layer coatings were then treated with commercially available photographic developer for color paper, washed and the samples were stored for four days at room temperature with access to air. The discoloration of the layer surface that occurred during storage was determined according to DIN 4512 as a change in the optical density compared to the initial value and is shown in Table 2.
Figure imgb0003

Diese Reihe zeigt, daß die Verfärbung der Schicht durch Titanoxid-Pigmente mit 2 Gew.-% und mehr als 2 Gew.-% Fremdoxidbelegung vermindert werden kann. Dabei dient Versuch 1a als Vergleich, und die übrigen Versuche zeigen die Abnahme der Verfärbung mit zunehmender Belegung.This series shows that the discoloration of the layer can be reduced by titanium oxide pigments with 2% by weight and more than 2% by weight of foreign oxide coating. Experiment 1a serves as a comparison, and the remaining experiments show the decrease in discoloration with increasing occupancy.

Beispiel 2Example 2

Eine Grundmischung aus 50 Gew.-% Tripropylenglykoldiacrylat, 45 Gew.-% Trimethylolpropantriacrylat und 5 Gew.-% Glycidilmethacrylat wurde einerseits ohne Pigmentzusatz (2a) und andererseits mit Zusatz von 30 Gew.-% Titanoxidpigment (2b) auf ein fotografisches Basispapier gebracht, mit Hilfe eines Rakelstabes zu einer Dicke von ca. 35 µm egalisiert und mittels Elektronenstrahlen in bekannter Weise gehärtet.A B a mixture of 50 wt .-% of tripropylene glycol diacrylate, 45 wt .-% trimethylolpropane triacrylate and 5 wt .-% glycidyl methacrylate was brought on the one hand without added pigment (2a) and on the other hand with the addition of 30 wt .-% titanium oxide pigment (2b) on a photographic base paper , leveled with the aid of a doctor rod to a thickness of approx. 35 µm and hardened in a known manner by means of electron beams.

Die Schichtüberzüge wurden wie im Beispiel 1 mit Colorentwickler behandelt und die Verfärbung bestimmt. Die Ergebnisse sind in Tabelle 3 zusammengestellt.

Figure imgb0004
The layer coatings were treated with color developer as in Example 1 and the discoloration was determined. The results are summarized in Table 3.
Figure imgb0004

Auch diese Reihe bestätigt, daß die durch Colorentwickler verursachte Verfärbung durch solche Titanoxid-Pigmente vermindert wird, die wenigstens 2 Gew.-% einer Fremdoxidbelegung enthalten. Selbst bei einer infolge des Glycidylmethacrylat-Zusatzes stark anfärbenden Schicht kann die Verfärbung durch stärkere Belegung der Titanoxidoberfläche so stark vermindert werden, daß die Schicht nahezu weiß erscheint (Versuche 2h und 2p). Im Rahmen der Erfindung ist entscheidend, daß auch hier der Wendepunkt hinsichtlich der Verfärbung bei einer Belegung von 2 Gew.-% liegt.This series also confirms that the discoloration caused by color developers is reduced by those titanium oxide pigments which contain at least 2% by weight of a foreign oxide coating. Even in the case of a layer which strongly stains as a result of the addition of glycidyl methacrylate, the discoloration can be caused by a stronger coating of the titanium oxide surface be reduced so much that the layer appears almost white (tests 2h and 2p). It is crucial in the context of the invention that the turning point with regard to the discoloration is an occupancy of 2% by weight.

Beispiel 3Example 3

Eine Grundmischung aus 45 Gew.-% Pentaerythritoltriacrylat, 50 Gew.-% Triethylenglykoldiacrylat und 5 Gew.-% Hydroxyethylacrylat wurde wie im Beispiel 1 einerseits ohne Pigmentzusatz und andererseits mit Zusatz von 40 Gew.-% verschiedener Titanoxid-Pigmente gleichmäßig auf ein Polyethylen/Papier-Laminat gebracht und mittels Elektronenstrahlen ausgehärtet. Der gehärtete Uberzug hatte jeweils eine Dicke von ca. 20 µm. Die OH-Molalität der Grundmischung ist 2.A basic mixture of 45% by weight of pentaerythritol triacrylate, 50% by weight of triethylene glycol diacrylate and 5% by weight of hydroxyethyl acrylate was uniformly applied to a polyethylene on the one hand without pigment addition and on the other hand with the addition of 40% by weight of different titanium oxide pigments / Paper laminate brought and cured by means of electron beams. The cured coating each had a thickness of approximately 20 microns. The OH M olalität the base mixture 2.

Die Schichten wurden wie im Beispiel 1 geprüft. Die Prüfergebnisse sind in Tabelle 4 zusammengestellt.

Figure imgb0005
The layers were tested as in Example 1. The test results are summarized in Table 4.
Figure imgb0005

Auch diese Versuchsreihe, bei der hydroxifunktionelle härtbare Komponenten zum Einsatz kamen, bestätigt den Vorteil einer Verwendung von Titanoxiden mit einer Fremdomidbelegung von wenigstens 2 Gew.-%. Gleichzeitig demonstriert diese Reihe die besonderen Vorteile der Kombination von hydroxifunktionellen härtbaren Stoffen gemeinsam mit einem fremdbelegten Titanoxid mit wenigstens 2% Belegung.This series of experiments, in which hydroxyl-functional curable components were used, also confirms the advantage of using titanium oxides with a foreign domide coating of at least 2% by weight. At the same time, this series demonstrates the special advantages of combining hydroxy-functional curable materials together with an externally coated titanium oxide with at least 2% coating.

Claims (10)

1. Fotografisches Trägermaterial für schwarz/weiß- und farbfotografische Schichten, das zumindest einseitig mit einer Weißpigment enthaltenden Schicht überzogen ist, deren Binderkomponente überwiegend aus ungesättigten Verbindungen hergestellt und vermittels energieliefernder Strahlung gehärtet ist, dadurch gekennzeichnet, daß als Weißpigment ein Pigment verwendet wird, das eine anorganische Oberflächenbelegung trägt, die wenigstens 2 Gew.-% des Gesamtpigments ausmacht.1. Photographic support material for black / white and color photographic layers, which is coated at least on one side with a layer containing white pigment, the binder component of which is predominantly made from unsaturated compounds and hardened by means of energy-providing radiation, characterized in that a pigment is used as the white pigment bears an inorganic surface coating which makes up at least 2% by weight of the total pigment. 2. Trägermaterial nach Anspruch 1, dadurch gekennzeichnet, daß die anorganische Oberflächenbelegung vorzugsweise 3 bis 20 Gew.-% des Gesamtpigments ausmacht.2. Support material according to claim 1, characterized in that the inorganic surface coating preferably makes up 3 to 20% by weight of the total pigment. 3. Trägermaterial nach Anspruch 1, dadurch gekennzeichnet, daß das Weißpigment ein Titandioxid oder Titanmischoxid oder ein weißes pigmentartiges Titanat ist.3. Support material according to claim 1, characterized in that the white pigment is a titanium dioxide or titanium mixed oxide or a white pigment-like titanate. 4. Trägermaterial nach Anspruch 1, dadurch gekennzeichnet, daß die anorganische Oberflächenbelegung der Weißpigmentteilchen aus einem Oxid oder Oxidhydrat des Aluminiums, des Siliziums, des Zinks, des Magnesiums, des Zinns, des Zirkons, des Antimons oder der Erdalkalimetalle oder aus Mischungen dieser Oxide und Oxidhydraten besteht.4. Support material according to claim 1, characterized in that the inorganic surface coating of the white pigment particles of an oxide or hydrated oxide of aluminum, silicon, zinc, magnesium, tin, zirconium, antimony or alkaline earth metals or mixtures of these oxides and Oxide hydrates exist. 5. Trägermaterial nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß das mit wenigstens 2 Gew.- % Fremdoxid oberflächenbelegte Titandioxid in eine härtbare Binderkomponente eingearbeitet ist, die hydroxifunktionelle ungesättigte Substanzen enthält. 5 . Support material according to Claims 1 to 3, characterized in that the titanium dioxide surface-coated with at least 2% by weight of foreign oxide is incorporated into a hardenable binder component which contains hydroxyl-functional unsaturated substances. 6. Trägermaterial nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß die Teilchen des Weißpigments eine Belegung haben, die überwiegend aus Kieselsäure besteht.6. Support material according to claim 1 to 4, characterized in that the particles of the white pigment have an occupancy which consists predominantly of silica. 7. Trägermaterial nach Anspruch 5, dadurch gekennzeichnet, daß die Titandioxidteilchen mit einer Oberflächenbelegung versehen sind, die überwiegend aus Kieselsäure und kleinen Anteilen eines Aluminiums und/oder Zinkoxids und/oder Antimon- und/oder Zirkonoxids und/oder Erdalkalimetall besteht.7. Support material according to claim 5, characterized in that the titanium dioxide particles are provided with a surface covering which consists predominantly of silica and small proportions of aluminum and / or zinc oxide and / or antimony and / or zirconium oxide and / or alkaline earth metal. 8. Trägermaterial nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß die Binderkomponente, in der das Weißpigment dispergiert ist, mindestens einen Stoff enthält, der zwei oder mehr Doppelbindungen enthält.8. Support material according to claim 1 to 6, characterized in that the binder component in which the white pigment is dispersed contains at least one substance which contains two or more double bonds. 9. Verwendung eines Trägermaterils nach Anspruch 1 als Träger für fotografische Schichten, die wenigstens eine anorganische oder organische Silberverbindung enthalten.9. Use of a carrier material according to claim 1 as a carrier for photographic layers which contain at least one inorganic or organic silver compound. 10. Verwendung eines Trägermaterials nach Anspruch 1 als Träger für fotografische Schwarz/Weiß- oder Farbschichten, die durch Wärmeeinwirkung entwickelt werden können.10. Use of a support material according to claim 1 as a support for photographic black / white or color layers which can be developed by the action of heat.
EP85103457A 1984-09-28 1985-03-23 Support material for black and white and colour photography Expired - Lifetime EP0176656B1 (en)

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US4752559A (en) * 1987-03-24 1988-06-21 Helland Randall H Primer/antihalation coating for photothermographic constructions
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JP2726087B2 (en) * 1988-12-23 1998-03-11 三菱製紙株式会社 Manufacturing method of photographic support
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JPH0619521B2 (en) 1994-03-16
GR852331B (en) 1985-11-27
EP0176656A3 (en) 1988-09-21
DE3435639A1 (en) 1986-04-10
ATE57773T1 (en) 1990-11-15
ES8609749A1 (en) 1986-07-16
DE3435639C2 (en) 1988-09-22
PT80747B (en) 1987-09-30
PT80747A (en) 1985-08-01
EP0176656B1 (en) 1990-10-24
JPS6186747A (en) 1986-05-02
ES545895A0 (en) 1986-07-16
US4665013A (en) 1987-05-12
DE3580232D1 (en) 1990-11-29

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