DE102021106964A1 - COLORLESS SURFACE COATING - Google Patents
COLORLESS SURFACE COATING Download PDFInfo
- Publication number
- DE102021106964A1 DE102021106964A1 DE102021106964.5A DE102021106964A DE102021106964A1 DE 102021106964 A1 DE102021106964 A1 DE 102021106964A1 DE 102021106964 A DE102021106964 A DE 102021106964A DE 102021106964 A1 DE102021106964 A1 DE 102021106964A1
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- Germany
- Prior art keywords
- nir
- led
- vis
- free
- colorless
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0209—Multistage baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0263—After-treatment with IR heaters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2270/00—Compositions for creating interpenetrating networks
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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Abstract
Vorgeschlagen wird eine farblose Oberflächenbeschichtung, die man dadurch erhält, dass man eine zu beschichtende Oberfläche mit einer wässrigen Lackdispersion in Kontakt bringt, die so behandelte Oberfläche zunächst mit Hilfe von NIR-Strahlung trocknet und verfilmt und anschließend den getrockneten Film mit Hilfe von UV-VIS-Strahlung vernetzt.A colorless surface coating is proposed, which is obtained by bringing a surface to be coated into contact with an aqueous paint dispersion, first drying and filming the surface treated in this way using NIR radiation and then applying the dried film using UV-VIS -Radiation networked.
Description
GEBIET DER ERFINDUNGFIELD OF THE INVENTION
Die Erfindung befindet sich auf dem Gebiet der Lacke und Farben und betrifft Oberflächenbeschichtungen auf Basis von wässrigen Dispersionen mit polymeren Bindemitteln, die sich dadurch auszeichnen, dass sie nach Trocknung/Verfilmung und Vernetzung für das menschliche Auge farblos sind.The invention is in the field of lacquers and paints and relates to surface coatings based on aqueous dispersions with polymeric binders, which are characterized in that they are colorless to the human eye after drying/filming and crosslinking.
TECHNOLOGISCHER HINTERGRUNDTECHNOLOGICAL BACKGROUND
Lacke und Farben stellen die bei weitem wichtigsten Mittel zur Beschichtung von Oberflächen dar. Neben ästhetischen Gesichtspunkten stehen Schutzfunktionen, insbesondere Korrosionsschutz im Vordergrund. Jährlich werden weltweit mehr als 30 Milliarden Tonnen an Lacken produziert, von denen mehr als die Hälfte in der Bauindustrie benötigt werden, gefolgt von Industrie- und Pulverlacken.Lacquers and paints are by far the most important means of coating surfaces. In addition to aesthetic aspects, protective functions, in particular corrosion protection, are in the foreground. More than 30 billion tons of coatings are produced worldwide every year, more than half of which are used in the construction industry, followed by industrial and powder coatings.
Die Oberflächenbeschichtung mit Lacken oder Farben beruht darauf, dass eine wässrige Dispersion mit einem Bindemittel aufgebracht wird, welches dann abtrocknet und durch Polymerisation verfilmt. Die Trocknung erfolgt dabei in der Regel physikalisch, d.h. in einem Ofen wird das Wasser verdampft und der trockene Film bleibt zurück. Ein solcher Prozess ist jedoch zeitaufwendig und bedarf der Zuführung von Energie von außen.The surface coating with lacquers or paints is based on the fact that an aqueous dispersion with a binder is applied, which then dries and forms a film through polymerisation. The drying usually takes place physically, i.e. the water is evaporated in an oven and the dry film remains. However, such a process is time-consuming and requires the supply of energy from the outside.
Eine Alternative besteht darin, die für die Verdampfung des Wassers erforderliche Wärme im Innern der Dispersion zu erzeugen. Wie beispielsweise in der Veröffentlichung C. Schmitz et. Al. „Neue Hochleistungs-LEDs ermöglichen Photochemie für die Nahinfrarotsensibilisierte radikalische und kationische Photopolymerisation“, Angewandte Chemie, 2019, 131(13), 4445-4450 beschrieben, kann man den Dispersionen Farbstoffe zusetzen, die im nahen Infrarotbereich absorbieren. Werden diese dann mit entsprechendem NIR-Licht bestrahlt, wird dieses in Wärme umgewandelt, das ausreicht, die in der Dispersion enthaltene Menge an Wasser rasch und vollständig zu entfernen. Problematisch ist jedoch, dass die dabei resultierenden Filme regelmäßig einen grünlichen Farbton aufweisen, der in der Mehrzahl kommerzieller Anwendungen unerwünscht ist. In einigen Fällen kommt es auch zu einer Blaufärbung nach NIR Belichtung wie oben beschriben in Schmitz et. al. oder Pang et. al. in „NIR-Sensitized Activated Photoreaction between Cyanines and Oxime Esters: Free-Radical Photopolymerization“ Angew. Chem. Int. Ed. 2020, 59, 11440-11447 beschrieben, oder die Beschichtung weist einen intensiv gelben bzw. bräunlichen Ton auf, was Brömme et.al. in „Photochemical Oxidation of NIR Photosensitizers in the Presence of Radical Initiators and Their Prospective Use in Dental Applications“ ChemistrySelect 2016, 1, 524-532 berichtet wurde. Es besteht seit langen der Wunsch mit NIR Belichtung Beschichtungsstoffe zu applizieren, welche nach Belichtung für das menschliche Auge erscheinen. Zudem werden aufgrund der VOC Verordnung verstärkt Beschichtungsstoffe eingesetzt, welche wässrig basierend sind. Überrascherweise wurde in dieser Erfindung gefunden, dass diese Anforderungen mit den hier beschriebenen Lösungen gelöst werden. Die verfilmten wässrig basierenden Beschichtungsstoffe waren nach NIR und UV-VIS Belichtung farblos für das menschliche Auge und nicht löslich in herkömmlichen Lösungsmitteln.An alternative consists in generating the heat required for the evaporation of the water inside the dispersion. As for example in the publication C. Schmitz et. Al. "New high-performance LEDs enable photochemistry for near-infrared-sensitized radical and cationic photopolymerization", Angewandte Chemie, 2019, 131(13), 4445-4450, dyes that absorb in the near-infrared range can be added to the dispersions. If these are then irradiated with the appropriate NIR light, this is converted into heat that is sufficient to quickly and completely remove the amount of water contained in the dispersion. The problem, however, is that the resulting films regularly have a greenish hue, which is undesirable in the majority of commercial applications. In some cases there is also a blue coloration after NIR exposure as described above in Schmitz et. al. or Pang et. al. in "NIR-Sensitized Activated Photoreaction between Cyanines and Oxime Esters: Free-Radical Photopolymerization" Angew. Chem. Int. Ed. 2020, 59, 11440-11447, or the coating has an intense yellow or brownish hue, which Brömme et al. in "Photochemical Oxidation of NIR Photosensitizers in the Presence of Radical Initiators and Their Prospective Use in Dental Applications" ChemistrySelect 2016, 1, 524-532. There has long been a desire to use NIR exposure to apply coating materials that appear to the human eye after exposure. In addition, due to the VOC regulation, coating materials that are water-based are increasingly being used. Surprisingly, it was found in this invention that these requirements are solved with the solutions described here. After NIR and UV-VIS exposure, the filmed water-based coating materials were colorless to the human eye and not soluble in conventional solvents.
RELEVANTER STAND DER TECHNIKRELEVANT PRIOR ART
Die Referenz Brömme et.al. in „Photochemical Oxidation of NIR Photosensitizers in the Presence of Radical Initiators and Their Prospective Use in Dental Applications“ ChemistrySelect 2016, 1, 524-532 beschreibt die chemische Trocknung von Lacken mit NIR-Strahlung, wobei der verfestigte Beschichtungsstoff nach dem Applizieren für das Auge eine farbige Erscheinung besitzt.The reference Brömme et al. in "Photochemical Oxidation of NIR Photosensitizers in the Presence of Radical Initiators and Their Prospective Use in Dental Applications" ChemistrySelect 2016, 1, 524-532 describes the chemical drying of paints with NIR radiation, the solidified coating material being visible to the eye after application has a colored appearance.
ZU LÖSENDE AUFGABETASK TO BE SOLVED
Die Aufgabe der vorliegenden Erfindung hat daher darin bestanden, farblose Oberflächenbeschichtungen, seien es Lacke oder Farben, auf Basis wässriger Dispersionen zur Verfügung zu stellen, die nach photonischer Trocknung und Härtung farblos und nahezu wasserfrei sind.The object of the present invention was therefore to provide colorless surface coatings, be they lacquers or paints, based on aqueous dispersions which are colorless and almost water-free after photonic drying and curing.
BESCHREIBUNG DER ERFINDUNGDESCRIPTION OF THE INVENTION
In einer ersten Ausführungsform betrifft die Erfindung farblose Oberflächenbeschichtung, die dadurch erhältlich sind oder erhalten werden, dass man
- (i) eine zu beschichtende Oberfläche zur Verfügung stellt,
- (ii) die zu beschichtende Oberfläche mit einer wässrigen Lackdispersion in Kontakt bringt,
- (iii) die so behandelte Oberfläche zunächst mit Hilfe von NIR-Strahlung trocknet und verfilmt und anschließend
- (iv) den getrockneten Film mit Hilfe von UV-VIS Strahlung bzw. sichtbarem Licht vernetzt, wobei die wässrige Lackdispersion
- (a) wenigstens ein polymeres Bindemittel,
- (b) wenigstens ein radikalisch polymerisierbares Vernetzungsmittel,
- (c) wenigstens einen NIR-Absorber, und
- (d) wenigstens einen radikalbildenden UV-VIS Photoinitiator bzw. -system enthalten.
- (i) provides a surface to be coated,
- (ii) bringing the surface to be coated into contact with an aqueous paint dispersion,
- (iii) the surface treated in this way first dries and forms a film with the aid of NIR radiation and then
- (iv) crosslinking the dried film with the aid of UV-VIS radiation or visible light, the aqueous paint dispersion
- (a) at least one polymeric binder,
- (b) at least one free-radically polymerizable crosslinking agent,
- (c) at least one NIR absorber, and
- (d) contain at least one radical-forming UV-VIS photoinitiator or system.
Ebenfalls beansprucht wird ein analoges Verfahren zur Herstellung farbloser Oberflächenbeschichtungen, umfassend oder bestehend aus den folgenden Schritten:
- (i) Bereitstellen einer wässrigen Lackdispersion enthaltend
- (a) wenigstens ein polymeres Bindemittel,
- (b) wenigstens ein radikalisch polymerisierbares Vernetzungsmittel
- (c) wenigstens einen NIR-Absorber, und
- (d) wenigstens einen radikalbildenden UV-VIS-Photoinitiator
- (ii) Inkontaktbringen einer zu beschichtenden Oberfläche mit der wässrigen Lackdispersion aus (i);
- (iii) Trocknung und Verfilmung der so behandelten Oberfläche durch Behandlung mit NIR-Strahlung und
- (iv) Vernetzung des getrockneten Films durch Behandlung mit UV bzw. sichtbarer Strahlung.
- (i) providing an aqueous paint dispersion containing
- (a) at least one polymeric binder,
- (b) at least one free radically polymerizable crosslinking agent
- (c) at least one NIR absorber, and
- (d) at least one radical-forming UV-VIS photoinitiator
- (ii) contacting a surface to be coated with the aqueous paint dispersion from (i);
- (iii) drying and film formation of the surface treated in this way by treatment with NIR radiation and
- (iv) crosslinking of the dried film by treatment with UV or visible radiation.
Nachdem aus dem Stand der Technik bekannt war, dass sich polymere Bindemittel wie beispielsweise Acrylatverbindungen mit einer Funktionalität von wenigstens 2 durch photonische Trocknung zu grün-gefärbten Überzügen verfilmen, war es überraschend, dass die anschließende Vernetzung der Überzüge in Gegenwart von radikalbildenden Photoinitiatoren und Bestrahlung mit UV-VIS Licht im Bereich von 350 bis 450 nm zu harten Filmen führt, die nun völlig farblos sind.After it was known from the prior art that polymeric binders such as acrylate compounds with a functionality of at least 2 form a film through photonic drying to form green-colored coatings, it was surprising that the subsequent crosslinking of the coatings in the presence of free-radical photoinitiators and irradiation with UV-VIS light in the range of 350 to 450 nm leads to hard films that are now completely colorless.
Polymere Bindemittelpolymeric binders
Als polymere Bindemittel kommen in den Dispersionen vorzugsweise Umsetzungsprodukte von Di- und Tri-isocyanatverbindungen mit Hydroxylverbindungen in Betracht, die nach dem Aufbringen auf die Oberflächen und Trocknung einen Polyurethanfilm bilden. Dabei können im Sinne der vorliegenden Erfindungen die Isocyanat- und die Hydroxylkomponenten einzeln der Dispersion zugesetzt werden, es ist aber auch möglich, ein Vorkondensat aus beiden Stoffen zu verwenden.Preferred polymeric binders in the dispersions are reaction products of di- and tri-isocyanate compounds with hydroxyl compounds, which form a polyurethane film after application to the surfaces and drying. In accordance with the present invention, the isocyanate and the hydroxyl components can be added individually to the dispersion, but it is also possible to use a precondensate of the two substances.
Während die Isocyanatverbindungen aliphatischen Ursprungs sein können, wie beispielsweise das Hexamethylendiisocyanat,
Als cycloaliphatische Alternative kommt auch Isophorondiisocyanat in Betracht.
Als Hydroxylverbindungen eignen sich insbesondere Polyether, speziell Polyethylen- und Polypropylenglycolether mit Molekulargewichten im Bereich von 150 bis 1.500, die auch einseitig mit Methyl- oder Butylfunktionen endgruppenverschlossen sein können. Besonders geeignet sind PEG300, PEG500, PEG1000, MPEG300, MPEG350, MPEG1000, BPEG300 oder BPEG350. Üblicherweise werden die Isocyanate und die Hydroxylverbindungen im molaren Verhältnis von etwa 1:1 bis etwa 1:5 und insbesondere etwa 1,2 bis etwa 1:3 eingesetzt.Particularly suitable hydroxyl compounds are polyethers, specifically polyethylene and polypropylene glycol ethers with molecular weights in the range from 150 to 1,500, which can also be end-capped with methyl or butyl functions at one end. PEG300, PEG500, PEG1000, MPEG300, MPEG350, MPEG1000, BPEG300 or BPEG350 are particularly suitable. The isocyanates and the hydroxyl compounds are usually used in a molar ratio of from about 1:1 to about 1:5 and in particular from about 1.2 to about 1:3.
Generell sind für diese Erfindung weitere wässrige Dispersionen geeignet, die z. B. auf Basis von (Meth)acrylverbindungen aufgebaut sind. Diese können aus einem oder mehreren (Meth)acrylsäurederivaten und weiteren Vinylderivaten aufgebaut sein, welche radikalisch polymerisieren.In general, other aqueous dispersions are suitable for this invention, z. B. based on (meth) acrylic compounds are constructed. These can be built up from one or more (meth)acrylic acid derivatives and other vinyl derivatives which undergo free-radical polymerization.
Vernetzungsmittelcrosslinking agent
Als radikalisch polymerisierbare Vernetzungsmittel (Komponente b) können alle Verbindungen zum Einsatz kommen, welche entsprechend dem Mechanismus der freien radikalischen Polymerisation polymerisieren und bei einer Funktionalität >2 vernetzen. Hierzu zählen insbesondere Acrylsäure- und/oder Methacrylsäurederivate und daraus ableitbare Ester wie z.B. 1,6-Hexandioldiarylat, Trimethylolpropantriacrylat, Urethandimethacrylat, oder auch Tri(propylenglycol)-diacrylat, wobei auch Mischungen von mehreren vernetzenden Monomeren zum Einsatz kommen können. Die folgenden Monomere M1-M4 bilden einige der weiteren zahlreichen Alternativen ab. Optional können bei Bedarf Additive hinzugesetzt werden, um die Dispergierbarkeit der Monomeren/des Monomeren in der wässrigen Dispersion zu verbessern.
NIR-AbsorberNIR absorber
Als NIR-Absorber (Komponente c) werden vorzugsweise Polymethine („Polymethine dyes“ Physical Sciences Reviews 2019, 5, 20190084) eingesetzt, welche idealerweise aus der Klasse der Cyanine („Cyanine dyes“ Physical Sciences Reviews 2020, 20190145) mit Heptamethin Struktur ausgewählt. Diese absorbieren idealerweise in einem Spektralbereich von 700-1500 nm. Die Verbindungen A1-A16 bilden nur einige der vielen möglichen Stukturen ab. Generell sind weitere Strukturen möglich, die u. a. in „Photophysics and photochemistry of NIR absorbers derived from cyanines: key to new technologies based on chemistry 4.0“ Beilstein J Org Chem 2020, 16, 415; „Photochemistry with Cyanines in the Near Infrared: A Step to Chemistry 4.0 Technologies“ Chemistry - A European Journal 2019, 25, 12855; „NIR-Dyes for Photopolymers and Laser Drying in the Graphic Industry, in Dyes and Chromophores in Polymer Science“, John Wiley & Sons, Inc., 2015, pp. 213-249; Verfahren zur Herstellung von Cyaninfarbstoffen, 1995, Bayer A.-G., Germany, DE4331162A1; „Cyanines during the 1990s: A Review“ Chemical Reviews 2000, 100, 1973; F. E. Hamer, The Cyanine Dyes and Related Compounds; Interscience Publishers, John Wiley & Sons: New York, 1964; „Near-infrared absorbing dyes“ Chemical Reviews 1992, 92, 1197 oder auch „Syntheses and Properties of Cyanine and Related Dyes. In Chemistry of Heterocyclic Compounds“; Taylor, E. C., Ed.; John Wiley & Sons, 1977; Vol. 30, pp 441 abgebildet sind. Weitere Strukturelemente sind in den Katalogen von FEW Chemicals GmbH (www.few.de), Spectrum Info, Ltd. (www.spec-info.com) und HAYASHIBARA Co, Ltd. (www.hayashibara.co.jp) abgebildet.
UV-VIS-PhotoinitiatorenUV-VIS photoinitiators
Als Photoinitiatoren (Komponente d) werden bevorzugt solche eingesetzt, welche nach Norrish Type I Spaltung mit einer UV/VIS LED initiierende Radikale für eine freie radikalischen Polymerisation bilden. Generell ist der Einsatz weiterer Photoinitiatoren möglich, welche u.a. in „Photoinitiators for Polymer Synthesis“, Wiley-VCH, Weinheim, 2012 oder auch „Industrial Photoinitiators: A Technical Guide“, CRC Press, Boca Raton, 2010 abgebildet sind. Grundsätzlich kommen daher alle Stoffe in Betracht, die radikalbildend sind und Licht im Bereich von 350 bis 450 nm absorbieren. Stellvertretend hierfür sind die Strukturen PI1 bis PI3 genannt.
Generell sind auch Typ II Initiatoren geeignet, welche u.a. Derivate des Thioxanthons als lichtabsorbierende Komponente und einen Coinitiator enthalten. Der Einsatz von Campherchinon ist auch möglich. Mögliche Coinitiatoren sind Oniumsalze wie z.B. Iodonium- oder Sulfoniumsalze, oder auch Amine wie DABCO oder Dimethylamino(ethylbenzoat).In general, type II initiators are also suitable, which contain, among other things, derivatives of thioxanthone as a light-absorbing component and a coinitiator. Camphorquinone can also be used. Possible co-initiators are onium salts such as iodonium or sulfonium salts, or amines such as DABCO or dimethylamino(ethyl benzoate).
Lackdispersionenpaint dispersions
Die erfindungsgemäßen Lackdispersionen enthalten zwingend ein polymeres Bindemittel (entweder eine Mischung aus Isocyanat- und Hydroxylverbindung oder ein daraus hergestelltes Präkondensat) sowie ein Vernetzungsmittel. Für den ersten Schritt der photonischen Trocknung muss ferner ein NIR-Absorber und für die Härtung ein UV-Photoinitiator vorhanden sein. Ferner können die Dispersionen noch Radikalstarter wie beispielsweise Hydrazin, Lösungsmittel, nämlich Wasser, und pH-Regulatoren enthalten. Eine typische Dispersion gemäß vorliegender Erfindung weist die folgende Zusammensetzung (alle Angaben als Gew.-%) auf:
Die Lackdispersion kann auch in Etappen hergestellt werden, beispielsweise indem man eine wässrige Prädispersion aus Bindemittel und Radikalstarter herstellt, den pH-Wert justiert und erst dann die weiteren Bestandteile, also Vernetzungsmittel, Absorber und Photoinitiator zusetzt.The coating dispersion can also be produced in stages, for example by preparing an aqueous predispersion from binder and free-radical initiator, adjusting the pH and only then adding the other components, i.e. crosslinking agent, absorber and photoinitiator.
Die photonische Trocknung kann vorzugsweise mit Halbleiterlichtquellen wie LED oder Laser erfolgen, sofern diese die erforderliche Emission im Bereich von 700 bis 1.200 nm besitzen. Besonders bevorzugt sind großflächige LEDs mit Emissionen bei 800 bis 870 nm, 920 bis 950 nm und 950 bis 1.050 nm. Es ist grundsätzlich möglich, photonische und physikalische Trocknung miteinander zu kombinieren. Die physikalische Trocknung erfolgt mit einer NIR Lichtquelle, wobei die Generierung von Wärme, die zur physikalischen Trocknung des Beschichtungsstoffs benötigt wird, an einen photonischen Prozess gekoppelt ist. Nach erfolgter Lichtabsorption erfolgt eine Kopplung der unteren Schwingungsmoden des angeregten Zustands mit höheren Schwingungsmoden des Grundzustandes. Die Effizienz dieses Prozesses ist >75% und wird in der Fachwelt als interne Konversion bezeichnet. Die Abgabe überschüssiger Energie aus höheren Moden des Grundzustandes erfolgt durch Stöße mit Matrixmolekülen.Photonic drying can preferably be carried out using semiconductor light sources such as LEDs or lasers, provided these have the required emission in the range from 700 to 1,200 nm. Large-area LEDs with emissions at 800 to 870 nm, 920 to 950 nm and 950 to 1050 nm are particularly preferred. In principle, it is possible to combine photonic and physical drying with one another. The physical drying takes place with an NIR light source, whereby the generation of heat, which is required for the physical drying of the coating material, is coupled to a photonic process. After light absorption has taken place, the lower vibrational modes of the excited state are coupled with higher vibrational modes of the ground state. The efficiency of this process is >75% and is referred to in the professional world as internal conversion. The release of excess energy from higher modes of the ground state occurs through collisions with matrix molecules.
Als UV-VIS Lichtquellen sind konventionelle Quecksilbermitteldruckstrahler oder ebenfalls Halbleiterlichtquellen wie LEDs einsetzbar, sofern eine Emission im Bereich von 350 bis 450 nm vorliegt. Auch hier sind großflächige LEDs bevorzugt, die bei 350-370 nm, 380 bis 395 nm, 400 bis 420 nm und 440 bis 470 nm emittieren.Conventional medium-pressure mercury lamps or semiconductor light sources such as LEDs can be used as UV-VIS light sources, provided there is an emission in the range from 350 to 450 nm. Here, too, large-area LEDs are preferred which emit at 350-370 nm, 380-395 nm, 400-420 nm and 440-470 nm.
GEWERBLICHE ANWENDBARKEITCOMMERCIAL APPLICABILITY
Ein weiterer Gegenstand der Erfindung betrifft die Verwendung von wässrigen Dispersionen enthaltend
- (a) wenigstens ein polymeres Bindemittel,
- (b) wenigstens ein radikalisch polymerisierbares Vernetzungsmittel
- (c) wenigstens einen NIR-Absorber, und
- (d) wenigstens einen radikalbildenden UV-VIS-Photoinitiator
- (a) at least one polymeric binder,
- (b) at least one free radically polymerizable crosslinking agent
- (c) at least one NIR absorber, and
- (d) at least one radical-forming UV-VIS photoinitiator
Der guten Ordnung halber sei darauf hingewiesen, dass im Sinne der vorliegenden Erfindung alle vorstehend genannten bevorzugten Ausführungsformen, Stoffe, Stoffmischungen, Reaktionsbedingungen und dergleichen auch im Zusammenhang mit der beanspruchten Verwendung mitgelten, ohne dass es dazu einer Wiederholung bedarf.For the sake of good order, it should be pointed out that, within the meaning of the present invention, all the above-mentioned preferred embodiments, substances, substance mixtures, reaction conditions and the like also apply in connection with the claimed use, without there being a need to repeat them.
BEISPIELEEXAMPLES
Beispiel 1example 1
Herstellung der Dispersion 1Preparation of the
Die verwendete Polyurethan-Dispersion wurde nach folgender Rezeptur erstellt. Tabelle 1 Zusammensetzung PU Dispersion
Der Polyether (Voranol 1010L) wurde von Dow-Chemicals unverändert eingesetzt. Weiteren Chemikalien, die zur Synthese verwendeten wurden waren: Dimethylolpropionsäure (2,2-Bis(hydroxymethyl)propionsäure), Isophorondiisocyanat, Triethylamin und Hydrazinhydrat. Die Verbindungen aus den Positionen 1-3 in o.g. Tabelle wurden im Reaktionskolben vorgelegt und unter Rühren langsam auf 90°C aufgeheizt. Nach ca. 60 min. wurde der IsocyanatGehalt bestimmt. Sobald dieser unter 8,9 % war, wurde auf 60 °C abgekühlt. Die Verbindung in Position 4 vorsichtig zugetropft und die Heizung von der Reaktionslösung entfernt. Unter kräftigem Rühren wurde dann das Wasser (Position 5) zügig zugetropft, sodass eine Emulsion ohne Phasentrennung entsteht. Anschließend wurde auf Raumtemperatur abgekühlt. Zuletzt wurde Hydrazinhydrat (Position 6) innerhalb von ca. 10 min. zugetropft und die Dispersion mindestens eine Stunde weiter gerührt. Anschließend ist die milchig trübe Dispersion durch ein 260 µm Schnellsieb filtriert worden. Die erhaltene Dispersion hat einen pH-Wert von ungefähr 7 bis 8. Diese Dispersion hatte einen nichtflüchtigen Anteil 38,5% (Bestimmung nach DIN EN ISO 3251:2019). Die Glasübergangtemperatur des isolierten Polymeren betrug im 2. Heizlauf der DSC -32°C. Die mittlere Partikelgröße war 260 nm.The polyether (Voranol 1010L) was used unchanged by Dow Chemicals. Other chemicals used in the synthesis were: dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid), isophorone diisocyanate, triethylamine, and hydrazine hydrate. The compounds from items 1-3 in the above table were placed in the reaction flask and slowly heated to 90° C. while stirring. The isocyanate content was determined after about 60 minutes. As soon as this was below 8.9%, it was cooled to 60.degree. The compound in
Beispiel 2example 2
Verfilmung der Dispersion mit einer NIR Quelle im 1. Schritt und Generierung eines klaren, farblosen und vernetzten Films im 2. Schritt mit einer UV-VIS QuelleFilm formation of the dispersion with an NIR source in the 1st step and generation of a clear, colorless and crosslinked film in the 2nd step with a UV-VIS source
In einer bestehend aus der in Tabelle 1 dargestellten wässrigen Dispersion, welche Monomer (M) und Photoinitiator (PI) enthielt, wurden 1mg Absorber auf ein 1g einer wässrigen Dispersion von Methylacrylat hinzugegeben. Dabei wurde die Konzentration an Acrylat so gewählt, dass im getrockneten Zustand ein Massenverhältnis von polymerem Bindemittel zu Acrylat von ca. 1:1 vorlag. Die Konzentration an Photoinitiator betrug 2 Gew.-% bezogen auf die Mischung. Die so erhaltene Lösung wurde mit einer Nassfilmdicke von 80 µm auf einer Fläche von 2,6 × 1,2 cm aufgetragen, was einer Fläche von 3,12 cm2 entsprach. Der Auftrag erfolgte mit einer Rakel auf dem Substrat. Die so erhaltene Beschichtung wurde dann mit einer NIR Quelle, welche zweckmäßigerweise eine NIR LED mit Emission bei 805 nm oder 860 nm oder NIR Laser mit Linienfokus mit einer Emission bei 980 nm (Länge der Laserlinie: 2 cm, Breite der Laserlinie: 1 mm) belichtet. Dabei verfilmte die applizierte Lösung, welche anschließend mit einer UV-LED belichtet wurde. Dabei verlor die mit einer NIR Quelle verfilmte farbige Beschichtung die Farbe und war nach UV-Belichtung farblos und vernetzt. Die Glasübergangstemperatur war bei diesen semi-interpenetrierenden Netzwerken angestiegen, was auf eine Reaktion des Monomeren hindeutet. Diese Filme wurden mit dynamisch-mechanischer Analyse charakterisiert. Die Ergebnisse sind in Tabelle 2 zusammengefasst. Die auf diese Weise applizierten Beschichtungen waren nach dem zweiten Belichtungsschritt nicht klebrig und zeigten ein klares, farbloses Erscheinungsbild. Nach FTIR Untersuchungen waren die gehärteten Filme praktisch wasserfrei.1 mg of absorber per 1 g of an aqueous dispersion of methyl acrylate was added to an aqueous dispersion shown in Table 1, which contained monomer (M) and photoinitiator (PI). The concentration of acrylate was chosen so that in the dried state there was a mass ratio of polymeric binder to acrylate of approximately 1:1. The concentration of photoinitiator was 2% by weight, based on the mixture. The solution obtained in this way was applied with a wet film thickness of 80 μm to an area of 2.6×1.2 cm, which corresponded to an area of 3.12 cm 2 . The application was carried out with a doctor blade on the substrate. The coating obtained in this way was then treated with an NIR source, which is suitably an NIR LED with emission at 805 nm or 860 nm or NIR laser with line focus with emission at 980 nm (length of the laser line: 2 cm, width of the laser line: 1 mm). exposed. The applied solution filmed and was then exposed to a UV LED. The colored coating filmed with an NIR source lost its color and was colorless and crosslinked after UV exposure. The glass transition temperature had increased in these semi-interpenetrating networks, indicating indicates a reaction of the monomer. These films were characterized using dynamic mechanical analysis. The results are summarized in Table 2. The coatings applied in this way were not tacky after the second exposure step and had a clear, colorless appearance. According to FTIR investigations, the cured films were practically free of water.
Charakteristische Daten der NIR LEDs
- • Intensität: 1 W/cm2
- • Belichtungsfläche: 9 cm × 1,5 cm
- • Bestrahlungszeit: 5 min
- • Wellenlänge in
Tabelle 2
- • Intensity: 1W/ cm2
- • Exposure area: 9 cm × 1.5 cm
- • Irradiation time: 5 min
- • Wavelength in Table 2
Charakteristische Daten der UV-VIS-LEDs
- • Intensität: 1,2 W/cm2
- • Belichtungsfläche: 3 cm × 10 cm
- • Bestrahlungszeit: 2 min
- • Wellenlänge in
Tabelle 2
- • Intensity: 1.2 W/ cm2
- • Exposure area: 3 cm × 10 cm
- • Irradiation time: 2 min
- • Wavelength in Table 2
Charakteristische Daten des NIR Lasers
- • Intensität: 200 W/cm2
- • Typ: Diodenlaser mit Linienfokus
- • Breite der Laserline: 2 cm
- • Linienfokus der Laserlinie: 1 mm
- • Belichtungsfläche: d= 4,5 mm A= 15,9 cm2
- • Prozessgeschwindigkeit bei der Laserbelichtung: 10 cm/min
- • Intensity: 200 W/ cm2
- • Type: Diode laser with line focus
- • Width of the laser line: 2 cm
- • Line focus of the laser line: 1 mm
- • Exposure area: d= 4.5 mm A= 15.9 cm 2
- • Laser exposure process speed: 10 cm/min
Dabei wurden die in Tabelle 2 dargestellten Ergebnisse erhalten. Die Beispiele V1 und V2 dienen zur Kontrolle, die Beispiele 1 bis 29 sind erfindungsgemäß.The results shown in Table 2 were obtained. Examples C1 and C2 serve as controls, examples 1 to 29 are according to the invention.
Die
ZITATE ENTHALTEN IN DER BESCHREIBUNGQUOTES INCLUDED IN DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
Zitierte PatentliteraturPatent Literature Cited
- DE 102012205807 A1 [0005]DE 102012205807 A1 [0005]
- WO 2012063964 A1 [0006]WO 2012063964 A1 [0006]
- WO 2014078140 A1 [0007]WO 2014078140 A1 [0007]
- US 6140384 A [0008]US6140384A [0008]
- JP 2002189291 A1 [0009]JP 2002189291 A1 [0009]
- JP 2014172333 A [0010]JP 2014172333 A [0010]
- US 10767064 B2 [0011]US 10767064 B2 [0011]
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