EP0350534A2 - Lacquer-coating printable with sublimable dispersion dyes, coating material therefor and method for the preparation of printed objects - Google Patents

Lacquer-coating printable with sublimable dispersion dyes, coating material therefor and method for the preparation of printed objects Download PDF

Info

Publication number
EP0350534A2
EP0350534A2 EP88120218A EP88120218A EP0350534A2 EP 0350534 A2 EP0350534 A2 EP 0350534A2 EP 88120218 A EP88120218 A EP 88120218A EP 88120218 A EP88120218 A EP 88120218A EP 0350534 A2 EP0350534 A2 EP 0350534A2
Authority
EP
European Patent Office
Prior art keywords
weight
lacquer
paint
coating
binder
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.)
Granted
Application number
EP88120218A
Other languages
German (de)
French (fr)
Other versions
EP0350534A3 (en
EP0350534B1 (en
Inventor
Siegfried Wisser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BEUTELROCK, CAROLIN
Original Assignee
Beutelrock Carolin
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beutelrock Carolin filed Critical Beutelrock Carolin
Priority to AT88120218T priority Critical patent/ATE86924T1/en
Publication of EP0350534A2 publication Critical patent/EP0350534A2/en
Publication of EP0350534A3 publication Critical patent/EP0350534A3/en
Application granted granted Critical
Publication of EP0350534B1 publication Critical patent/EP0350534B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
    • B41M5/0355—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic characterised by the macromolecular coating or impregnation used to obtain dye receptive properties

Definitions

  • the image or pattern to be printed is first printed on a subcarrier, in particular made of paper, using sublimable disperse dyes. Then it is placed on the plastic-coated surface with the printed side, after which the disperse dyes are transferred from the auxiliary carrier into the plastic lacquer by heating, if appropriate under low pressure.
  • FR-A-2 230 794 and DE-A-2 424 949 also describe a method for printing heat-resistant sheets, such as metal sheets or ceramic tiles, according to the transfer printing method, in which the substrate is coated with an epoxy resin.
  • the substrate is coated in a transfer printing process with a hardened unsaturated polyester resin.
  • the substrate to be printed is coated with a crosslinked thermoset, such as a radiation-hardened unsaturated polyester resin, and those with relatively high molecular weights between 340 and 1000 are used as sublimable emulsion paints .
  • This has the advantage that even with longer and relatively the printed images remain stable and show practically no migration.
  • this process it is possible to obtain a sufficient transfer of the dyes during transfer printing using very short transfer printing times, such as in the band coating process.
  • scratch resistance and surface hardness are of particular importance. It is known that glass powder, aluminum oxide, silicon carbide or other hard inorganic powders can improve the abrasion resistance of paint coatings. The scratch resistance and surface hardness are only slightly improved. This may be due to the sedimentation behavior of such inorganic powders.
  • the object on which the invention is based was to improve the scratch resistance and surface hardness of a coated object by means of a special coating which is suitable for printing with sublimable dispersion dyes. Surprisingly, this object is achieved with the present invention.
  • the lacquer coating according to the invention on the surface of a printable object for printing with sublimable disperse dyes made from a hardened thermoplastic or thermosetting lacquer binder and filler distributed therein and, if appropriate, customary lacquer additives is characterized in that it contains 10 to 100 parts by weight per 100 parts by weight of dry substance of the binder of irregularly shaped glass flakes , of which at least 90% by weight is the largest dimension solution of maximum 0.5 mm and a smallest dimension of at least 0.05 mm and a thickness of 0.5 to 20 ⁇ m.
  • Such paint coatings result in an amazing increase in surface hardness and scratch resistance. If the lacquer has a Mohs hardness of 0 without the addition of glass flakes, the hardness is increased to 2 to 3 by the addition of glass flakes according to the invention, which already comes close to ceramic tiles.
  • the lacquer coating according to the invention thus makes it possible for the first time to obtain utility tiles with an acceptable scratch resistance and surface hardness, which can be printed or colored with sublimable disperse dyes, for example using the transfer printing process.
  • the test according to DIN EN154 for the determination of the resistance to surface wear of glazed tiles and plates resulted in a classification in group 2 with the lacquer coating according to the invention, which enables the use of such coated tiles in wet cells or for ceramic wall coverings.
  • the lacquer coatings modified with glass flakes for sublimable dispersion dyes have excellent color absorption, the disperse dyes being distributed over the entire height of the lacquer coating and not only accumulating in the surface area of the lacquer coating . This was confirmed by abrasion tests, in which a substantial part of the paint coating was rubbed off, but nevertheless a strong amount of color was present in the rest of the paint coating.
  • the uniform distribution of the disperse dyes over the height of the lacquer coating results in the brilliance of the printed image or the coloring, which is customary for such dispersion dyes, and also the advantage that the printed image remains unharmed even in the event of partial abrasion of the surface coating.
  • the excellent dye absorption and print quality of the lacquer coatings according to the invention can be obtained even if a thixotropic agent, such as colloidal silica, bentones or castor oils, is incorporated into the coating. This is particularly surprising in view of the fact that in the case of glass powder, the use of thixotropic agents leads to a severe deterioration in printability.
  • a thixotropic agent such as colloidal silica, bentones or castor oils
  • the perceptible effect of the lacquer coatings according to the invention is difficult or impossible to explain.
  • the glass flakes may have increased absorbency due to their ability to be stacked or due to pores or cracks, which means that the paint binder penetrates the entire filler and also allows the dyes to penetrate into the lowest areas of the coating.
  • Glass flakes with the dimensions mentioned are obtained by crushing, such as hammer milling, extremely thin glass plates with the indicated thicknesses.
  • the crushing process allows particles in the dimensional ranges indicated above and with irregular and jagged, i.e. H. get rounded contours.
  • glass flakes in which at least 90% by weight have a maximum dimension of at most 0.25 mm.
  • the thickness thereof is preferably in the range from 1 to 10, in particular in the range from 1 to 6 ⁇ m.
  • the preferred amount of glass flakes in the lacquer coating is 20 to 60, especially 25 to 45 parts by weight.
  • Suitable binders are the thermoplastic or thermosetting lacquer binders known in the transfer printing process. For various reasons, such as the migration resistance of the disperse dyes in the coating, thermosetting paint binders are preferred.
  • thermoplastics to be used as binders are, for example, polyacrylonitrile, polyesters, polyurethanes, cellulose derivatives, polyamides, polyacrylates and others.
  • crosslinked thermosets such as phenoplasts, aminoplasts, polyesters, polyphenylene sulfide resins, silicone resins, acrylate resins, alkyd resins, polyethylene sulfide resins, unsaturated polyester resins, epoxy resins and polyurethanes, are particularly preferred as binders.
  • Appropriate binders are silicone resins and radiation-hardened unsaturated acrylate resins or polyester resins.
  • Particularly favorable binders in the present coatings are aliphatic crosslinked hydroxyl-containing aliphatic, saturated polyesters. These are particularly suitable for printing on mineral and metallic substrates, since they have increased adhesive strength on them.
  • these preferably contain 2 to 12% by weight of hydroxyl groups, 40 to 60% of which are crosslinked by a crosslinking agent, such as an aliphatic polyisocyanate or an aliphatic polyalcohol.
  • these polyesters preferably contain 7 to 9% by weight of hydroxyl groups, 45 to 55% of the hydroxyl groups being crosslinked.
  • the crosslinking is expediently carried out using a diisocyanate, especially hexamethylene diisocyanate.
  • polyesters As binders, it is essential that both the polyester and the crosslinking components are aliphatic in nature.
  • polyesters When talking about aliphatic polyesters, so can these are straight-chain or branched-chain, with branched-chain ones being preferred.
  • the polyesters may also contain other organic groups, such as ether groups, in addition to the ester groups.
  • the molecular weights of the polyesters used according to the invention are preferably in the range from 700 to 5000 in the uncrosslinked state. They are formed by known reaction of di- or tricarboxylic acids with excess di- or polyalcohols, so that they carry hydroxyl groups at the chain ends.
  • the dicarboxylic acid that can be used for this is, for example, adipic acid.
  • the diols and polyols which can be used in the production of the uncrosslinked polyesters are, for example, neopentyl glycol, ethylene glycol, propane-1,2-diol, 1,4-bis (hydroxymethyl) cyclohexane, glycerol, trimethylol propane and pentaerythritol.
  • a part of the free hydroxyl groups of the polyester can be crosslinked with different polyfunctional aliphatic compounds, especially with aliphatic polyisocyanates or aliphatic polyalcohols. This is understood to mean isocyanates and alcohols with at least two isocyanate or hydroxyl groups. Crosslinking with polyisocyanates creates urethane groups, crosslinking with polyalcohols creates ether groups. Crosslinking can also be carried out with both types of compounds in order to obtain mixed urethane-ether crosslinks.
  • the coatings according to the invention can be applied both as wet lacquers and as powder lacquers. If a wet lacquer, ie a solvent-based lacquer binder, is used, it is expedient, together with the glass flakes, to use a thixotropic agent, such as colloidal silica, bentone or castor oils, preferably in an amount of 0.3 to 5% by weight, based on the dry weight the coating. Powder coatings have the advantage that they give extremely high adhesion to mineral substrates and even to a ceramic glaze.
  • the coatings according to the invention surprisingly have a high UV stability, which is significantly higher than the corresponding paint coatings without glass flake storage.
  • the lacquer coatings according to the invention can be used for printing with any sublimable disperse dyes, advantageously with those which have a molecular weight between 340 and 1000, preferably between 400 and 1000, since they have a lower tendency to migrate and are generally lightfast.
  • Preferred groups of disperse dyes for printing on lacquer coatings according to the invention are anthraquinone, monoazo and azomethine dyes, but the applicability is not limited to these groups of dyes.
  • Anthraquinone, monoazo and azomethine dyes are preferred, the molecules of which are heavily occupied with amino, alkoxy, oxalkyl, nitro, halogen and cyano groups.
  • These dye groups are defined in the Color Index, Volume 1, pages 1655 to 1742. In this regard, reference is made to pages 9 to 11 of EP-A-0 014 901.
  • the sublimable disperse dyes can either be transferred to the lacquer coatings according to the invention in a transfer printing process from an auxiliary carrier or printed directly on. In both cases, however, it is essential that the dyes go into the lacquer coating due to the application of heat and migrate into the depth of the binder layer, which results in the high brilliance of such printed images.
  • the invention also relates to coating compositions for the production of the paint coatings defined above for printing with sublimable disperse dyes.
  • These coating compositions consist of a thermoplastic or preferably thermosetting paint binder, if appropriate at least one organic solvent for the paint binder, 10 to 100 parts by weight, based on the weight of the dry substance of the paint binder, of irregularly shaped glass flakes, of which at least 90% by weight have a largest dimension of at most 0.5 mm and a smallest dimension of at least 0 , 05 mm and a thickness of 0.5 to 20 ⁇ m, as well as, where appropriate, conventional paint additives, such as thixotropic agents.
  • the coating compositions usually consist only of mixtures of the binder in powder form and the glass flakes.
  • This method consists in providing the object with a lacquer coating which consists of a hardened thermoplastic or thermosetting lacquer binder and glass flakes distributed therein in the proportions given above and with the dimensions given above and, if appropriate, conventional lacquer additives, then the lacquer coating, directly or in Transfer printing process, printed with sublimable disperse dyes and allowing them to penetrate the paint coating by heating.
  • Preferred temperatures for the heating are in the range of 210 to 260 ° C, the heating times can be in the range of seconds to minutes.
  • the sublimable disperse dyes are sublimed out of the printing on the auxiliary carrier and simultaneously introduced into the coating.
  • printing and subsequent heating are carried out in order to allow the disperse dyes on the coating to penetrate the coating.
  • thermoplastic binders If the description refers to hardened thermoplastic binders, this means that the thermoplastic softened in the heat is solidified by cooling. In the case of thermosets, the term curing means crosslinking, so that the binder no longer softens when heated.
  • the diameter of the irregularly shaped flakes perpendicular to the thickness direction i.e. H. in top view of the flakes.
  • the largest dimension could also be referred to as the length of the flakes and the smallest dimension as the width of the flakes.
  • the flakes are therefore at most 0.5 mm long and at least 0.05 mm wide.
  • a wet paint was produced in the following way: 20 parts by weight of glass flakes with a thickness of approximately 3 ⁇ m, of which 98% by weight had a largest dimension of less than 0.25 mm and a smallest dimension of more than 0.1 mm, and 1.0 part by weight of colloidal silica (Aerosil 380) and 40.0 parts by weight of butyl acetate were thoroughly stirred together.
  • 20 parts by weight of diisocyanate (Desmodur N) in 75% solution in xylene / methoxypropylacetate and 100 parts by weight of hydroxyl-containing saturated polyester paint as 65% solution in methoxypropylacetate were added and stirred vigorously.
  • the wet paint thus produced was used to coat glazed ceramic tiles with an automatic spray gun, after which the coating was baked at 180 ° C. for 10 minutes.
  • Table I shows the properties obtained for the two coated tiles compared: Table I with glass flakes without glass flakes Mohs hardness 2 to 3 0 Color recording 220 degrees / 3 ⁇ Good Good Color absorption of the lower lacquer layer Good Good UV resistance xenon test wool scale 7 1000 h 650 h
  • a powder coating was prepared from 100 parts by weight of a commercially available powder coating hardened with TGIC and 40 parts by weight of the glass flakes specified in Example 1. The powder coating was applied in the customary manner to glazed ceramic tiles and baked in the infrared channel at 200 ° C. for 5 minutes.

Landscapes

  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

To improve the scratch resistance and surface hardness, a lacquer coating on the surface of an imprintable object for printing with sublimable disperse dyes from a cured thermoplastic or thermosetting lacquer binder and a filler dispersed therein and, if appropriate, conventional lacquer additives is characterised in that it contains, per 100 parts by weight of dry solids of the lacquer binder, 10 to 100 parts by weight of irregularly shaped glass flocks as a filler, of which at least 90% by weight have a greatest dimension of at most 0.5 mm and a smallest dimension of at least 0.05 mm and a thickness of 0.5 to 20 mu m.

Description

Aus der DE-A-2 642 350 ist es bekannt, Flächengebilde, wie beispielsweise Holz, Metalle, Kunststoffe, Glas, Keramikma­terialien, Natur- und Kunststeinerzeugnisse oder derglei­chen, nach dem sogenannten Transferdruckverfahren zu bedruk­ken. Da diese Materialien die im Transferdruckverfahren ver­wendeten sublimierbaren Dispersionsfarbstoffe nicht anneh­men, werden die Substrate vor dem Transferdruck mit einer Oberflächenschicht eines Kunststofflackes versehen, der sich mit der Oberfläche des Substrates fest verbindet und die su­blimierbaren Dispersionsfarbstoffe aufnimmt.From DE-A-2 642 350 it is known to print sheet-like structures such as wood, metals, plastics, glass, ceramic materials, natural and artificial stone products or the like by the so-called transfer printing process. Since these materials do not accept the sublimable disperse dyes used in the transfer printing process, the substrates are provided with a surface layer of a plastic varnish before the transfer print, which is firmly bonded to the surface of the substrate and absorbs the sublimable disperse dyes.

Das aufzudruckende Bild oder Muster wird mit Hilfe von su­blimierbaren Dispersionsfarbstoffen zunächst auf einem Hilfsträger, insbesondere aus Papier, aufgedruckt. Sodann wird dieser auf die mit Kunststoff beschichtete Fläche mit der bedruckten Seite aufgelegt, wonach durch Erhitzen, gege­benenfalls unter geringem Druck, die Dispersionsfarbstoffe von dem Hilfsträger in den Kunststofflack übertragen werden.The image or pattern to be printed is first printed on a subcarrier, in particular made of paper, using sublimable disperse dyes. Then it is placed on the plastic-coated surface with the printed side, after which the disperse dyes are transferred from the auxiliary carrier into the plastic lacquer by heating, if appropriate under low pressure.

Die FR-A-2 230 794 und die DE-A-2 424 949 beschreiben eben­falls ein Verfahren zum Bedrucken hitzebeständiger Flächenge­bilde, wie von Metallblechen oder Keramikkacheln, nach dem Transferdruckverfahren, wobei man das Substrat mit einem Epoxyharz beschichtet. Gemäß der GB-A-1 517 832 erfolgt die Beschichtung des Substrates im Transferdruckverfahren mit einem gehärteten ungesättigten Polyesterharz. Gemäß der DE-­A-2 914 704 und der EP-A-0 014 901 wird das zu bedruckende Substrat mit einem vernetzten Duroplasten, wie einem strah­lungsgehärteten ungesättigten Polyesterharz beschichtet, und als sublimierbare Dispersionsfarben werden solche mit rela­tiv hohen Molekulargewichten zwischen 340 und 1000 verwen­det. Dies hat den Vorteil, daß auch bei längerem und relativ hohem Erwärmen die umgedruckten Bilder beständig bleiben und praktisch keine Migration zeigen. Außerdem gelingt es mit diesem Verfahren, unter Anwendung sehr kurzer Umdruckzeiten, wie im Bandlackierverfahren, beim Umdruck eine ausreichende Übertragung der Farbstoffe zu bekommen.FR-A-2 230 794 and DE-A-2 424 949 also describe a method for printing heat-resistant sheets, such as metal sheets or ceramic tiles, according to the transfer printing method, in which the substrate is coated with an epoxy resin. According to GB-A-1 517 832, the substrate is coated in a transfer printing process with a hardened unsaturated polyester resin. According to DE-A-2 914 704 and EP-A-0 014 901, the substrate to be printed is coated with a crosslinked thermoset, such as a radiation-hardened unsaturated polyester resin, and those with relatively high molecular weights between 340 and 1000 are used as sublimable emulsion paints . This has the advantage that even with longer and relatively the printed images remain stable and show practically no migration. In addition, with this process it is possible to obtain a sufficient transfer of the dyes during transfer printing using very short transfer printing times, such as in the band coating process.

Bei bestimmten Anwendungsgebieten, wie bei Gebrauchsfliesen, sind Kratzfestigkeit und Oberflächenhärte von besonderer Be­deutung. Man weiß, daß man durch Glaspulver, Elektrokorund, Siliziumkarbid oder andere harte anorganische Pulver die Ab­riebfestigkeit von Lackbeschichtungen verbessern kann. Die Kratzfestigkeit und Oberflächenhärte werden dabei aber nur unwesentlich verbessert. Dies beruht möglicherweise auf dem Sedimentierungsverhalten solcher anorganischer Pulver.In certain areas of application, such as utility tiles, scratch resistance and surface hardness are of particular importance. It is known that glass powder, aluminum oxide, silicon carbide or other hard inorganic powders can improve the abrasion resistance of paint coatings. The scratch resistance and surface hardness are only slightly improved. This may be due to the sedimentation behavior of such inorganic powders.

Bei Vorarbeiten zu der vorliegenden Erfindung wurde ver­sucht, das Sedimentieren beispielsweise von Glaspulver durch Mitverwendung von Thixotropiermitteln zu vermindern, doch bekommt man dann eine sehr schlechte Bedruckbarkeit, da of­fenbar die Lackbeschichtungsoberfläche die Dispersionsfarb­stoffe nicht ausreichend aufnimmt.In the course of preparatory work on the present invention, attempts have been made to reduce the sedimentation of, for example, glass powder by using thixotropic agents, but this results in very poor printability, since the surface of the paint coating apparently does not absorb the disperse dyes sufficiently.

Die der Erfindung zugrundeliegende Aufgabe bestand nun da­rin, durch eine spezielle Beschichtung, die für das Bedruk­ken mit sublimierbaren Disperionsfarbstoffen geeignet ist, die Kratzfestigkeit und Oberflächenhärte eines beschichteten Gegenstandes zu verbessern. Überraschenderweise wird diese Aufgabe mit der vorliegenden Erfindung gelöst.The object on which the invention is based was to improve the scratch resistance and surface hardness of a coated object by means of a special coating which is suitable for printing with sublimable dispersion dyes. Surprisingly, this object is achieved with the present invention.

Die erfindungsgemäße Lackbeschichtung auf der Oberfläche ei­nes bedruckbaren Gegenstandes zur Bedruckung mit sublimier­baren Dispersionsfarbstoffen aus einemgehärteten thermopla­stischen oder duroplastischen Lackbindemittel und darin ver­teiltem Füllstoff sowie gegebenenfalls üblichen Lackzusatz­stoffen ist dadurch gekennzeichnet, daß sie als Füllstoff 10 bis 100 Gewichtsteile je 100 Gewichtsteile Trockensub­stanz des Bindemittels unregelmäßig geformter Glasflocken enthält, von denen wenigstens 90 Gew.-% eine größte Abmes­ sung von maximal 0,5 mm und eine kleinste Abmessung von min­destens 0,05 mm sowie eine Dicke von 0,5 bis 20 µm besitzen.The lacquer coating according to the invention on the surface of a printable object for printing with sublimable disperse dyes made from a hardened thermoplastic or thermosetting lacquer binder and filler distributed therein and, if appropriate, customary lacquer additives is characterized in that it contains 10 to 100 parts by weight per 100 parts by weight of dry substance of the binder of irregularly shaped glass flakes , of which at least 90% by weight is the largest dimension solution of maximum 0.5 mm and a smallest dimension of at least 0.05 mm and a thickness of 0.5 to 20 µm.

Solche Lackbeschichtungen ergeben eine erstaunliche Erhöhung der Oberflächenhärte und Kratzfestigkeit. Wenn der Lack ohne Zusatz der Glasflocken eine Härte nach Mohs von 0 besitzt, so wird die Härte durch den erfindungsgemäßen Zusatz von Glasflocken auf 2 bis 3 erhöht, was bereits in die Nähe von Keramikfliesen kommt. Die erfindungsgemäße Lackbeschichtung ermöglicht es somit erstmals, Gebrauchsfliesen mit annehmba­rer Kratzfestigkeit und Oberflächenhärte zu bekommen, die mit sublimierbaren Dispersionsfarbstoffen etwa nach dem Transferdruckverfahren bedruckbar oder einfärbbar sind. Die Prüfung nach DIN EN154 zur Bestimmung des Widerstandes gegen Oberflächenverschleiß glasierter Fliesen und Platten er­brachte mit der erfindungsgemäßen Lackbeschichtung eine Ein­gruppierung in Gruppe 2, was die Verwendbarkeit solchermaßen beschichteter Fliesen in Naßzellen oder für keramische Wand­beläge ermöglicht.Such paint coatings result in an amazing increase in surface hardness and scratch resistance. If the lacquer has a Mohs hardness of 0 without the addition of glass flakes, the hardness is increased to 2 to 3 by the addition of glass flakes according to the invention, which already comes close to ceramic tiles. The lacquer coating according to the invention thus makes it possible for the first time to obtain utility tiles with an acceptable scratch resistance and surface hardness, which can be printed or colored with sublimable disperse dyes, for example using the transfer printing process. The test according to DIN EN154 for the determination of the resistance to surface wear of glazed tiles and plates resulted in a classification in group 2 with the lacquer coating according to the invention, which enables the use of such coated tiles in wet cells or for ceramic wall coverings.

Das Überraschende am Erfindungsgegenstand ist aber insbeson­dere, daß im Gegensatz zu Glaspulver und anderen anorgani­schen Pulvern die mit Glasflocken modifizierten Lackbe­schichtungen für sublimierbare Disperionsfarbstoffe eine hervorragende Farbaufnahme besitzen, wobei sich die Disper­sionsfarbstoffe über die gesamte Höhe der Lackbeschichtung verteilen und sich nicht nur im Oberflächenbereich der Lack­beschichtung ansammeln. Dies wurde durch Abriebversuche be­stätigt, bei denen ein wesentlicher Teil der Lackbeschich­tung abgerieben wurde, dennoch aber ein starker Farbanteil in dem verbleibenden Rest der Lackbeschichtung vorhanden war. Die gleichmäßige Verteilung der Dispersionsfarbstoffe über die Höhe der Lackbeschichtung ergibt die für solche Disperionsfarbstoffe übliche Brillanz des Druckbildes oder der Einfärbung und außerdem den Vorteil, daß selbst im Falle eines Teilabriebes der Oberflächenbeschichtung das Druckbild unverletzt vorhanden bleibt.The surprising thing about the subject of the invention, however, is that, in contrast to glass powder and other inorganic powders, the lacquer coatings modified with glass flakes for sublimable dispersion dyes have excellent color absorption, the disperse dyes being distributed over the entire height of the lacquer coating and not only accumulating in the surface area of the lacquer coating . This was confirmed by abrasion tests, in which a substantial part of the paint coating was rubbed off, but nevertheless a strong amount of color was present in the rest of the paint coating. The uniform distribution of the disperse dyes over the height of the lacquer coating results in the brilliance of the printed image or the coloring, which is customary for such dispersion dyes, and also the advantage that the printed image remains unharmed even in the event of partial abrasion of the surface coating.

Die hervorragende Farbstoffaufnahme und Druckqualität der erfindungsgemäßen Lackbeschichtungen bekommt man selbst dann, wenn man ein Thixotropiermittel, wie kolloidale Kie­selsäur, Bentone oder Rizinusöle, in die Beschichtung einar­beitet. Dies ist besonders überraschend im Hinblick auf die Tatsache, daß im Falle von Glaspulver die Mitverwendung von Thixotropiermitteln zu einer starken Verschlechterung der Bedruckbarkeit führt.The excellent dye absorption and print quality of the lacquer coatings according to the invention can be obtained even if a thixotropic agent, such as colloidal silica, bentones or castor oils, is incorporated into the coating. This is particularly surprising in view of the fact that in the case of glass powder, the use of thixotropic agents leads to a severe deterioration in printability.

Der wahrnehmbare Effekt der erfindungsgemäßen Lackbeschich­tungen ist nicht oder nur schwer erklärbar. Möglicherweise besitzen die Glasflocken aufgrund ihrer Übereinanderlegbar­keit oder aufgrund von Poren oder Rissen erhöhte Saugfähig­keit, die dazu führt, daß das Lackbindemittel den gesamten Füllstoff durchdringt und auch die Farbstoffe bis in die un­tersten Bereiche der Beschichtung vordringen läßt.The perceptible effect of the lacquer coatings according to the invention is difficult or impossible to explain. The glass flakes may have increased absorbency due to their ability to be stacked or due to pores or cracks, which means that the paint binder penetrates the entire filler and also allows the dyes to penetrate into the lowest areas of the coating.

Glasflocken mit den genannten Dimensionierungen werden durch Zerkleinern, wie durch Hammermahlen, extrem dünner Glas­plättchen mit den angegebenen Dicken erhalten. Durch das Zerkleinerungsverfahren kann man Teilchen in den oben ange­gebenen Abmessungsbereichen und mit unregelmäßigen und zak­kigen, d. h. unabgerundeten Konturen bekommen.Glass flakes with the dimensions mentioned are obtained by crushing, such as hammer milling, extremely thin glass plates with the indicated thicknesses. The crushing process allows particles in the dimensional ranges indicated above and with irregular and jagged, i.e. H. get rounded contours.

Bevorzugt ist es, erfindungsgemäß solche Glasflocken zu ver­wenden, bei denen wenigstens 90 Gew.-% eine größte Abmessung von maximal 0,25 mm besitzen. Die Dicke der Glasflocken liegt bei 90 % derselben vorzugsweise im Bereich von 1 bis 10, besonders im Bereich von 1 bis 6 µm.It is preferred according to the invention to use glass flakes in which at least 90% by weight have a maximum dimension of at most 0.25 mm. In the case of 90% of the glass flakes, the thickness thereof is preferably in the range from 1 to 10, in particular in the range from 1 to 6 μm.

Die Angabe, daß wenigstens 90 % innerhalb der genannten Ab­messungsbereiche liegen sollen, bedeutet, daß es nicht stört, wenn ein kleiner Prozentsatz über oder unter diesen Bereichen liegt, da dieser kleine Prozentsatz den Effekt nicht beeinträchtigen kann.The indication that at least 90% should lie within the stated dimensional ranges means that it does not bother if a small percentage lies above or below these ranges, since this small percentage cannot impair the effect.

Die bevorzugte Menge an Glasflocken in der Lackbeschichtung, bezogen auf 100 Gewichtsteile Trockensubstanz des Bindemit­ tels, beträgt 20 bis 60, besonders 25 bis 45 Gewichtsteile.The preferred amount of glass flakes in the lacquer coating, based on 100 parts by weight of dry substance of the binder tels, is 20 to 60, especially 25 to 45 parts by weight.

Als Bindemittel kommen die im Transferdruckverfahren bekann­ten thermoplastischen oder duroplastischen Lackbindemittel in Betracht. Aus verschiedenen Gründen, wie aus Gründen der Migrationsbeständigkeit der Dispersionsfarbstoffe in der Be­schichtung, sind duroplastische Lackbindemittel bevorzugt.Suitable binders are the thermoplastic or thermosetting lacquer binders known in the transfer printing process. For various reasons, such as the migration resistance of the disperse dyes in the coating, thermosetting paint binders are preferred.

Die als Bindemittel zu verwendenden Thermoplasten sind bei­spielsweise Polyacrylnitril, Polyester, Polyurethane, Cellu­losederivate, Polyamide, Polyacrylate und andere. Wie er­wähnt, sind aber als Bindemittel besonders bevorzugt ver­netze Duroplasten, wie Phenoplasten, Aminoplasten, Poly­ester, Polyphenylensulfidharze, Siliconharze, Acrylatharze, Alkydharze, Polyethylensulfidharze, ungesättigte Polyester­harze, Epoxyharze und Polyurethane. Zweckmäßige Bindemittel sind Siliconharze und strahlungsgehärtete ungesättigte Acry­latharze oder Polyesterharze.The thermoplastics to be used as binders are, for example, polyacrylonitrile, polyesters, polyurethanes, cellulose derivatives, polyamides, polyacrylates and others. As mentioned, crosslinked thermosets, such as phenoplasts, aminoplasts, polyesters, polyphenylene sulfide resins, silicone resins, acrylate resins, alkyd resins, polyethylene sulfide resins, unsaturated polyester resins, epoxy resins and polyurethanes, are particularly preferred as binders. Appropriate binders are silicone resins and radiation-hardened unsaturated acrylate resins or polyester resins.

Besonders günstige Bindemittel in den vorliegenden Beschich­tungen sind aliphatisch vernetzte hydroxylgruppenhaltige aliphatische, gesättigte Polyester. Diese eignen sich beson­ders für das Bedrucken mineralischer und metallischer Unter­gründe, da sie auf diesen erhöhte Haftfestigkeit haben. Be­vorzugt enthalten diese im unvernetzten Zustand 2 bis 12 Gew.-% Hydroxylgruppen, von denen 40 bis 60 % durch ein Ver­netzungsmittel, wie ein aliphatisches Polyisocyanat oder ei­nen aliphatischen Polyalkohol, vernetzt sind. Bevorzugt ent­halten diese Polyester im unvernetzten Zustand 7 bis 9 Gew.-­% Hydroxylgruppen, wobei von den Hydroxylgruppen 45 bis 55 % vernetzt sind. Die Vernetzung erfolgt zweckmäßig mit einem Diisocyanat, besonders Hexamethylendiisocyanat.Particularly favorable binders in the present coatings are aliphatic crosslinked hydroxyl-containing aliphatic, saturated polyesters. These are particularly suitable for printing on mineral and metallic substrates, since they have increased adhesive strength on them. In the uncrosslinked state, these preferably contain 2 to 12% by weight of hydroxyl groups, 40 to 60% of which are crosslinked by a crosslinking agent, such as an aliphatic polyisocyanate or an aliphatic polyalcohol. In the uncrosslinked state, these polyesters preferably contain 7 to 9% by weight of hydroxyl groups, 45 to 55% of the hydroxyl groups being crosslinked. The crosslinking is expediently carried out using a diisocyanate, especially hexamethylene diisocyanate.

Bei diesen Polyestern als Bindemittel ist es wesentlich, daß sowohl die Polyester als auch die Vernetzungskomponenten aliphatischer Natur sind.With these polyesters as binders, it is essential that both the polyester and the crosslinking components are aliphatic in nature.

Wenn von aliphatischen Polyestern die Rede ist, so können diese geradkettig oder verzweigtkettig sein, wobei ver­zweigtkettige bevorzugt sind. Auch können die Polyester ge­gebenenfalls zusätzlich zu den Estergruppen noch andere or­ganische Gruppen, wie Ethergruppen, enthalten. Die Moleku­largewichte der erfindungsgemäß verwendeten Polyester liegen im unvernetzten Zustand vorzugsweise im Bereich von 700 bis 5000. Sie entstehen durch bekannte Umsetzung von Di- oder Tricarbonsäuren mit überschüssigen Di- oder Polyalkoholen, so daß sie an den Kettenenden Hydroxylgruppen tragen. Die hierfür einsetzbare Dicarbonsäure ist beispielsweise Adipin­säure.When talking about aliphatic polyesters, so can these are straight-chain or branched-chain, with branched-chain ones being preferred. The polyesters may also contain other organic groups, such as ether groups, in addition to the ester groups. The molecular weights of the polyesters used according to the invention are preferably in the range from 700 to 5000 in the uncrosslinked state. They are formed by known reaction of di- or tricarboxylic acids with excess di- or polyalcohols, so that they carry hydroxyl groups at the chain ends. The dicarboxylic acid that can be used for this is, for example, adipic acid.

Die bei der Herstellung der unvernetzten Polyester verwend­baren Diole und Polyole sind beispielsweise Neopentylglycol, Ethylenglycol, Propan-1,2-diol, 1,4-Bis-(hydroxymethyl)-cyc­lohexan, Glycerin, Trimethylolpropan und Pentaerythrit.The diols and polyols which can be used in the production of the uncrosslinked polyesters are, for example, neopentyl glycol, ethylene glycol, propane-1,2-diol, 1,4-bis (hydroxymethyl) cyclohexane, glycerol, trimethylol propane and pentaerythritol.

Die Vernetzung eines Teils der freien Hydroxylgruppen des Polyesters kann mit unterschiedlichen mehrfunktionellen ali­phatischen Verbindungen erfolgen, besonders mit aliphati­schen Polyisocyanaten oder aliphatischen Polyalkoholen. Da­runter werden Isocyanate und Alkohole mit wenigstens zwei Isocyanat- bzw. Hydroxylgruppen verstanden. Bei einer Ver­netzung mit Polyisocyanaten entstehen Urethangruppen, bei der Vernetzung mit Polyalkoholen Ethergruppen. Die Vernet­zung kann auch mit beiden Verbindungstypen erfolgen, um ge­mischte Urethan-Ether-Vernetzungen zu erhalten.A part of the free hydroxyl groups of the polyester can be crosslinked with different polyfunctional aliphatic compounds, especially with aliphatic polyisocyanates or aliphatic polyalcohols. This is understood to mean isocyanates and alcohols with at least two isocyanate or hydroxyl groups. Crosslinking with polyisocyanates creates urethane groups, crosslinking with polyalcohols creates ether groups. Crosslinking can also be carried out with both types of compounds in order to obtain mixed urethane-ether crosslinks.

Die erfindungsgemäßen Beschichtungen können sowohl als Naß­lacke als auch als Pulverlacke aufgebracht werden. Im Falle der Verwendung eines Naßlackes, d. h. eines lösungsmittel­haltigen Lackbindemittels, ist es zweckmäßig, zusammen mit den Glasflocken ein Thixotropiermittel, wie kolloidale Kie­selsäure, Bentone oder Rizinusöle, vorzugsweise in einer Menge von 0,3 bis 5 Gew.-%, bezogen auf das Trockengewicht der Beschichtung, einzuarbeiten. Pulverlacke haben den Vor­teil, daß sie eine extrem hohe Haftung auf mineralischen Un­tergründen und sogar auf einer Keramikglasur ergeben.The coatings according to the invention can be applied both as wet lacquers and as powder lacquers. If a wet lacquer, ie a solvent-based lacquer binder, is used, it is expedient, together with the glass flakes, to use a thixotropic agent, such as colloidal silica, bentone or castor oils, preferably in an amount of 0.3 to 5% by weight, based on the dry weight the coating. Powder coatings have the advantage that they give extremely high adhesion to mineral substrates and even to a ceramic glaze.

Außer den oben erwähnten Vorteilen hoher Kratzfestigkeit und Oberflächenhärte sowie guter Farbaufnahme für sublimierbare Dispersionsfarbstoffe haben die erfindungsgemäßen Beschich­tungen überraschenderweise eine hohe UV-Stabilität, die we­sentlich höher als die entsprechender Lackbeschichtungen oh­ne Glasflockeneinlagerung ist.In addition to the above-mentioned advantages of high scratch resistance and surface hardness and good ink absorption for sublimable disperse dyes, the coatings according to the invention surprisingly have a high UV stability, which is significantly higher than the corresponding paint coatings without glass flake storage.

Die erfindungsgemäßen Lackbeschichtungen können zur Bedruk­kung mit beliebigen sublimierbaren Dispersionsfarbstoffen verwendet werden, günstigerweise mit solchen, die ein Mole­kulargewicht zwischen 340 und 1000, vorzugsweise zwischen 400 und 1000 besitzen, da diese geringere Migrationsneigung haben und im Regelfall lichtecht sind. Bevorzugte Gruppen von Dispersionsfarbstoffen für das Bedrucken von Lackbe­schichtungen nach der Erfindung sind Anthrachinon-, Monoazo- und Azomethinfarbstoffe, doch ist die Anwendbarkeit nicht auf diese Farbstoffgruppen beschränkt. Bevorzugt sind An­thrachinon-, Monoazo- und Azomethinfarbstoffe, deren Molekü­le stark mit Amino-, Alkoxy-, Oxalkyl-, Nitro-, Halogen- und Cyanogruppen besetzt sind. Diese Farbstoffgruppen sind im Colour-Index, Volume 1, Seiten 1655 bis 1742 definiert. Diesbezüglich wird auf die Seiten 9 bis 11 der EP-A-0 014 901 hingewiesen.The lacquer coatings according to the invention can be used for printing with any sublimable disperse dyes, advantageously with those which have a molecular weight between 340 and 1000, preferably between 400 and 1000, since they have a lower tendency to migrate and are generally lightfast. Preferred groups of disperse dyes for printing on lacquer coatings according to the invention are anthraquinone, monoazo and azomethine dyes, but the applicability is not limited to these groups of dyes. Anthraquinone, monoazo and azomethine dyes are preferred, the molecules of which are heavily occupied with amino, alkoxy, oxalkyl, nitro, halogen and cyano groups. These dye groups are defined in the Color Index, Volume 1, pages 1655 to 1742. In this regard, reference is made to pages 9 to 11 of EP-A-0 014 901.

Die sublimierbaren Dispersionsfarbstoffe können auf die er­findungsgemäßen Lackbeschichtungen entweder im Transfer­druckverfahren von einem Hilfsträger aus übertragen oder di­rekt aufgedruckt werden. In beiden Fällen ist es aber we­sentlich, daß durch Wärmeanwendung die Farbstoffe in die Lackbeschichtung gehen und in die Tiefe der Bindemittel­schicht wandern, was die hohe Brillanz solcher Druckbilder ergibt.The sublimable disperse dyes can either be transferred to the lacquer coatings according to the invention in a transfer printing process from an auxiliary carrier or printed directly on. In both cases, however, it is essential that the dyes go into the lacquer coating due to the application of heat and migrate into the depth of the binder layer, which results in the high brilliance of such printed images.

Die Erfindung betrifft auch Beschichtungsmittel für die Her­stellung der oben definierten Lackbeschichtungen zur Bedruk­kung mit sublimierbaren Dispersionsfarbstoffen. Diese Be­schichtungsmittel bestehen aus einem thermoplastischen oder vorzugsweise duroplastischen Lackbindemittel, gegebenenfalls wenigstens einem organischen Lösungsmittel für das Lackbin­demittel, 10 bis 100 Gewichtsteilen, bezogen auf das Gewicht der Trockensubstanz des Lackbindemittels, unregelmäßig ge­formter Glasflocken, von denen wenigstens 90 Gew.-% eine größte Abmessung von maximal 0,5 mm und eine kleinste Abmes­sung von mindestens 0,05 mm sowie eine Dicke von 0,5 bis 20 µm besitzen, sowie gegebenenfalls übliche Lackzusatzstof­fe, wie Thixotropiermittel. Im Falle von Pulverlacken beste­hen die Beschichtungsmittel gewöhnlich nur aus Gemischen des Bindemittels in Pulverform und den Glasflocken.The invention also relates to coating compositions for the production of the paint coatings defined above for printing with sublimable disperse dyes. These coating compositions consist of a thermoplastic or preferably thermosetting paint binder, if appropriate at least one organic solvent for the paint binder, 10 to 100 parts by weight, based on the weight of the dry substance of the paint binder, of irregularly shaped glass flakes, of which at least 90% by weight have a largest dimension of at most 0.5 mm and a smallest dimension of at least 0 , 05 mm and a thickness of 0.5 to 20 µm, as well as, where appropriate, conventional paint additives, such as thixotropic agents. In the case of powder coatings, the coating compositions usually consist only of mixtures of the binder in powder form and the glass flakes.

Die oben aufgeführten bevorzugten Angaben bezüglich der Di­mensionierungen der Glasflocken, bezüglich weiterer Zusatz­stoffe und bezüglich des Lackbindemittels gelten auch für das Beschichtungsmittel sowie auch für das nachfolgend be­schriebene Verfahren zur Herstellung bedruckter Oberflächen von Gegenständen.The preferred details given above with regard to the dimensions of the glass flakes, with regard to further additives and with regard to the paint binder also apply to the coating agent and also to the process described below for the production of printed surfaces of objects.

Dieses Verfahren besteht darin, daß man den Gegenstand mit einer Lackbeschichtung versieht, die aus einem gehärteten thermoplastischen oder duroplastischen Lackbindemittel und darin verteilten Glasflocken in den oben angegebenen Mengen­verhältnissen und mit den oben angegebenen Abmessungen sowie gegebenenfalls üblichen Lackzusatzstoffen besteht, sodann die Lackbeschichtung, direkt oder im Transferdruckverfahren, mit sublimierbaren Dispersionsfarbstoffen bedruckt und diese durch Erhitzen in die Lackbeschichtung eindringen läßt. Be­vorzugte Temperaturen für das Erhitzen liegen im Bereich von 210 bis 260 °C, die Erhitzungszeiten können im Sekundenbe­reich bis Minutenbereich liegen. Im Falle der Bedruckung nach dem Transferdruckverfahren werden durch das Erhitzen die sublimierbaren Dispersionsfarbstoffe aus der Bedruckung des Hilfsträgers heraussublimiert und gleichzeitig in die Lackbeschichtung eingeführt. Im Falle von Pulverlacken er­folgt zunächst die Bedruckung und anschließende Erhitzung, um die auf der Lackbeschichtung liegenden Dispersionsfarb­stoffe in die Lackbeschichtung eindringen zu lassen.This method consists in providing the object with a lacquer coating which consists of a hardened thermoplastic or thermosetting lacquer binder and glass flakes distributed therein in the proportions given above and with the dimensions given above and, if appropriate, conventional lacquer additives, then the lacquer coating, directly or in Transfer printing process, printed with sublimable disperse dyes and allowing them to penetrate the paint coating by heating. Preferred temperatures for the heating are in the range of 210 to 260 ° C, the heating times can be in the range of seconds to minutes. In the case of printing using the transfer printing process, the sublimable disperse dyes are sublimed out of the printing on the auxiliary carrier and simultaneously introduced into the coating. In the case of powder coatings, printing and subsequent heating are carried out in order to allow the disperse dyes on the coating to penetrate the coating.

Wenn in der Beschreibung von gehärteten thermoplastischen Bindemitteln die Rede ist, so bedeutet dies eine durch Ab­kühlung erfolgte Erstarrung der in der Hitze erweichten Thermoplasten. Im Falle von Duroplasten bedeutet der Begriff der Härtung eine Vernetzung, so daß beim Erhitzen keine Er­weichung des Bindemittels mehr eintritt.If the description refers to hardened thermoplastic binders, this means that the thermoplastic softened in the heat is solidified by cooling. In the case of thermosets, the term curing means crosslinking, so that the binder no longer softens when heated.

Wenn hier von einer größten und einer kleinsten Abmessung der Glasflocken die Rede ist, so meint dies die Durchmesser der unregelmäßig geformten Flocken senkrecht zur Dickenrich­tung, d. h. in Draufsicht auf die Flocken. Dabei könnte man die größte Abmessung auch als Länge der Flocken und die kleinste Abmessung als Breite der Flocken bezeichnen. Die Flocken sind also höchstens 0,5 mm lang und mindestens 0,05 mm breit.When we speak of a largest and a smallest dimension of the glass flakes, this means the diameter of the irregularly shaped flakes perpendicular to the thickness direction, i.e. H. in top view of the flakes. The largest dimension could also be referred to as the length of the flakes and the smallest dimension as the width of the flakes. The flakes are therefore at most 0.5 mm long and at least 0.05 mm wide.

Beispiel 1example 1

Ein Naßlack wurde in folgender Weise hergestellt:
20 Gewichtsteile Glasflocken mit einer Dicke von etwa 3 µm, von denen 98 Gew.-% eine größte Abmessung von weniger als 0,25 mm und eine kleinste Abmessung von mehr als 0,1 mm be­saßen, sowie 1,0 Gewichtsteile kolloidale Kieselsäure (Aero­sil 380) und 40,0 Gewichtsteile Butylacetat wurden intensiv miteinander verrührt. Hierzu wurden 25 Gewichtsteile Diiso­cyanat (Desmodur N) in 75 %iger Lösung in Xylol/Methoxypro­pylacetat, sowie 100 Gewichtsteile hydroxylhaltiger gesät­tigter Polyesterlack als 65 %ige Lösung in Methoxypropylace­tat zugegeben und intensiv verrührt.A wet paint was produced in the following way:
20 parts by weight of glass flakes with a thickness of approximately 3 µm, of which 98% by weight had a largest dimension of less than 0.25 mm and a smallest dimension of more than 0.1 mm, and 1.0 part by weight of colloidal silica (Aerosil 380) and 40.0 parts by weight of butyl acetate were thoroughly stirred together. For this purpose, 25 parts by weight of diisocyanate (Desmodur N) in 75% solution in xylene / methoxypropylacetate and 100 parts by weight of hydroxyl-containing saturated polyester paint as 65% solution in methoxypropylacetate were added and stirred vigorously.

Mit dem so hergestellten Naßlack wurden glasierte Keramik­kacheln mit einem Spritzautomaten beschichtet, wonach die Beschichtung 10 min bei 180 °C eingebrannt wurde.The wet paint thus produced was used to coat glazed ceramic tiles with an automatic spray gun, after which the coating was baked at 180 ° C. for 10 minutes.

In einem Vergleichsversuch wurde der gleiche Naßlack ohne Glasflocken hergestellt. Die folgende Tabelle I zeigt die bei beiden verglichenen beschichteten Kacheln erhaltenen Ei­genschaften: Tabelle I mit Glasflocken ohne Glasflocken Härte nach Mohs 2 bis 3 0 Farbaufnahme 220 Grad/3˝ gut gut Farbaufnahme untere Lackschicht gut gut UV-Beständigkeit Xenon-Test Wollskala 7 1000 h 650 h In a comparative experiment, the same wet paint was produced without glass flakes. The following Table I shows the properties obtained for the two coated tiles compared: Table I with glass flakes without glass flakes Mohs hardness 2 to 3 0 Color recording 220 degrees / 3˝ Good Good Color absorption of the lower lacquer layer Good Good UV resistance xenon test wool scale 7 1000 h 650 h

Beispiel 2Example 2

Ein Pulverlack wurde aus 100 Gewichtsteilen eines handelsüb­lichen mit TGIC gehärteten Pulverlackes und 40 Gewichtstei­len der im Beispiel 1 angegebenen Glasflocken hergestellt. Der Pulverlack wurde in üblicher Weise auf glasierten Kera­mikkacheln aufgetragen und 5 min im Infrarotkanal bei 200 °C eingebrannt.A powder coating was prepared from 100 parts by weight of a commercially available powder coating hardened with TGIC and 40 parts by weight of the glass flakes specified in Example 1. The powder coating was applied in the customary manner to glazed ceramic tiles and baked in the infrared channel at 200 ° C. for 5 minutes.

Wiederum wurden Kacheln mit dem gleichen Pulverlack ohne Glasflocken beschichtet. Die Eigenschaften wurden ermittelt und finden sich in der Tabelle II. Tabelle II mit Glasflocken ohne Glasflocken Härte nach Mohs 2 bis 3 0 Farbaufnahme 220 Grad/3˝ gut gut Farbaufnahme untere Lackschicht gut gut UV-Beständigkeit Xenon-Test Wollskala 7 1000 h 700 h Again, tiles were coated with the same powder coating without glass flakes. The properties were determined and can be found in Table II. Table II with glass flakes without glass flakes Mohs hardness 2 to 3 0 Color recording 220 degrees / 3˝ Good Good Color absorption of the lower lacquer layer Good Good UV resistance xenon test wool scale 7 1000 h 700 h

Claims (10)

1. Lackbeschichtung auf der Oberfläche eines bedruckbaren Gegenstandes zur Bedruckung mit sublimierbaren Dispersi­onsfarbstoffen aus einem gehärteten thermoplastischen oder duroplastischen Lackbindemittel und darin verteiltem Füllstoff sowie gegebenenfalls üblichen Lackzusatzstof­fen, dadurch gekennzeichnet, daß sie als Füllstoff 10 bis 100 Gewichtsteile je 100 Gewichtsteile Trockensubstanz des Lackbindemittels unregelmäßig geformter Glasflocken enthält, von denen wenigstens 90 Gew.-% eine größte Ab­messung von maximal 0,5 mm und eine kleinste Abmessung von mindestens 0,05 mm sowie eine Dicke von 0,5 bis 20 µm besitzen.1. Lacquer coating on the surface of a printable object for printing with sublimable disperse dyes made of a hardened thermoplastic or thermosetting lacquer binder and filler distributed therein and, if appropriate, conventional lacquer additives, characterized in that they contain 10 to 100 parts by weight per 100 parts by weight of dry substance of the lacquer binder of irregularly shaped glass flakes contains, of which at least 90 wt .-% have a largest dimension of maximum 0.5 mm and a smallest dimension of at least 0.05 mm and a thickness of 0.5 to 20 microns. 2. Lackbeschichtung nach Anspruch 1, dadurch gekennzeichnet, daß von den Glasflocken wenigstens 90 Gew.-% eine größte Abmessung von maximal 0,25 mm besitzen.2. Lacquer coating according to claim 1, characterized in that at least 90% by weight of the glass flakes have a maximum dimension of at most 0.25 mm. 3. Lackbeschichtung nach Anspruch 1 oder 2, dadurch gekenn­zeichnet, daß die Glasflocken eine Dicke von 1 bis 10, vorzugsweise 1 bis 6 µm besitzen.3. Lacquer coating according to claim 1 or 2, characterized in that the glass flakes have a thickness of 1 to 10, preferably 1 to 6 µm. 4. Lackbeschichtung nach einem der Ansprüche 1 bis 3, da­durch gekennzeichnet, daß sie die Glasflocken in einer Menge von 20 bis 60, vorzugsweise 25 bis 45 Gewichtstei­len je 100 Gewichtsteile Trockensubstanz des Lackbinde­mittels enthält.4. Paint coating according to one of claims 1 to 3, characterized in that it contains the glass flakes in an amount of 20 to 60, preferably 25 to 45 parts by weight per 100 parts by weight of dry substance of the paint binder. 5. Lackbeschichtung nach einem der Ansprüche 1 bis 4, da­durch gekennzeichnet, daß sie zusätzlich ein Thixotropier­mittel, vorzugsweise in einer Menge von 0,3 bis 5 Gew.-%, bezogen auf das Gewicht der Lackbeschichtung, enthält.5. Paint coating according to one of claims 1 to 4, characterized in that it additionally contains a thixotropic agent, preferably in an amount of 0.3 to 5 wt .-%, based on the weight of the paint coating. 6. Lackbeschichtung nach einem der Ansprüche 1 bis 5, da­durch gekennzeichnet, daß sie als Lackbindemittel einen aliphatisch vernetzten hydroxylgruppenhaltigen aliphati­schen, gesättigten Polyester enthält, der in unvernetztem Zustand 2 bis 12 Gew.-%, vorzugsweise 6 bis 10, besonders 7 bis 9 Gew.-% Hydroxylgruppen enthält, von denen nur 40 bis 60, vorzugsweise 45 bis 55 % vernetzt sind.6. Paint coating according to one of claims 1 to 5, characterized in that it as a paint binder Contains aliphatic crosslinked hydroxyl group-containing aliphatic, saturated polyester, which in the uncrosslinked state contains 2 to 12% by weight, preferably 6 to 10, particularly 7 to 9% by weight of hydroxyl groups, of which only 40 to 60, preferably 45 to 55% crosslinked are. 7. Beschichtungsmittel zur Herstellung einer Lackbeschich­tung nach einem der Ansprüche 1 bis 6, dadurch gekenn­zeichnet, daß es ein thermoplastisches oder duroplasti­sches Lackbindemittel sowie je 100 Gewichtsteile Trocken­substanz dieses Lackbindemittels 10 bis 100 Gewichtsteile unregelmäßig geformter Glasflocken, von denen wenigtens 90 Gew.-% eine größte Abmessung von maximal 0,5 mm und eine kleinste Abmessung von mindestens 0,05 mm sowie eine Dicke von 0,5 bis 20 µm besitzen, und außerdem gegebenen­falls übliche Lackzusatzstoffe und/oder übliche organi­sche Lösungsmittel für das Lackbindemittel enthält.7. Coating agent for producing a paint coating according to one of claims 1 to 6, characterized in that it is a thermoplastic or thermosetting paint binder and 100 parts by weight of dry substance of this paint binder 10 to 100 parts by weight of irregularly shaped glass flakes, of which at least 90% by weight is a largest Have a maximum dimension of 0.5 mm and a smallest dimension of at least 0.05 mm and a thickness of 0.5 to 20 µm, and also optionally contains customary paint additives and / or customary organic solvents for the paint binder. 8. Verfahren zur Herstellung einer bedruckten Oberfläche eines Gegenstandes mit Hilfe einer Lackbeschichtung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man auf der Oberfläche des Gegenstandes eine Lackbe­schichtung aus einem gehärteten thermoplastischen oder duroplastischen Lackbindemittel und, je 100 Gewichtsteile Trockensubstanz des Lackbindemittels, 10 bis 100 Ge­wichtsteilen darin verteilter unregelmäßig geformter Glasflocken, von denen wenigstens 90 Gew.-% eine größte Abmessung von maximal 0,5 mm und eine kleinste Abmessung von mindestens 0,05 mm sowie eine Dicke von 0,5 bis 20 µm besitzen, sowie gegebenenfalls üblichen Lackzusatz­stoffen aufbringt, die Lackbeschichtung mit sublimierba­ren Dispersionsfarbstoffen bedruckt und die Disperions­farbstoffe durch Erhitzen in die Lackbeschichtung ein­dringen läßt.8. A process for producing a printed surface of an object with the aid of a lacquer coating according to one of claims 1 to 6, characterized in that a lacquer coating of a hardened thermoplastic or thermosetting lacquer binder and, in each case 100 parts by weight of dry substance of the lacquer binder, on the surface of the object. 10 to 100 parts by weight of irregularly shaped glass flakes distributed therein, of which at least 90% by weight have a largest dimension of at most 0.5 mm and a smallest dimension of at least 0.05 mm and a thickness of 0.5 to 20 µm, and optionally applying customary paint additives, printing the paint coating with sublimable dispersion dyes and allowing the dispersion dyes to penetrate the paint coating by heating. 9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß man die Lackbeschichtung nach dem Transferdruckverfahren mit den sublimierbaren Disperionsfarbstoffen bedruckt.9. The method according to claim 8, characterized in that the varnish coating by the transfer printing process printed with the sublimable dispersion dyes. 10. Lackbeschichtung nach Anspruch 8 oder 9, dadurch gekenn­zeichnet, daß man die Disperionsfarbstoffe durch Erhit­zen auf 210 bis 260 °C in die Lackbeschichtung eindrin­gen läßt.10. Lacquer coating according to claim 8 or 9, characterized in that the dispersion dyes are allowed to penetrate into the lacquer coating by heating to 210 to 260 ° C.
EP88120218A 1988-07-15 1988-12-03 Lacquer-coating printable with sublimable dispersion dyes, coating material therefor and method for the preparation of printed objects Expired - Lifetime EP0350534B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88120218T ATE86924T1 (en) 1988-07-15 1988-12-03 VARNISH COATING PRINTABLE WITH SUBLIMABLE DISPERSION DYES, COATING MEANS THEREOF AND PROCESS FOR MANUFACTURING PRINTED ARTICLES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3824012A DE3824012A1 (en) 1988-07-15 1988-07-15 VARNISH COATING PRINTED WITH SUBLIMIBLE DISPERSION DYES, COATING AGENTS THEREFOR AND METHOD FOR THE PRODUCTION OF PRINTED OBJECTS
DE3824012 1988-07-15

Publications (3)

Publication Number Publication Date
EP0350534A2 true EP0350534A2 (en) 1990-01-17
EP0350534A3 EP0350534A3 (en) 1990-06-27
EP0350534B1 EP0350534B1 (en) 1993-03-17

Family

ID=6358741

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88120218A Expired - Lifetime EP0350534B1 (en) 1988-07-15 1988-12-03 Lacquer-coating printable with sublimable dispersion dyes, coating material therefor and method for the preparation of printed objects

Country Status (3)

Country Link
EP (1) EP0350534B1 (en)
AT (1) ATE86924T1 (en)
DE (2) DE3824012A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0721848A1 (en) * 1994-07-26 1996-07-17 Sony Corporation Image transfer method, and substrate for transfer and ink ribbon used therefor
EP1558399A2 (en) * 2002-10-15 2005-08-03 Basic Research, L.L.C. Natural-appearing, penetrating, ink sublimation printing process
US9856055B2 (en) 2014-04-29 2018-01-02 At Promotions Ltd Drinking or eating vessel
US10125270B2 (en) 2012-04-24 2018-11-13 At Promotions Ltd Anti-microbial drinking or eating vessel
US10947011B2 (en) 2014-12-22 2021-03-16 At Promotions Ltd Drinking or eating vessel
US10973349B2 (en) 2017-01-10 2021-04-13 At Promotions, Ltd Vacuum decoration of a drinking or eating vessel

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5888623A (en) * 1993-03-20 1999-03-30 Hans Grohe Gmbh & Co. Kg Sanitary article or plumbing fitting with a coated surface and a print image applied thereto and a process for making the same
DE4308977A1 (en) * 1993-03-20 1994-09-22 Grohe Kg Hans Sanitary article with a coated surface and process for its manufacture
DE102006048092A1 (en) * 2006-10-10 2008-04-17 Meinberg, Kurt Furniture plate decorating method, involves printing coated broadside and circular edges with sublimable dispersed dye for decoration, and fixing imprint in and/or at powder lacquer under pressing pressure and heat
CN104553429B (en) * 2014-12-25 2018-06-19 广州市龙珠化工有限公司 A kind of color crystal glass UV shifting process

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076130A2 (en) * 1981-09-28 1983-04-06 RAYCHEM CORPORATION (a California corporation) Printing on low surface energy polymers
DE3303427A1 (en) * 1982-02-03 1983-08-11 Canon K.K., Tokyo MATERIAL TO BE USED AS WRITING AND PRINTING MEDIA
US4603079A (en) * 1983-08-02 1986-07-29 Ricoh Co., Ltd. Overcoated sheet
EP0265139A2 (en) * 1986-10-15 1988-04-27 Polyplastics Co., Ltd. Impregnation-printed moulded article
EP0276075A1 (en) * 1987-01-21 1988-07-27 Polyplastics Co. Ltd. Method of producing characters, symbols, patterns on thermoplastic resin moulded articles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0076130A2 (en) * 1981-09-28 1983-04-06 RAYCHEM CORPORATION (a California corporation) Printing on low surface energy polymers
DE3303427A1 (en) * 1982-02-03 1983-08-11 Canon K.K., Tokyo MATERIAL TO BE USED AS WRITING AND PRINTING MEDIA
US4603079A (en) * 1983-08-02 1986-07-29 Ricoh Co., Ltd. Overcoated sheet
EP0265139A2 (en) * 1986-10-15 1988-04-27 Polyplastics Co., Ltd. Impregnation-printed moulded article
EP0276075A1 (en) * 1987-01-21 1988-07-27 Polyplastics Co. Ltd. Method of producing characters, symbols, patterns on thermoplastic resin moulded articles

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6793988B2 (en) 1994-01-24 2004-09-21 Sony Corporation Ink ribbon for image transcription
EP0721848A4 (en) * 1994-07-26 1997-11-05 Sony Corp Image transfer method, and substrate for transfer and ink ribbon used therefor
US6417138B1 (en) 1994-07-26 2002-07-09 Sony Corporation Method for transcribing an image and a support for transcription and ink ribbon employed therefor
EP0721848A1 (en) * 1994-07-26 1996-07-17 Sony Corporation Image transfer method, and substrate for transfer and ink ribbon used therefor
EP1558399A2 (en) * 2002-10-15 2005-08-03 Basic Research, L.L.C. Natural-appearing, penetrating, ink sublimation printing process
EP1558399A4 (en) * 2002-10-15 2009-01-14 Basic Res L L C Natural-appearing, penetrating, ink sublimation printing process
US10125270B2 (en) 2012-04-24 2018-11-13 At Promotions Ltd Anti-microbial drinking or eating vessel
US9856055B2 (en) 2014-04-29 2018-01-02 At Promotions Ltd Drinking or eating vessel
US20180155082A1 (en) 2014-04-29 2018-06-07 At Promotions Ltd Drinking or eating vessel
US10273055B2 (en) 2014-04-29 2019-04-30 At Promotions Ltd Drinking or eating vessel
US10611525B2 (en) 2014-04-29 2020-04-07 At Promotions, Ltd Drinking or eating vessel
US10947011B2 (en) 2014-12-22 2021-03-16 At Promotions Ltd Drinking or eating vessel
US10973349B2 (en) 2017-01-10 2021-04-13 At Promotions, Ltd Vacuum decoration of a drinking or eating vessel

Also Published As

Publication number Publication date
EP0350534A3 (en) 1990-06-27
EP0350534B1 (en) 1993-03-17
DE3824012A1 (en) 1990-01-18
DE3879482D1 (en) 1993-04-22
ATE86924T1 (en) 1993-04-15

Similar Documents

Publication Publication Date Title
DE19725829C1 (en) Surface coating material for wood used in furniture, wall panels etc.
EP0350534B1 (en) Lacquer-coating printable with sublimable dispersion dyes, coating material therefor and method for the preparation of printed objects
EP3322596B1 (en) Method for the preparation of a laminate consisting of support plate and decorative paper
DE3304826A1 (en) LAYERED BODY, PARTICULARLY DECORATIVE FLOORING TILE
WO2008080746A2 (en) Conductive, organic coatings with low layer thickness and good plasticity
EP3757178B1 (en) Production method for at least one material with printed decorative element
DE2714593B2 (en) Process for coating surfaces, in particular industrial floors, for protection against abrasion and corrosion
DE4317302A1 (en) Conductive floor coating
EP3291989B1 (en) Laser engravable pad printing plate
DE2948140C2 (en) Magnetic recording medium and method for producing such a magnetic recording medium
EP1931565B1 (en) Polyurethane lacquers as abrasion-resistant coatings
DE2756908A1 (en) FILM MATERIAL FOR THE MANUFACTURING OF WALL PANELS OR DGL.
DE2345607C2 (en) Coating material for radar-safe camouflage and / or for securing radar location and method for its production
EP0047814A1 (en) Registration support for electroerosion printing
DE102018116359A1 (en) Water-based inkjet ink
DE3728884A1 (en) Binder for printing mineral or metallic substrates
DE2940370A1 (en) Sublimation-printing plastic surfaces - applied to fibres, metals, etc. from thermosetting lacquer contg. poly:isocyanate and (meth)acrylate! polymer
DE1669137A1 (en) Paints with thixotropic properties
DE2724371C3 (en) Magnetic coating composition and process for its preparation
EP0061121A1 (en) Process for producing a plane support having a matt surface coated with a varnish cured by electron beams
DE102008008779A1 (en) Aqueous coating material, process for its preparation and its use
EP2260161B1 (en) Coated wooden floor panel
EP0567940B1 (en) Curable mixture for the preparation of a highly abrasion resistant coating
DE2254981A1 (en) METHOD OF MANUFACTURING MAGNETIC PLATES WITH THIN MAGNETIC LAYERS
WO2023247775A1 (en) Aqueous topcoat composition for decorative-finish films

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19900123

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BEUTELROCK, CAROLIN

17Q First examination report despatched

Effective date: 19911118

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19930317

Ref country code: SE

Effective date: 19930317

Ref country code: BE

Effective date: 19930317

Ref country code: NL

Effective date: 19930317

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19930317

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19930317

REF Corresponds to:

Ref document number: 86924

Country of ref document: AT

Date of ref document: 19930415

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3879482

Country of ref document: DE

Date of ref document: 19930422

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19930614

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19931203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19931231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: OSTERMANN & SCHEIWE GMBH & CO.

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19961125

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19961126

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19961128

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970124

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971231

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19971231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971231

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19971203

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980901

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST