EP0028003B1 - Recording material containing diazo compounds and a filter layer and process for the production of same - Google Patents

Recording material containing diazo compounds and a filter layer and process for the production of same Download PDF

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Publication number
EP0028003B1
EP0028003B1 EP80106437A EP80106437A EP0028003B1 EP 0028003 B1 EP0028003 B1 EP 0028003B1 EP 80106437 A EP80106437 A EP 80106437A EP 80106437 A EP80106437 A EP 80106437A EP 0028003 B1 EP0028003 B1 EP 0028003B1
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EP
European Patent Office
Prior art keywords
layer
filter layer
recording material
polymer
light
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
EP80106437A
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German (de)
French (fr)
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EP0028003A1 (en
Inventor
Siegfried Dr. Scheler
Klaus Dr. Thoese
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Hoechst AG
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Hoechst AG
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Priority to AT80106437T priority Critical patent/ATE5673T1/en
Publication of EP0028003A1 publication Critical patent/EP0028003A1/en
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Publication of EP0028003B1 publication Critical patent/EP0028003B1/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
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • 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
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/08—Photoprinting; Processes and means for preventing photoprinting
    • 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
    • Y10S430/132—Anti-ultraviolet fading

Definitions

  • the invention relates to a recording material containing diazo compounds, in particular a microfilm, comprising a layer support which is at least partially transparent to visible radiation, a light-sensitive layer on one side and a filter layer absorbing in the boring UV and short-wave, visible spectral range on the other side of the layer support and a Process for its production.
  • the materials should therefore be such that the light-absorbing materials cannot be removed. For example, they should no longer be separate from the layer support, or they should only be removable by partially destroying the layer support and reducing the information contained therein.
  • the solution to this problem is based on a recording material containing diazo compounds, in particular a microfilm, a layer support which is at least partially transparent to visible radiation, a light-sensitive layer on the one hand and a filter layer absorbing in the long-wave UV and short-wave, visible spectral range on the other hand of the layer support, which is characterized in that the filter layer is a polymer which is insoluble in acetone or an isopropanol / water mixture or is made less soluble by crosslinking in these solvents and at least one dye which is compatible with the constituents of the polymer and has an absorption in the range between 360 nm and 500 nm contains.
  • the filter layer preferably contains a yellow to orange dye.
  • the filter layer offers the possibility of economically influencing the properties of the film by incorporating further tension shocks in the same work step.
  • Suitable layer supports which are at least partially transparent to visible radiation are, for example, cellulose esters or polymers, mixed or copolymers which are processed from the melt into transparent films, such as polystyrene or polycarbonate. Films made from polyethylene terephthalate or from its copolymers or copolymers, which are selected essentially on the basis of their optical and mechanical properties, have proven to be particularly advantageous.
  • the light-sensitive layers used are those based on diazo compounds.
  • Photosensitive layers which contain at least one diazonium compound and at least one coupling component as the photosensitive substance are preferably used.
  • the filter layer absorbing in the long-wave UV and short-wave visible spectral range contains modified terephthalic acid ester as insoluble polymer, for example a terephthalic acid copolyester with a content of bisoxyethyl-b13phenol A, isophthalic acid or neopentyl glycol.
  • modified terephthalic acid ester as insoluble polymer, for example a terephthalic acid copolyester with a content of bisoxyethyl-b13phenol A, isophthalic acid or neopentyl glycol.
  • polymers which are made less soluble by crosslinking in aggressive solvents those with suitable functional groups can be used.
  • cellulose esters can be used together with a curing agent, such as urea or melamine-formaldehyde resins, and a curing accelerator, such as p-toluenesulfonic acid.
  • the polymers made less soluble by crosslinking are also intended to include poly
  • the dye compatible with the components of the polymer is colored yellow to orange.
  • it In addition to the required spectral properties, such as absorption in the range between 360 and 500 nm and the greatest possible light stability, it must be soluble in the coating solvent and sufficiently heat-stable. It must neither emerge or sublime from the filter layer as a result of exudation before nor after the copying process, nor can other film materials be transferred to the surface as a result of clapping.
  • chemical compounds from the suitable dye and the polymer used are advantageous.
  • the dye In the case of application by coextrusion or from the melt, the dye must also, in addition to the required spectral properties at the usual high temperatures, be well compatible with the polymer and so heat-stable that it does not change its spectral properties under extreme stress.
  • Suitable dyes are, for example, mono- and bis-azo dyes such as Sudangelb GGN (C.I. Solvent Yellow 56), provided they meet the required solubility criteria, such as solubility in alcohols, ketones and / or ethers, or the required compatibility criteria.
  • solubility criteria such as solubility in alcohols, ketones and / or ethers, or the required compatibility criteria.
  • a layer applied to the back of the layer support can furthermore contain conventional additives such as finely divided slip agents or commercially available antistatic agents.
  • the filter layer according to the invention thus fulfills further important application requirements without additional work steps.
  • the invention also relates to a process for the preparation of the recording material containing diazo compounds, in particular a microfilm, by applying a filter layer absorbing in the boring UV and in the short-wave, visible spectral range to one side and by applying a solution and drying a light-sensitive layer to the other side layer carrier which is at least partially permeable to visible radiation, which is characterized in that first the filter layer is composed of a polymer which is insoluble in acetone or an isopropanol / water mixture or a polymer which is less soluble by crosslinking in these solvents and at least one, with the constituents of the polymer compatible dye with an absorption in the range between 360 nm and 500 nm and hardens and then provides the support on the other side with the photosensitive layer.
  • the filter layer is preferably applied using an adhesion-promoting intermediate layer with the aid of a lacquer solution which contains the polymer which is less soluble by crosslinking, together with the dye, and is then dried and cured.
  • the recording material according to the invention can be produced by coextrusion of the support and filter layer or by melt coating on the stretched or undrawn support.
  • the layer support material and the colored filter layer material are simultaneously coextruded and brought together from a multi-slot die. This process is of great advantage because it usually does not require an additional intermediate layer to improve adhesion.
  • the application after the melt coating is preferably carried out on the stretched substrate.
  • melt containing dye can be prepared separately, for example also via a color masterbatch. It is also possible to use polymers which are more easily meltable or more miscible with the dye and which, for reasons of mechanical strength, are less suitable for the production of film carrier materials. Because the filter layer is very thin is, measured on the total film thickness, the dye can also be incorporated more economically than when coloring the support. Furthermore, temperature / time ratios for the thin melt layer that are compatible with the decomposability of the dyes can be selected.
  • the coating of the support with a colored lacquer requires an intermediate adhesive layer, as described for example in DE-B-1 694 534. After the coating solution has been applied, it is dried and, as a result of a heat treatment, the filter layer is inseparably connected to the correspondingly subbed surface of the support.
  • the filter layer is additionally ratzif by the crosslinked structure is less K.
  • the dry layer weight is generally 5 to 20 g / m 2.
  • the light-absorbing filter layers as far as they are processed as lacquer, can be applied by printing, casting or other known methods. After the solvent has evaporated, ensure that the filter layer is sufficiently hardened by heating, exposure to UV light or the like.
  • a preferred embodiment for dyes with lower thermal stability is their use in a hardened filter layer which, if required, can also be advantageously printed with colored title strips. While in the case of uncured filter layers, printing can be difficult due to the partial or complete dissolution of the lacquer layer by the solvent of the printing ink, the printing of hardened filter layers without process engineering difficulties is much easier. The selection of a suitable base printing system is easier and less critical than with unhardened lacquer layers.
  • the yellow layers of paint are each dried for 3 minutes at 100 ° C. and then cured for up to 5 minutes by heating. During the drying and curing phase, the coated film samples lie on an aluminum plate as a flat surface.
  • the dry layer weights are about 7 g / m 2.
  • a 7% solution of cellulose acetopropionate in a solvent mixture of acetone, methanol, n-butanol and ethylene glycol monomethyl ether serves as the basecoat.
  • the crosslinkable, yellow-colored lacquer is obtained from the non-crosslinkable lacquer by adding so much hexamethoxymethylmelamine that a ratio of cellulose ester to melamine resin of 9: 1 is obtained.
  • P-Toluenesulfonic acid serves as a curing accelerator.
  • the yellow film pattern B is produced with this crosslinkable, yellow lacquer.
  • the cellulose acetopropionate used here contains 3.6% acetyl groups, 44.7% propionyl groups and 1.8% hydroxyl groups and, as a 20% solution in acetone / ethanol (72: 8), has a viscosity of 53-91 dPas.
  • photosensitive yellow film samples A and B 1 are obtained.
  • the dry layer weight of the photosensitive layer is 6 g / m 2.
  • the light-sensitive layer of the yellow film patterns A1 and B1 is exposed in contact under a transparent silver image template and then the latent copy of the diazo film is developed in a humid ammonia atmosphere. Exposure and development takes place in a commercially available »diazomicrofilm duplicating device «. High-contrast two-color copies of the original are obtained, with a blue dye image on one side and an orange-yellow background on the other side of the film. When viewed in transmitted light, the image parts of the copies appear black, the background image orange-yellow.
  • the second generation of diazo films A 2 and B 2 cannot be produced from the diazo film copies A 1 and B 1 obtained, since it is no longer possible to differentiate between image and non-image areas.
  • the diazo film copies A 1 and B 1 cannot be duplicated.
  • the non-crosslinked yellow filter layer of the diazo film copy A 1 can be removed in a few seconds with a cotton ball soaked in acetone, for example. Those parts of the image of the diazo film copy A 1 which are opposite the detached filter layer on the other side of the film can be duplicated again.
  • the production of the second generation diazo film A 2 is possible by removing the yellow filter layer.
  • the comparative experiment shows that a hardened yellow filter layer considerably increases the security of a non-duplicable microfilm, even if an aggressive solvent such as acetone is used for detachment.
  • the procedure for producing the diazo film copy C 1 is as described in Example 1, except that the same weight amount of a butylated urea-formaldehyde resin is used as the cross-linking component for the cellulose acetopropionate.
  • the urea resin used is a commercial product with an acid number of less than 3.
  • a 65% solution of this resin in isobutanol has a viscosity of 10-12dPas at 20 ° C.
  • the solvent resistance of the crosslinked yellow filter layer of the diazo film copy C 1 is again compared with the non-crosslinked yellow filter layer of the diazo film copy A 1 of Example 1.
  • a mixture of 80 parts by weight of isopropanol and 20 parts by weight of water is used as the solvent in this experiment.
  • a duplication attempt is then carried out.
  • Example 1 the superiority of the crosslinked yellow filter layer of the diazo film copy C 1 over the uncrosslinked of the diazo film copy A 1 is evident both in the solvent treatment and in the subsequent duplication attempt. While A 1 shows the known results, the diazo film copy C 1 can only be duplicated with significant loss of information. The production of the second generation of diazo film C 2 is considerably more difficult here.
  • Example 2 The procedure is as in Example 1, except that dimethyl yellow (C.I. Solvent Yellow 2) is used as the dye for the yellow filter layer. To produce the yellow colored absorbent filter layer, 8.75 g of dimethyl yellow are dissolved in 700 g of basecoat.
  • dimethyl yellow C.I. Solvent Yellow 2
  • the non-crosslinked yellow filter layer of the diazo film copy D 1 is compared with the crosslinked of the diazo film copy E 1 in terms of solvent resistance and generation ability.
  • a mixture of 80 parts by weight of isopropanol and 20 parts by weight of water is used as the solvent, as described in Example 2.
  • the non-crosslinked yellow filter layer of the diazo film copy D 1 is easier to remove at the same time than the crosslinked one of the diazo film copy E 1.
  • the duplicability of the solvent-treated diazo film copy E 1 is worse than that of D 1.
  • the production of the second generation of diazo film E 2 is less significantly more difficult than D 2.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Luminescent Compositions (AREA)
  • Testing Or Measuring Of Semiconductors Or The Like (AREA)

Abstract

This invention relates to a recording material containing diazo compounds, in particular a microfilm, comprising a film base which is at least partially pervious to visible radiation, a light-sensitive layer and, on the reverse side of the film base, a filter layer which absorbs light in the long-wave ultraviolet spectral range and in the short-wave visible spectral range, wherein the filter layer is composed of a polymer which is insoluble or has been rendered insoluble by cross-linking, and of at least one yellow to orange-colored dye which is compatible with the constituents of the polymer and absorbs light in the range between about 360 nm and about 500 nm. The invention also relates to a process for the manufacture of a recording material.

Description

Die Erfindung betrifft ein Diazoverbindungen enthaltendes Aufzeichnungsmaterial, insbesondere einen Mikrofilm, aus einem für sichtbare Strahlung mindestens teilweise durchlässigen Schichtträger, einer lichtempfindlichen Schicht auf der einen und einer im langweiligen UV- und im kurzwelligen, sichtbaren Spektralbereich absorbierenden Filterschicht auf der anderen Seite des Schichtträgers und ein Verfahren zu seiner Herstellung.The invention relates to a recording material containing diazo compounds, in particular a microfilm, comprising a layer support which is at least partially transparent to visible radiation, a light-sensitive layer on one side and a filter layer absorbing in the boring UV and short-wave, visible spectral range on the other side of the layer support and a Process for its production.

Aufzeichnungsmaterialien der genannten Art erlangen ihrer vorzüglichen Eigenschaften wegen immer mehr an Bedeutung. Sie werden für die verschiedenen Anwendungsgebiete speziell ausgerüstet und erlauben als entscheidenden Vorteil eine erhebliche Verdichtung von Informationen zum Beispiel in Archiven, in der Industrie und in der Verwalung.Recording materials of the type mentioned are becoming increasingly important due to their excellent properties. They are specially equipped for the various areas of application and, as a decisive advantage, allow a considerable compression of information, for example in archives, in industry and in administration.

Man kann in der Regel von Duplikaten, die zum Beispiel vom Silberoriginal erstellt werden, beliebig viele weitere Kopien anfertigen. Diese Eigenschaft ist in vielen Fällen wünschenswert und von großem Nutzen. Wo jedoch etwa von einem urheberrechtlich geschützten Original Kopien nur als Lese- oder Arbeitskopien angefertigt und verkauft werden, ist die Weiterduplizierfähigkeit dieser Kopien nachteilig. Lesekopien für den Marktsektor »Micropublishing« sollten deshalb so beschaffen sein, daß keine weitern Kopien, sogenannte »Raubkopien«, angefertigt werden können.As a rule, you can make any number of additional copies of duplicates, for example those created by the silver original. In many cases, this property is desirable and of great use. However, where copies of a copyrighted original are only made and sold as read or working copies, the ability to duplicate these copies is disadvantageous. Read copies for the »micropublishing« market sector should therefore be such that no further copies, so-called »pirated copies«, can be made.

Vorschläge zur Herstellung von Filmmaterialien mit kopiersicheren Eigenschaften sind bekannt. So kann man zum Beispiel mit Hilfe einer lichtstreuenden Schicht (DE-B-1 915 210) oder mit Hilfe einer lichtabsorbierenden Schicht (DE-C-671 641, DE-A-2 344 089), das Anfertigen von weiteren Kopien im Durchlichtverfahren unmöglich machen. Es hat sich jedoch angezeigt, daß lichtstreuende Schichten nur unter großem technischem Aufwand hergestellt werden können und selbst dann nur bei relativ großer Schichtdicke wirksam sind. Damit ist aber der Vorteil dünner Materialien als Voraussetzung für große Informationsdichte verloren. Die Verwendung von lichtabsorbierenden Materialien erfolgt entweder eingearbeitet in den Schichtträger oder getrennt in einzelner Schicht, wobei man solche Stoffe einbaut, die im Empfindlichkeitsbereich der bekannten Diazoverbindungen lichtundurchlässig sind. Die Einarbeitung dieser Stoffe in den Schichtträger ist bei dessen Herstellung nachteilig, da dies nur unter speziellen Verfahrensbedingungen erfolgen kann, was zum Beispiel nur bei Produktion großer Mengen überhaupt wirtschaftlich ist. So fallen bei einer späteren Extruderreinigung mehr oder minder gefärbte, unerwünscht große Mengen Polyestermasse als Abfall an. Andererseits treten bei Einarbeitung lichtabsorbierender Materialien in die lichtempfindliche Schicht Auflösungs- und Kontrastverluste ein.Proposals for the production of film materials with copy-proof properties are known. For example, it is impossible with the aid of a light-scattering layer (DE-B-1 915 210) or with the aid of a light-absorbing layer (DE-C-671 641, DE-A-2 344 089) to make further copies using the transmitted light method do. However, it has been found that light-scattering layers can only be produced with great technical outlay and even then are only effective with a relatively large layer thickness. However, the advantage of thin materials as a prerequisite for high information density is lost. The use of light-absorbing materials is either incorporated into the layer support or separately in a single layer, with substances being incorporated which are opaque in the sensitivity range of the known diazo compounds. The incorporation of these substances into the layer support is disadvantageous during its production, since this can only take place under special process conditions, which is only economical, for example, only when large quantities are produced. In a later extruder cleaning, more or less colored, undesirably large amounts of polyester mass are generated as waste. On the other hand, resolution and contrast losses occur when light-absorbing materials are incorporated into the light-sensitive layer.

Es ist im Prinzip auch möglich (US-A-4080208), die lichtabsorbierende Filterschicht zwischen Schichtträger und lichtempfindlicher Schicht anzuordnen. Lichtabsorbierende Schichten in dieser Anordnung sind aber nur dann geeignet, wenn die Rollneigung des Films nicht verstärkt wird. Außerdem muß man dafür Sorge tragen, daß ein Eindiffundieren des lichtabsorbierenden Materials in die lichtempfindliche Schicht vermieden wird. Es ist aus dieser Patentschrift auch bekannt, die lichtabsorbierende Filterschicht auf der Rückseite des Schichtträgers anzuordnen. Diese Schicht erfüllt aber nur dann ihre Aufgabe ausreichend, wenn sie nicht durch mechanische Behandlung oder Abwaschen mit Lösungsmitteln so leicht entfernt werden kann, daß danach das Aufzeichnungsmaterial ohne weiteres als Kopiervorlage verwendet werden kann. Daß man zunächst den lichtabsorbierenden Stoff aufträgt und dann die lichtempfindliche Schicht, ist der DE-C-671 641 zu entnehmen.In principle, it is also possible (US-A-4080208) to arrange the light-absorbing filter layer between the support and the light-sensitive layer. However, light-absorbing layers in this arrangement are only suitable if the curl of the film is not increased. In addition, care must be taken to prevent the light-absorbing material from diffusing into the light-sensitive layer. It is also known from this patent to arrange the light-absorbing filter layer on the back of the layer support. However, this layer only fulfills its task adequately if it cannot be removed so easily by mechanical treatment or washing off with solvents that the recording material can then be used as a template. DE-C-671 641 shows that first the light-absorbing substance is applied and then the light-sensitive layer.

Es war deshalb Aufgabe der Erfindung, Diazoverbindungen enthaltende Aufzeichnungsmaterialien zusammen mit lichtabsorbierenden Stoffen zur Verfügung zu stellen, welche sich nicht zum Weiterkopieren eignen. Die Materialien sollten deshalb so beschaffen sein, daß die lichtabsorbierenden Stoffe nicht entfernbar sind. Sie sollten zum Beispiel von dem Schichtträger nicht mehr getrennt, oder nur unter teilweiser Zerstörung des Schichtträgers und unter Verminderung der beinhaltenden Information entfernbar sein.It was therefore an object of the invention to provide recording materials containing diazo compounds together with light-absorbing substances which are not suitable for further copying. The materials should therefore be such that the light-absorbing materials cannot be removed. For example, they should no longer be separate from the layer support, or they should only be removable by partially destroying the layer support and reducing the information contained therein.

Die Lösung dieser Aufgabe geht aus von einem Diazoverbindungen enthaltenden Aufzeichnungsmaterial, insbesondere einem Mikrofilm, aus einem für sichtbare Strahlung mindestens teilweise durchlässigen Schichtträger, einer lichtempfindlichen Schicht auf der einen und einer im langwelligen UV- und im kurzwelligen, sichtbaren Spektralbereich absorbierenden Filterschicht auf der anderen Seite des Schichtträgers, welches dadurch gekennzeichnet ist, daß die Filterschicht ein in Aceton oder einem Isopropanol/Wasser-Gemisch unlösliches oder ein durch Vernetzung in diesen Lösungsmitteln weniger löslich gemachtes Polymer und mindestens einen mit den Bestandteilen des Polymers verträglichen Farbstoff mit einer Absorption im Bereich zwischen 360 nm und 500 nm enthält. Vorzugsweise enthält die Filterschicht einen gelben bis orangenen Farbstoff.The solution to this problem is based on a recording material containing diazo compounds, in particular a microfilm, a layer support which is at least partially transparent to visible radiation, a light-sensitive layer on the one hand and a filter layer absorbing in the long-wave UV and short-wave, visible spectral range on the other hand of the layer support, which is characterized in that the filter layer is a polymer which is insoluble in acetone or an isopropanol / water mixture or is made less soluble by crosslinking in these solvents and at least one dye which is compatible with the constituents of the polymer and has an absorption in the range between 360 nm and 500 nm contains. The filter layer preferably contains a yellow to orange dye.

Hierdurch wird erreicht, daß ein Diazoverbindungen enthaltendes Aufzeichnungsmaterial erhältlich ist, welches, auch nach unerlaubter Handhabung, nicht weiter kopierbar ist. Außerdem bietet die Filterschicht die Möglichkeit, durch die Einarbeitung weiterer Zugschläge im gleichen Arbeitsgang die Eigenschaften des Films in wirtschaftlicher Weise vorteilhaft zu beeinflussen.This ensures that a recording material containing diazo compounds is available which, even after unauthorized handling, cannot be copied any further. In addition, the filter layer offers the possibility of economically influencing the properties of the film by incorporating further tension shocks in the same work step.

Als für sichtbare Strahlung mindestens teilweise durchlässige Schichtträger sind beispielsweise Celluloseester oder Polymere, Misch-oder Copolymere geeignet, die aus der Schmelze zu transparenten Folien verarbeitet werden, wie zum Beispiel Polystyrol oder Polycarbonat. Als besonders vorteilhaft haben sich Folien aus Polyethylenterephthalat oder aus dessen Co-oder Mischpolymeren erwiesen, die im wesentlichen aufgrund ihrer optischen und mechanischen Eigenschaften ausgewählt werden.Suitable layer supports which are at least partially transparent to visible radiation are, for example, cellulose esters or polymers, mixed or copolymers which are processed from the melt into transparent films, such as polystyrene or polycarbonate. Films made from polyethylene terephthalate or from its copolymers or copolymers, which are selected essentially on the basis of their optical and mechanical properties, have proven to be particularly advantageous.

Als lichtempfindliche Schichten dienen solche, die auf Basis von Diazoverbindungen aufgebaut sind. Vorzugsweise werden lichtempfindliche Schichten eingesetzt, die als lichtempfindliche Substanz mindestens eine Diazoniumverbindung und mindestens eine Kupplungskomponente enthalten.The light-sensitive layers used are those based on diazo compounds. Photosensitive layers which contain at least one diazonium compound and at least one coupling component as the photosensitive substance are preferably used.

Die im langwelligen UV- und kurzwelligen sichtbaren Spektralbereich absorbierende Filterschicht enthält als unlösliches Polymer modifizierte Terephthalsäureester zum Beispiel einen Terephthalsäurecopolyester mit einem Gehalt an Bisoxyethyl-b13phenol A, Isophthalsäure oder Neopentylglykol. Als durch Vernetzung in aggressiven Lösungsmitteln weniger löslich gemachte Polymere können solche eingesetzt werden mit geeigneten funktionellen Gruppen. So können zum Beispiel Celluloseester zusammen mit einem Härtungsmittel, wie Harnstoff-oder Melamin-Formaldehydharze, und einem Härtungsbeschleuniger, wie p-Toluolsulfonsäure, verwendet werden. Unter die durch Vernetzung weniger löslich gemachten Polymere sollen auch fallen Polyamide, Polyisocyanate, Formaldehydharze und geeignete Prepolymere.The filter layer absorbing in the long-wave UV and short-wave visible spectral range contains modified terephthalic acid ester as insoluble polymer, for example a terephthalic acid copolyester with a content of bisoxyethyl-b13phenol A, isophthalic acid or neopentyl glycol. As polymers which are made less soluble by crosslinking in aggressive solvents, those with suitable functional groups can be used. For example, cellulose esters can be used together with a curing agent, such as urea or melamine-formaldehyde resins, and a curing accelerator, such as p-toluenesulfonic acid. The polymers made less soluble by crosslinking are also intended to include polyamides, polyisocyanates, formaldehyde resins and suitable prepolymers.

Der mit den Bestandteilen des Polymers verträgliche Farbstoff ist gelb bis orange gefärbt. Er muß außer den geforderten spektralen Eigenschaften, wie Absorption im Bereich zwischen 360 und 500 nm und möglichst großer Lichtstabilität, im Lacklösungsmittel löslich und ausreichend wärmestabil sein. Er darf weder vor noch nach dem Kopiervorgang aus der Filterschicht infolge Ausschwitzens austreten oder sublimieren, noch sich infolge Abklatschens auf die Oberfläche andere Filmmaterialien übertragen lassen. In dieser Hinsicht sind chemische Verbindungen aus dem geeigneten Farbstoff und dem eingesetzten Polymer von Vorteil. Im Falle der Auftragung durch Coextrusion oder aus der Schmelze muß der Farbstoff ebenfalls neben den geforderten spektralen Eigenschaften bei den üblichen hohen Temperaturen mit dem Polymer gut verträglich und so wärmestabil sein, daß er bei der extremen Beanspruchung seine spektralen Eigenschaften nicht verändert.The dye compatible with the components of the polymer is colored yellow to orange. In addition to the required spectral properties, such as absorption in the range between 360 and 500 nm and the greatest possible light stability, it must be soluble in the coating solvent and sufficiently heat-stable. It must neither emerge or sublime from the filter layer as a result of exudation before nor after the copying process, nor can other film materials be transferred to the surface as a result of clapping. In this regard, chemical compounds from the suitable dye and the polymer used are advantageous. In the case of application by coextrusion or from the melt, the dye must also, in addition to the required spectral properties at the usual high temperatures, be well compatible with the polymer and so heat-stable that it does not change its spectral properties under extreme stress.

Gut geeignete Farbstoffe sind zum Beispiel Mono- und Bis-Azofarbstoffe wie Sudangelb GGN (C. I. Solvent Yellow 56), soweit sie die geforderten Löslichkeitskriterien, wie Löslichkeit zum Beispiel in Alkoholen, Ketonen und/oder Äthern, bzw. die geforderten Verträglichkeitskriterien erfüllen.Suitable dyes are, for example, mono- and bis-azo dyes such as Sudangelb GGN (C.I. Solvent Yellow 56), provided they meet the required solubility criteria, such as solubility in alcohols, ketones and / or ethers, or the required compatibility criteria.

Eine auf der Rückseite des Schichtträgers aufgebrachte Schicht kann ferner übliche Zuschläge wie feinteiliges Schlupfmittel oder handelsübliche Antistatika enthalten. Die erfindungsgemäße Filterschicht erfüllt damit ohne zusätzliche weitere Arbeitsschritte weitere, wichtige anwendungstechnische Anforderungen.A layer applied to the back of the layer support can furthermore contain conventional additives such as finely divided slip agents or commercially available antistatic agents. The filter layer according to the invention thus fulfills further important application requirements without additional work steps.

Will man vermeiden, daß der Farbton einer aufgedruckten Titelleiste durch die Filterschicht beeinflußt wird, ist es notwendig, die Schicht nur auf die Fläche anzutragen, die später nicht mit der Titelleiste bedruckt wird.If you want to avoid that the color tone of a printed title bar is influenced by the filter layer, it is necessary to apply the layer only to the area that will not be printed with the title bar later.

Die Erfindung betrifft auch ein Verfahren zur Herstellung des Diazoverbindungen enthaltenden Aufzeichnungsmaterials, insbesondere eines Mikrofilms durch Aufbringen einer im langweiligen UV- und im kurzwelligen, sichtbaren Spektralbereich absorbierenden Filterschicht auf die eine Seite und durch Aufbringen aus Lösung und Trocknen einer lichtempfindlichen Schicht auf die andere Seite eines für sichtbare Strahlung mindestens teilweise durchlässigen Schichtträgers, welches dadurch gekennzeichnet ist, daß man auf den Schichtträger zuerst die Filterschicht aus einem in Aceton oder einem lsopropanol/Wasser-Gemisch unlöslichen oder aus einem durch Vernetzung in diesen Lösungsmitteln weniger löslich zu machenden Polymer und mindestens einem, mit den Bestandteilen des Polymers verträglichen Farbstoff mit einer Absorption im Bereich zwischen 360 nm und 500 nm aufbringt und härtet und anschließend den Schichtträger auf der anderen Seite mit der lichtempfindlichen Schicht versieht. Vorzugsweise bringt man die Filterschicht unter Verwendung einer haftvermittelnden Zwischenschicht mit Hilfe einer Lacklösung, die das durch Vernetzung weniger löslich zu machende Polymer zusammen mit dem Farbstoff enthält auf, trocknet und härtet anschließend.The invention also relates to a process for the preparation of the recording material containing diazo compounds, in particular a microfilm, by applying a filter layer absorbing in the boring UV and in the short-wave, visible spectral range to one side and by applying a solution and drying a light-sensitive layer to the other side layer carrier which is at least partially permeable to visible radiation, which is characterized in that first the filter layer is composed of a polymer which is insoluble in acetone or an isopropanol / water mixture or a polymer which is less soluble by crosslinking in these solvents and at least one, with the constituents of the polymer compatible dye with an absorption in the range between 360 nm and 500 nm and hardens and then provides the support on the other side with the photosensitive layer. The filter layer is preferably applied using an adhesion-promoting intermediate layer with the aid of a lacquer solution which contains the polymer which is less soluble by crosslinking, together with the dye, and is then dried and cured.

Das erfindungsgemäße Aufzeichnungsmaterial kann durch Koextrusion von Schichtträger und Filterschicht oder durch Schmelzbeschichtung auf den verstreckten oder unverstreckten Schichtträger hergestellt werden. Bei der Koextrusion wird aus einer Mehrschlitzdüse gleichzeitig das Schichtträgermaterial und das gefärbte Filterschichtmaterial koextrudiert und zusammengeführt. Dieses Verfahren ist deswegen von großem Vorteil, weil hierbei meistens keine zusätzliche, die Haftung verbessernde Zwischenschicht notwendig ist. Das Aufbringen nach der Schmelzbeschichtung erfolgt vorzugsweise auf den verstreckten Schichtträger.The recording material according to the invention can be produced by coextrusion of the support and filter layer or by melt coating on the stretched or undrawn support. In the case of coextrusion, the layer support material and the colored filter layer material are simultaneously coextruded and brought together from a multi-slot die. This process is of great advantage because it usually does not require an additional intermediate layer to improve adhesion. The application after the melt coating is preferably carried out on the stretched substrate.

Gegenüber der Einarbeitung in das Polymer des Schichtträgers bietet die Koextrusion oder die Schmelzbeschichtung den Vorteil, daß die Farbstoff enthaltende Schmelze gesondert, zum Beispiel auch über ein Farbmasterbatch, angesetzt werden kann. So können auch leichter schmelzbare oder besser mit dem Farbstoff mischbare Polymere angewendet werden, die aus Gründen mechanischer Festigkeit für die Herstellung von Filmträgermaterialien weniger geeignet sind. Da die Filterschicht nur sehr dünn ist, gemessen an der Gesamtfolienstärke, läßt sich der Farbstoff auch wirtschaftlicher einarbeiten als bei einer Färbung des Schichtträgers. Weiterhin können der Zersetzlichkeit der Farbstoffe entgegenkommende Temperatur/Zeitverhältnisse für die dünne Schmelzschicht gewählt werden.Compared to incorporation into the polymer of the layer support, coextrusion or melt coating offers the advantage that the melt containing dye can be prepared separately, for example also via a color masterbatch. It is also possible to use polymers which are more easily meltable or more miscible with the dye and which, for reasons of mechanical strength, are less suitable for the production of film carrier materials. Because the filter layer is very thin is, measured on the total film thickness, the dye can also be incorporated more economically than when coloring the support. Furthermore, temperature / time ratios for the thin melt layer that are compatible with the decomposability of the dyes can be selected.

Die Beschichtung des Schichtträgers mit einem gefärbten Lack bedarf, wie schon ausgeführt, einer Haftzwischenschicht, wie sie zum Beispiel in DE-B-1 694 534 beschrieben ist. Nach Aufbringen der Lacklösung wird getrocknet und infolge einer Wärmebehandlung die Filterschicht mit entsprechend substrierter Oberfläche des Schichtträgers untrennbar verbunden. Die Filterschicht ist zusätzlich durch die vernetzte Struktur weniger Kratzempfindlich. Das Trockenschichtgewicht besagt im allgemeinen 5 bis 20 g/m2.The coating of the support with a colored lacquer, as already stated, requires an intermediate adhesive layer, as described for example in DE-B-1 694 534. After the coating solution has been applied, it is dried and, as a result of a heat treatment, the filter layer is inseparably connected to the correspondingly subbed surface of the support. The filter layer is additionally ratzempfindlich by the crosslinked structure is less K. The dry layer weight is generally 5 to 20 g / m 2.

Die lichtabsorbierenden Filterschichten können, soweit sie als Lack verarbeitet werden, durch Drucken, Gießen oder andere bekannte Verfahren aufgetragen werden. Nach dem Verdunsten des Lösungsmittels ist durch Erwärmung, Belichtung mit UV-Licht o. ä. dafür zu sorgen, daß die Filterschicht ausreichend gehärtet wird.The light-absorbing filter layers, as far as they are processed as lacquer, can be applied by printing, casting or other known methods. After the solvent has evaporated, ensure that the filter layer is sufficiently hardened by heating, exposure to UV light or the like.

Bevorzugte Ausführungsform für Farbstoffe mit geringerer Wärmestabilität ist ihre Verwendung in einer gehärteten Filterschicht, die bei Bedarf vorteilhaft auch mit farbigen Titelleisten bedruckt werden kann. Während bei nicht gehärteten Filterschichten das Bedrucken infolge teilweiser oder vollständiger Auflösung der Lackschicht durch das Lösungsmittel der Druckfarbe schwierig sein kann, ist das Bedrucken gehärteter Filterschichten ohne verfahrenstechnische Schwierigkeiten wesentlich leicher möglich. Die Auswahl eines geeigneten Basisdrucksystems ist einfacher und unkritischer als bei ungehärteten Lackschichten.A preferred embodiment for dyes with lower thermal stability is their use in a hardened filter layer which, if required, can also be advantageously printed with colored title strips. While in the case of uncured filter layers, printing can be difficult due to the partial or complete dissolution of the lacquer layer by the solvent of the printing ink, the printing of hardened filter layers without process engineering difficulties is much easier. The selection of a suitable base printing system is easier and less critical than with unhardened lacquer layers.

Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.

Beispiel 1example 1

Eine 125 µm dicke, glasklare Folie aus Polyethylenterephthalat, die auf beiden Seiten mit einer Haftschicht versehen ist, wird mit Hilfe eines 10 cm breiten Ziehgießers von 0,15 mm Spaltweite einseitig mit gelb eingefärbten Klarlacken beschichtet. Die gelben Lackschichten werden jeweils 3 Minuten bei 100° C getrocknet und anschließend bis zu 5 Minuten durch Erwärmen nachgehärtet. Während der Trocknungs- und Härtungsphase liegen die beschichteten Filmmuster auf einer Aluminiumplatte als ebene Unterlage. Die Trockenschichtgewichte betragen etwa 7 g/m2.A 125 µm thick, crystal-clear film made of polyethylene terephthalate, which is provided with an adhesive layer on both sides, is coated on one side with yellow-colored clear lacquers with the aid of a 10 cm wide die-casting mold with a gap of 0.15 mm. The yellow layers of paint are each dried for 3 minutes at 100 ° C. and then cured for up to 5 minutes by heating. During the drying and curing phase, the coated film samples lie on an aluminum plate as a flat surface. The dry layer weights are about 7 g / m 2.

Als Basislack dient eine 7%ige Lösung von Celluloseacetopropionat in einem Lösungsmittelgemisch aus Aceton, Methanol, n-Butanol und Ethylenglykolmonomethylether.A 7% solution of cellulose acetopropionate in a solvent mixture of acetone, methanol, n-butanol and ethylene glycol monomethyl ether serves as the basecoat.

In 1000 g dieser Lacklösung werden 12,5 g Sudangelb GGN (C. I. Solvent Yellow 56) aufgelöst. Dieser gelb eingefärbte Lack wird zur Herstellung des nicht vernetzten Gelbfolienmusters A als Vergleich verwendet.12.5 g of Sudangelb GGN (C.I. Solvent Yellow 56) are dissolved in 1000 g of this coating solution. This yellow-colored lacquer is used as a comparison for producing the non-crosslinked yellow film pattern A.

Den vernetzbaren, gelb eingefärbten Lack erhält man aus dem nicht vernetzbaren Lack durch Hinzufügen von so viel Hexamethoxymethylmelamin, daß sich ein Verhältnis von Celluloseester zu Melaminharz von 9 : 1 einstellt. Als Härtungsbeschleuniger dient p-Toluolsulfonsäure. Mit diesem vernetzbaren, gelben Lack wird das Gelbfolienmuster B hergestellt.The crosslinkable, yellow-colored lacquer is obtained from the non-crosslinkable lacquer by adding so much hexamethoxymethylmelamine that a ratio of cellulose ester to melamine resin of 9: 1 is obtained. P-Toluenesulfonic acid serves as a curing accelerator. The yellow film pattern B is produced with this crosslinkable, yellow lacquer.

Das hier verwendete Celluloseacetopropionat enthält 3,6% Acetylgruppen, 44,7% Propionylgruppen und 1,8% Hydroxylgruppen und hat als 20%ige Lösung in Aceton/Äthanol (72: 8) eine Viskosität von 53-91 dPas.The cellulose acetopropionate used here contains 3.6% acetyl groups, 44.7% propionyl groups and 1.8% hydroxyl groups and, as a 20% solution in acetone / ethanol (72: 8), has a viscosity of 53-91 dPas.

Auf die Rückseiten der Gelbfolienmuster A und B wird mit einem Ziehgießer von 10 cm Breite und 0,15 mm Spaltweite eine lichtempfindliche Lösung folgender Zusammensetzung aufgebracht:

  • 100 ml Basislack
  • 150 mg 5-Sulfosalicylsäure
  • 400 mg 2-Hydroxy-3-naphthoesäure-N(2-methylphenyl)-amid
  • 150 mg Zinkchlorid
  • 500 mg 2,5-Di-n-butoxy-4-morpholinobenzol- diazoniumfluorborat.
A light-sensitive solution of the following composition is applied to the back of the yellow film samples A and B using a die-caster with a width of 10 cm and a gap of 0.15 mm:
  • 100 ml basecoat
  • 150 mg 5-sulfosalicylic acid
  • 400 mg of 2-hydroxy-3-naphthoic acid N (2-methylphenyl) amide
  • 150 mg zinc chloride
  • 500 mg of 2,5-di-n-butoxy-4-morpholinobenzene diazonium fluoroborate.

Nach erneuter Trocknung bei 110°C während 1 -2 Minuten erhält man die lichtempfindlichen Gelbfolienmuster A und B 1. Das Trockenschichtgewicht der lichtempfindlichen Schicht liegt bei 6 - g/m2.After renewed drying at 110 ° C. for 1-2 minutes, photosensitive yellow film samples A and B 1 are obtained. The dry layer weight of the photosensitive layer is 6 g / m 2.

Zur Herstellung der 1. Diazofilmgenerationen wird die lichtempfindliche Schicht der Gelbfolienmuster A 1 und B 1, wie in der Diazotypie üblich, unter einer transparenten Silberbildvorlage im Kontakt belichtet und dann die latente Diazofilmkopie in einer feuchten Ammoniakatmosphäre entwickelt. Belichtung und Entwicklung erfolgt in einem handelsüblichen »Diazomikrofilm-Dupliziergerät«. Man erhält kontrastreiche zweifarbige Kopien der Vorlage mit einem blauen Farbstoffbild auf der einen und einem orange-gelben Bilduntergrund auf der anderen Seite der Folie. Im Durchlicht betrachtet erscheinen die Bildteile der Kopien schwarz, der Bilduntergrund orangegelb. Von den erhaltenen Diazofilmkopien A 1 und B 1 ist die 2. Diazo-filmgeneration A 2 und B 2 nicht herzustellen, da eine Differenzierung von Bild- und Nichtbildstellen nicht mehr möglich ist. Die Diazofilmkopien A 1 und B 1 sind nicht duplizierbar.To produce the first generation of diazo films, the light-sensitive layer of the yellow film patterns A1 and B1, as is customary in the diazo type, is exposed in contact under a transparent silver image template and then the latent copy of the diazo film is developed in a humid ammonia atmosphere. Exposure and development takes place in a commercially available »diazomicrofilm duplicating device«. High-contrast two-color copies of the original are obtained, with a blue dye image on one side and an orange-yellow background on the other side of the film. When viewed in transmitted light, the image parts of the copies appear black, the background image orange-yellow. The second generation of diazo films A 2 and B 2 cannot be produced from the diazo film copies A 1 and B 1 obtained, since it is no longer possible to differentiate between image and non-image areas. The diazo film copies A 1 and B 1 cannot be duplicated.

Zur vergleichenden Prüfung des durch die Vernetzung der gelben Filterschicht erreichten technischen Fortschritts gegenüber einem Filmmaterial mit einer bekannten, nicht vernetzten, löslichen gelben Filterschicht, wurde versucht, die Filterschicht der Diazofilmkopien A 1 und B 1, ohne die Bildschicht auf der anderen Folienseite zu zerstören und ohne die Folie selbst zu beschädigen, durch handelsübliche Lösungsmittel abzulösen. Von den auf diese Weise behandelten Diazofilmkopien A 1 und B 1 sollte es dann möglich sein, die 2. Diazofilmgeneration herzustellen.To compare the technical progress achieved by crosslinking the yellow filter layer compared to a film material with a known, non-crosslinked, soluble yellow filter layer, an attempt was made to destroy the filter layer of the diazo film copies A 1 and B 1 without destroying the image layer on the other side of the film and without damaging the film itself, using commercially available solutions to replace tel. From the diazo film copies A 1 and B 1 treated in this way, it should then be possible to produce the second generation of diazo film.

Die nicht vernetzte gelbe Filterschicht der Diazofilmkopie A 1 läßt sich mit einem zum Beispiel mit Aceton getränkten Wattebausch in wenigen Sekunden entfernen. Diejenigen Bildteile der Diazofilmkopie A 1, die der abgelösten Filterschicht auf der anderen Folienseite gegenüberliegen, sind wieder duplizierbar. Die Anfertigung der 2. Diazofilmgeneration A 2 ist durch das Entfernen der gelben Filterschicht möglich geworfen.The non-crosslinked yellow filter layer of the diazo film copy A 1 can be removed in a few seconds with a cotton ball soaked in acetone, for example. Those parts of the image of the diazo film copy A 1 which are opposite the detached filter layer on the other side of the film can be duplicated again. The production of the second generation diazo film A 2 is possible by removing the yellow filter layer.

Wird die vernetzte gelbe Filterschicht der Diazofilmkopie B 1 der gleichen Behandlung unterworfen, dann wird die Filterschicht in der gleichen Zeit deutlich weniger angegriffen. Die Anfertigung der 2. Diazofilmgeneration B 2 von der Diazofilmkopie B 1 ist deshalb mit erheblichen Informationsverlusten verbunden. Die praktische Auswertung der Diazofilmkopie B 2 ist deshalb praktisch nicht möglich.If the crosslinked yellow filter layer of the diazo film copy B 1 is subjected to the same treatment, then the filter layer is attacked significantly less in the same time. The production of the second generation of diazo film B 2 from the diazo film copy B 1 is therefore associated with considerable loss of information. The practical evaluation of the diazo film copy B 2 is therefore practically impossible.

Der Vergleichsversuch zeigt, daß durch eine gehärtete gelbe Filterschicht die Sicherheit eines nicht duplizierbaren Mikrofilms erheblich erhöht wird, selbst dann, wenn ein so aggressives Lösungsmittel wie Aceton zur Ablösung benutzt wird.The comparative experiment shows that a hardened yellow filter layer considerably increases the security of a non-duplicable microfilm, even if an aggressive solvent such as acetone is used for detachment.

Beispiel 2Example 2

Zur Herstellung der Diazofilmkopie C 1 wird, wie in Beispiel 1 beschrieben, verfahren, nur dient als Vernetzungskomponente für das Celluloseacetopropionat die gleiche Gewichtsmenge eines butylierten Harnstoff-Formaldehydharzes. Das verwendete Harnstoffharz ist ein handelsübliches Produkt mit einer Säurezahl von weniger als 3. Eine 65%ige Lösung dieses Harzes in Isobutanol besitzt bei 20°C eine Viskosität von 10-12dPas.The procedure for producing the diazo film copy C 1 is as described in Example 1, except that the same weight amount of a butylated urea-formaldehyde resin is used as the cross-linking component for the cellulose acetopropionate. The urea resin used is a commercial product with an acid number of less than 3. A 65% solution of this resin in isobutanol has a viscosity of 10-12dPas at 20 ° C.

Zur Prüfung wird erneut die Lösungsmittelresistenz der vernetzten gelben Filterschicht der Diazofilmkopie C 1 mit der nicht vernetzten gelben Filterschicht der Diazofilmkopie A 1 des Beispiels 1 verglichen. Als Lösungsmittel wird bei diesem Versuch ein Gemisch aus 80 Gewichtsteilen Isopropanol und 20 Gewichtsteilen Wasser verwendet. Anschließend wird ein Duplizierversuch durchgeführt.For the test, the solvent resistance of the crosslinked yellow filter layer of the diazo film copy C 1 is again compared with the non-crosslinked yellow filter layer of the diazo film copy A 1 of Example 1. A mixture of 80 parts by weight of isopropanol and 20 parts by weight of water is used as the solvent in this experiment. A duplication attempt is then carried out.

Wie in Beispiel 1 zeigt sich auch hier die Überlegenheit der vernetzten gelben Filterschicht der Diazofilmkopie C 1 gegenüber der unvernetzten der Diazofilmkopie A 1 sowohl bei der Lösungsmittelbehandlung als auch bei dem nachfolgenden Duplizierversuch. Während A 1 die bekannten Ergebnisse zeigt, ist die Diazofilmkopie C 1 nur mit deutlichen Informationsverlusten zu duplizieren. Das Anfertigen der 2. Diazofilmgeneration C 2 ist hier erheblich erschwert.As in Example 1, the superiority of the crosslinked yellow filter layer of the diazo film copy C 1 over the uncrosslinked of the diazo film copy A 1 is evident both in the solvent treatment and in the subsequent duplication attempt. While A 1 shows the known results, the diazo film copy C 1 can only be duplicated with significant loss of information. The production of the second generation of diazo film C 2 is considerably more difficult here.

Beispiel 3Example 3

Es wird wie in Beispiel 1 verfahren, nur dient Dimethylgelb (C. I. Solvent Yellow 2) als Farbstoff für die gelbe Filterschicht. Zur Herstellung der gelb eingefärbten absorbierenden Filterschicht werden 8,75 g Dimethylgelb in 700 g Basislack gelöst.The procedure is as in Example 1, except that dimethyl yellow (C.I. Solvent Yellow 2) is used as the dye for the yellow filter layer. To produce the yellow colored absorbent filter layer, 8.75 g of dimethyl yellow are dissolved in 700 g of basecoat.

Zur Prüfung wird die nicht vernetzte gelbe Filterschicht der Diazofilmkopie D 1 mit der vernetzten der Diazofilmkopie E 1 in bezug auf Lösungsmittelbeständigkeit und Generationsfähigkeit vergleichend geprüft. Als Lösungsmittel wird, wie im Beispiel 2 beschrieben, ein Gemisch aus 80 Gewichtsteilen Isopropanol und 20 Gewichtsteilen Wasser verwendet.For the test, the non-crosslinked yellow filter layer of the diazo film copy D 1 is compared with the crosslinked of the diazo film copy E 1 in terms of solvent resistance and generation ability. A mixture of 80 parts by weight of isopropanol and 20 parts by weight of water is used as the solvent, as described in Example 2.

Die nicht vernetzte gelbe Filterschicht der Diazofilmkopie D 1 ist in der gleichen Zeit leichter zu entfernen als die vernetzte der Diazofilmkopie E 1. Die Duplizierfähigkeit der mit Lösungsmittel behandelten Diazofilmkopie E 1 ist schlechter als bei D 1. Die Herstellung der 2. Diazofilmgeneration E 2 ist deutlich erschwert gegenüber D 2.The non-crosslinked yellow filter layer of the diazo film copy D 1 is easier to remove at the same time than the crosslinked one of the diazo film copy E 1. The duplicability of the solvent-treated diazo film copy E 1 is worse than that of D 1. The production of the second generation of diazo film E 2 is less significantly more difficult than D 2.

Claims (8)

1. A recording material containing diazo compounds, in particular a microfilm, comprising a layer support which is at least partially pervious to visible radiation, a light-sensitive layer arranged on one side of the layer support and a filter layer which absorbs light in the long-wave ultraviolet spectral range and in the short-wave visible sprectral range and is arranged on the other side of the layer support, wherein the filter layer contains a polymer which is insoluble or has been rendered insoluble by crosslinking in acetone or an isopropanol/water mixture, and at least one dye which is compatible with the constituents of the polymer and absorbs light in the range between about 360 nm and about 500 nm.
2. A recording material as claimed in claim 1, wherein the fitter layer contains a yellow to orange-coloured dye.
3. A recording material as claimed in claim 1 and claim 2, wherein the filter layer contains at least one mono- and/or bis-azo dye.
4. A recording material as claimed in claim 3, wherein the filter layer contains Sudan yellow GGN (C. I. Solvent Yellow 56).
5. A recording material as claimed in claim 1, wherein the filter layer contains a copolymer of terephthalic acid as the insoluble polymer.
6. A recording material as claimed in claim 1, wherein the filter layer contains a cellulose ester as the polymer which has been rendered less soluble by crosslinking.
7. A process for producing a recording material containing diazo compounds, in particular a microfilm, by applying a filter layer, which absorbs light in the long-wave ultraviolet spectral range and in the short-wave visible spectral range, to one side of a layer support which is at least partially pervious to visible radiation, and applying and subsequently drying a light-sensitive layer in the form of a solution to the other side of said layer support, wherein first the filter layer, comprised of a polymer which is insoluble in acetone or an isopropanol/water mixture or which is to be rendered less soluble in these solvents by crosslinking, and of at least one dye which is compatible with the constituents of the polymer and absorbs light in a range between 360 nm and 500 nm, is applied to the layer support and hardened, and then the light-sensitive layer is applied to the other side of the layer support.
8. A process as claimed in claim 7, wherein the filter layer is applied using an adhesion-promoting intermediate layer, in the form of a lacquer solution which contains the polymer which is to be rendered less soluble by crosslinking together with the dye, the filter layer being dried after application and subsequently hardened.
EP80106437A 1979-10-29 1980-10-22 Recording material containing diazo compounds and a filter layer and process for the production of same Expired EP0028003B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80106437T ATE5673T1 (en) 1979-10-29 1980-10-22 RECORDING MATERIAL CONTAINING DIAZ COMPOUNDS WITH A FILTER LAYER AND METHOD OF MAKING THE SAME.

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Application Number Priority Date Filing Date Title
DE19792943632 DE2943632A1 (en) 1979-10-29 1979-10-29 DIAZO COMPOUNDS CONTAINING RECORDING MATERIAL AND METHOD FOR PRODUCING THE SAME
DE2943632 1979-10-29

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EP0028003A1 EP0028003A1 (en) 1981-05-06
EP0028003B1 true EP0028003B1 (en) 1983-12-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP80106437A Expired EP0028003B1 (en) 1979-10-29 1980-10-22 Recording material containing diazo compounds and a filter layer and process for the production of same

Country Status (12)

Country Link
US (1) US4317875A (en)
EP (1) EP0028003B1 (en)
JP (1) JPS5674243A (en)
AT (1) ATE5673T1 (en)
BR (1) BR8006914A (en)
CA (1) CA1148404A (en)
DE (2) DE2943632A1 (en)
DK (1) DK456080A (en)
ES (1) ES496357A0 (en)
FI (1) FI67964C (en)
PT (1) PT71960B (en)
ZA (1) ZA806588B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3827245A1 (en) * 1988-08-11 1990-02-15 Hoechst Ag PHOTOPOLYMERIZABLE RECORDING MATERIAL
JPH0474434U (en) * 1990-11-07 1992-06-30
US5382495A (en) * 1991-05-01 1995-01-17 Rexham Graphics, Inc. Overcoats for diazo-containing layers with chemicals and abrasion resistance

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1169227A (en) * 1966-11-17 1969-10-29 Bexford Ltd Diazotype Material
GB1250252A (en) * 1969-03-28 1971-10-20
US3912512A (en) * 1974-03-04 1975-10-14 Addressograph Multigraph Light-sensitive diazotype film and method of making and using same
US4080208A (en) * 1975-01-13 1978-03-21 Addressograph Multigraph Corporation Photosensitive diazomicrofilm adapted to be readable but nonreproducible upon processing
US4225659A (en) * 1979-04-10 1980-09-30 Drexler Technology Corporation Method for making thermochromic photomasks

Also Published As

Publication number Publication date
US4317875A (en) 1982-03-02
PT71960A (en) 1980-11-01
EP0028003A1 (en) 1981-05-06
FI803357L (en) 1981-04-30
ATE5673T1 (en) 1984-01-15
DE3065953D1 (en) 1984-01-26
FI67964C (en) 1985-06-10
BR8006914A (en) 1981-05-05
PT71960B (en) 1981-08-31
JPH0221573B2 (en) 1990-05-15
CA1148404A (en) 1983-06-21
ES8207358A1 (en) 1982-09-01
FI67964B (en) 1985-02-28
ZA806588B (en) 1981-10-28
DK456080A (en) 1981-04-30
JPS5674243A (en) 1981-06-19
DE2943632A1 (en) 1981-05-07
ES496357A0 (en) 1982-09-01

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