EP1235652A2 - Light curing of radiation curable materials under a protective gas - Google Patents

Light curing of radiation curable materials under a protective gas

Info

Publication number
EP1235652A2
EP1235652A2 EP00981286A EP00981286A EP1235652A2 EP 1235652 A2 EP1235652 A2 EP 1235652A2 EP 00981286 A EP00981286 A EP 00981286A EP 00981286 A EP00981286 A EP 00981286A EP 1235652 A2 EP1235652 A2 EP 1235652A2
Authority
EP
European Patent Office
Prior art keywords
radiation
protective gas
curable
weight
curing
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
EP00981286A
Other languages
German (de)
French (fr)
Other versions
EP1235652B1 (en
Inventor
Erich Beck
Oliver Deis
Peter Enenkel
Wolfgang Schrof
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09151021A priority Critical patent/EP2047916A3/en
Publication of EP1235652A2 publication Critical patent/EP1235652A2/en
Application granted granted Critical
Publication of EP1235652B1 publication Critical patent/EP1235652B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B3/00—Drying solid materials or objects by processes involving the application of heat
    • F26B3/28—Drying solid materials or objects by processes involving the application of heat by radiation, e.g. from the sun
    • F26B3/283—Drying solid materials or objects by processes involving the application of heat by radiation, e.g. from the sun in combination with convection
    • 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
    • B05D3/04—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 gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F26B21/14—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects using gases or vapours other than air or steam, e.g. inert gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B2210/00—Drying processes and machines for solid objects characterised by the specific requirements of the drying good
    • F26B2210/12—Vehicle bodies, e.g. after being painted

Definitions

  • the invention relates to a process for the production of molding compositions and coatings on substrates by curing radiation-curable compositions under protective gas by irradiation with light, characterized in that the protective gas is a gas which is heavier than air and the protective gas flows away during the process radiation curing is prevented by a suitable device or measures.
  • This oxygen inhibition effect can be achieved by using large amounts of photoinitiators, by using coinitiators, e.g. B. amines, high-dose UV radiation, e.g. with high-pressure mercury lamps or by adding barrier-forming waxes.
  • coinitiators e.g. B. amines
  • high-dose UV radiation e.g. with high-pressure mercury lamps
  • barrier-forming waxes e.g.
  • Radiation-curable compositions can be processed without water or organic solvents. Therefore, the process of radiation curing is suitable for paintwork that is carried out in medium or small craft businesses or in the home. So far, however, the complex implementation of the method and the devices required for this, in particular the UV lamps, have prevented the use of radiation curing in these areas.
  • the object of the invention was therefore a simple method of radiation curing which can also be used in small craft businesses or in the home and is generally suitable for curing three-dimensionally coated objects.
  • coatings on planar surfaces can be hardened on several sides or on all sides (three-dimensional hardening method).
  • a protective gas that is heavier than air is used in the process.
  • the molecular weight of the gas is therefore greater than 28.8 g / mol (corresponds to the molecular weight of a gas mixture of 20% oxygen and 80% nitrogen), preferably greater than 32, in particular greater than 35 g / mol.
  • Noble gases such as argon, hydrocarbons and halogenated hydrocarbons. Carbon dioxide is particularly preferred.
  • the supply of carbon dioxide can be obtained from pressure vessels, filtered combustion gases e.g. of natural gas or as dry ice.
  • the supply with dry ice is seen as advantageous, in particular for applications in the non-industrial or in the small industrial area. Because dry ice can be transported and stored as a solid in simple containers insulated with foam. The dry ice can be used as such, it is then gaseous at the usual use temperatures.
  • the protective gas is heavier than air, so air is displaced upwards. The lateral escape of the gas must be prevented.
  • One possibility is to use a container as a diving pool. This process is particularly suitable for the three-dimensional coating process.
  • the protective gas is filled into the container and the air is displaced from it.
  • the container now contains a protective gas atmosphere in which the substrate, which is coated with the radiation-curable composition, or the molded body can be immersed. Then can radiation curing is carried out, for example by sunlight or by means of suitable lamps.
  • the area to be hardened by te geeigne ⁇ devices, in particular partition walls are deferred, so that the protective gas during the irradiation time can not escape.
  • the method can also be used to coat printable or printed substrates and radiation-cure them.
  • Suitable substrates are e.g. Paper, cardboard, foils or textiles.
  • the radiation-curable coating can be the printing ink or an overprint varnish. Radiation curing can be used directly in the printing process, e.g. done in the printing press. His printing, offset, gravure, portrait, flexo or pad printing processes are mentioned as printing processes.
  • the oxygen content in the protective gas atmosphere is preferably less than 15% by weight, particularly preferably less than 10% by weight, very particularly preferably less than 5% by weight, based on the total amount of gas in the protective gas atmosphere; in particular, the method according to the invention can easily be used to set oxygen contents below 1%, below 0.1% and even below 0.01% by weight.
  • a protective gas atmosphere is understood to mean the gas volume which surrounds the substrate at a distance of up to 10 cm from its surface.
  • dry ice is used as protective gas, e.g. the plunge pools, which may also be storage containers for dry ice, can be easily loaded. Monitoring of carbon dioxide consumption must be determined directly from the consumption of dry ice solids. Dry ice evaporates directly to gaseous carbon dioxide at -78.5 ° C. In a pool, this causes air oxygen with little swirl to be displaced upwards out of the pool.
  • the residual oxygen can be determined using commercially available atmospheric oxygen measuring devices.
  • the basin can be covered to minimize gas losses and possibly also against heating during non-operating times. Appropriate safety measures should be taken due to the oxygen-reduced atmosphere in the immersion and storage basin and the associated choking hazard. Adequate ventilation and carbon dioxide drainage should also be ensured in adjacent work areas.
  • the painted objects can be lowered into the plunge pool for exposure individually using lifting and lowering devices or using assembly line-like devices in the case of series painting.
  • a slow lowering or lifting or the use of pre- and Nachflutern is suitable.
  • the upstream and downstream flooders are an extension of the inert gas basin to separate air turbulence zones from the radiation zone.
  • the inert gas basin can be expanded from the exposure zone both in height and in width on both sides.
  • the dimensions of the receiving water are primarily dependent on the speed of immersion and immersion and the geometry of the object.
  • the duration of the irradiation depends on the desired degree of hardening of the coating or of the shaped body.
  • the degree of hardening can be determined from the detackification or the scratch resistance, e.g. against the fingernail or against other objects such as pencil, metal or plastic tips.
  • resistance tests against chemicals e.g. Suitable solvents, inks, etc.
  • Spectroscopic methods, in particular Raman and infrared spectroscopy, or measurements of the dielectric or acoustic properties, etc. are particularly suitable without damaging the paint surfaces.
  • Radiation curing can be carried out by sunlight or by lamps, which are preferably installed in the immersion pool in such a way that the desired multi-sided or all-round curing of the coated substrates takes place.
  • the radiation-curable composition contains radiation-curable compounds as binders. These are compounds with free-radically or cationically polymerizable and therefore radiation-curable ethylenically unsaturated groups.
  • the radiation-curable composition 0.001 to 12, particularly preferably 0.1 to 8 and very particularly preferably 0.5 to 7 mol, radiation-curable ethylenically unsaturated groups per 1000 g of radiation-curable compounds.
  • (meth) acrylate compounds such as polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acylates, silicone (meth) acrylates, acrylated polyacrylates.
  • At least 40 mol%, particularly preferably at least 60 mol%, of the radiation-curable ethylenically unsaturated groups are (meth) acrylic groups.
  • the radiation curable compounds can contain other reactive groups, e.g. Melamine, isocyanate, epoxy, anhydride, alcohol, carboxylic acid groups for additional thermal curing, e.g. B. by chemical reaction of alcohol, carboxylic acid, amine, epoxy, anhydride, isocyanate or melamine groups, contain (dual your).
  • other reactive groups e.g. Melamine, isocyanate, epoxy, anhydride, alcohol, carboxylic acid groups for additional thermal curing, e.g. B. by chemical reaction of alcohol, carboxylic acid, amine, epoxy, anhydride, isocyanate or melamine groups, contain (dual your).
  • the radiation curable compounds can e.g. as a solution, e.g. in an organic solvent or water, as an aqueous dispersion, as a powder.
  • the radiation-curable compounds and thus also the radiation-curable compositions are preferably flowable at room temperature.
  • the radiation-curable compositions preferably contain less than 20% by weight, in particular less than 10% by weight, of organic solvents and / or water. They are preferably solvent-free and anhydrous (100% solids).
  • the radiation-curable compositions can contain further constituents as binders.
  • binders For example, Pigments, leveling agents, dyes, stabilizers etc.
  • Photoinitiators are generally used for curing with UV light.
  • suitable photoinitiators are benzophenone, alkylbenzophenones, halogen-methylated benzophenones, Michler's ketone, anthrone and halogenated benzophenones.
  • Benzoin and its derivatives are also suitable.
  • effective photoinitiators are anthraquinone and many of its derivatives, for example ⁇ -methylanthraquinone, tert.
  • acylphosphine oxide group such as acylphosphine oxides or bisacylphosphine oxides, for example 2,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO).
  • Suitable photoinitiators for visible light which contains no UV components, are in particular the above-mentioned photoinitiators with acylphosphino oxide groups.
  • the content of the photoinitiators in the radiation-curable composition can be low or that photoinitiators can be dispensed with entirely.
  • the radiation-curable compositions preferably contain less than 10 parts by weight, in particular less than 4 parts by weight, particularly preferably less than 1.5 parts by weight of photoinitiator per 100 parts by weight of radiation-curable compounds.
  • the radiation-curable composition can be applied to the substrate to be coated by conventional methods or can be shaped accordingly.
  • Radiation curing can take place as soon as the substrate is surrounded by the protective gas.
  • Radiation curing can be carried out with all lamps that have previously been used for radiation curing. Radiation curing can be carried out using electron beams, X-rays or gamma rays, UV radiation or visible light. It is an advantage of the method according to the invention that radiation curing can be carried out with visible light which contains only little or no (wavelengths below 300 nm). The radiation curing in the method according to the invention can therefore be carried out with sunlight or with lamps which serve as a substitute for sunlight. These lamps radiate in the visible range above 400 nm and have no or hardly any UV light components below 5300 nm).
  • the proportion of radiation in the wavelength range below 300 nm is less than 20%, preferably less than 10%, particularly preferably less than 0%, in particular less than 1 or 0.5% or less than 0.1% of the integral of the emitted intensity over the entire wavelength range below 1000 nm.
  • the above radiation is the 5 radiation actually available for curing, that is, when filters are used, the radiation after filter passage.
  • Lamps that have a line spectrum come into consideration, that is to say emit only at certain wavelengths, e.g. B. LEDs 0 or lasers.
  • Lamps with a broadband spectrum that is to say a distribution of the emitted light over a wavelength range, are also suitable.
  • the intensity maximum is preferably in the visible range above 400 nm.
  • Incandescent lamps for example, Incandescent lamps, halogen lamps, xenon lamps.
  • Mercury vapor lamps with filters to avoid or reduce radiation below 300 nm may also be mentioned.
  • Pulsed lamps are also suitable, e.g. Photo flash lamps or high-performance flash lamps (from VISIT).
  • a particular advantage of the process is the ability to use lamps with low energy requirements and a low UV component, e.g. of 500 watt halogen lamps as used for general lighting purposes. This means that there is no need for a high-voltage unit for the power supply (for mercury vapor lamps) and, if necessary, for light protection measures, and halogen lamps also pose no risk in air due to ozone development, such as 0 with short-wave UV lamps. This makes radiation hardening easier with portable radiation devices and applications "on site", ie independent of fixed industrial hardening systems, are possible.
  • lamps in particular including lamp housings with reflectors, may be required.
  • existing cooling devices, radiation filters and power source connection suitable which have a low weight, for example less than 20 kg, preferably less than 8 kg.
  • Particularly light lamps are e.g. Halogen lamps, incandescent lamps, light-emitting diodes, portable lasers, photo flash lamps etc. These lamps are also characterized by their particularly easy installation in container interiors or container walls. Likewise, the technical effort for power supply is reduced, especially in comparison to mercury vapor lamps in the medium and high pressure range that have been customary in the industry to date.
  • the preferred current sources for the lamps are household AC, e.g. 220 V / 50 Hz or the supply of portable generators, batteries, accumulators, solar cells, etc.
  • the method according to the invention is suitable for the production of coatings on substrates and for the production of moldings.
  • Suitable substrates include z. B. those made of wood, plastics, metal, mineral or ceramic materials.
  • the z. B. contain radiation-curable mass impregnated fiber materials or fabrics, or moldings for stereolithography.
  • Another advantage of the method is that the distances between lamps and radiation-curable mass can be increased compared to curing in air. Overall, lower radiation doses can be used and a radiator unit can be used to harden larger areas.
  • the process enables new applications in the field of curing coatings and molding compounds of complicated three-dimensionally shaped objects, e.g. Furniture, vehicle bodies, housing and equipment construction, for mobile applications such as floor and hall floor painting. Because of the low technical and material expenditure, the process is also suitable for medium and small craft businesses, the home work and do it your soap area.
  • example 1 A radiation-curable composition was produced by mixing the following components.
  • Laromer® LR 8987 (BASF Aktiengesellschaft), a urethane acrylate
  • Laromer® LR 8863 38.5% by weight Laromer® LR 8863, a polyether acrylate 3.5% by weight Iragucure® 184 (Ciba Specialty Chemicals), a photoinitiator 0.5% by weight Lucirin® TPO (BASF) a photoinitiator
  • Tinuvin®400 Ciba Specialty Chemicals
  • UV absorber 1.5% by weight of Tinuvin® 292
  • UV absorber 1.5% by weight of Tinuvin® 292
  • a glass pane was coated with this material (layer thickness 50 ⁇ m).
  • the glass pane is placed on the 45 cm level and irradiated for 2 min with a 500 watt halogen lamp at a distance of 50 cm from the halogen lamp.
  • the paint is highly scratch-resistant and cannot be scratched with a wooden spatula and white typewriter paper under manual pressure and rubbing.
  • the radiation-curable composition corresponded to Example 1.
  • the radiation-curable composition was applied as a clear lacquer to the housing of an exterior car mirror and cured according to the invention as described in Example 1.
  • the paint obtained was highly scratch-resistant.

Abstract

Production of a molded article and coating a substrate comprises curing by radiation with light whilst using a protective gas that is heavier than air.

Description

Lichthärtung von s rahlungshärtbaren Massen unter SchutzgasLight curing of radiation-curable materials under protective gas
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von Formmassen und Beschichtungen auf Substraten durch Härtung von strahlungshärtbaren Massen unter Schutzgas durch Bestrahlen mit Licht dadurch gekennzeichnet, daß es sich bei dem Schutzgas um ein Gas handelt, das schwerer ist als Luft und das seitliche Wegfließen des Schutzgases während der Strahlungshärtung durch eine geeignete Vorrichtung oder Maßnahmen verhindert wird.The invention relates to a process for the production of molding compositions and coatings on substrates by curing radiation-curable compositions under protective gas by irradiation with light, characterized in that the protective gas is a gas which is heavier than air and the protective gas flows away during the process radiation curing is prevented by a suitable device or measures.
Bei der Strahlungshärtung von radikalisch polymerisierbaren Verbindungen, z.B. von (Meth) acrylatverbindungen kann eine starke Inhibierung der Polymerisation bzw. Härtung durch Sauerstoff, auftreten. Diese Inhibierung führt zu einer unvollständigen Härtung an der Oberfläche und so z.B. zu klebrigen Beschichtungen.In the radiation curing of radically polymerizable compounds, e.g. A strong inhibition of the polymerization or curing by oxygen can occur with (meth) acrylate compounds. This inhibition leads to incomplete hardening on the surface and e.g. to sticky coatings.
Dieser Sauerstoffinhibierungseffekt kann durch den Einsatz hoher Fotoinitiatormengen, durch Mitverwendung von Coinitiatoren, z. B. Aminen, energiereicher UV-Strahlung hoher Dosis, z.B. mit Quecksilberhochdrucklampen oder durch Zusatz von barrierebildenden Wachsen vermindert werden.This oxygen inhibition effect can be achieved by using large amounts of photoinitiators, by using coinitiators, e.g. B. amines, high-dose UV radiation, e.g. with high-pressure mercury lamps or by adding barrier-forming waxes.
Bekannt ist auch die Durchführung der Strahlungshärtung unter einem inerten Schutzgas, z.B. aus EP -A- 540884, aus Joachim Jung, RadTech Europe 99, Berlin 08. bis 10.11.1999 in Berlin (UV-Ap- plications in Europe Yesterday-Today Tomorrow) .It is also known to carry out radiation curing under an inert protective gas, e.g. from EP -A- 540884, from Joachim Jung, RadTech Europe 99, Berlin, November 8-10, 1999 in Berlin (UV-Applications in Europe Yesterday-Today Tomorrow).
Gewünscht ist ein Verfahren der Strahlungshärtung bei dem auf energiereiche UV- ichtquellen und die damit verbundenen, notwendigen Sicherheitsmaßnahmen verzichtet werden kann. Gleichzeitig soll das Verfahren aber möglichst einfach durchzuführen sein.What is desired is a method of radiation curing in which high-energy UV light sources and the necessary safety measures associated therewith can be dispensed with. At the same time, the process should be as simple as possible.
Strahlungshärtbare Massen können ohne Wasser oder organische Lösungsmittel verarbeitet werden. Daher eignet sich das Verfahren der Strahlungshärtung für Lackierungen welche in mittleren oder kleinen Handwerksbetrieben oder im häuslichen Bereich durch- geführt werden. Bisher hat aber die aufwendige Durchführung des Verfahrens und die dazu benötigten Vorrichtungen, insbesondere die UV-Lampen, eine Anwendung der Strahlungshärtung in diesen Bereichen verhindert. Aufgabe der Erfindung war daher ein einfaches Verfahren der Strahlungshärtung, welches auch in kleinen Handwerksbetrieben oder im häuslichen Bereich anwendbar ist und generell geeignet ist, dreidimensional beschichtete Gegenstände auszuhärten.Radiation-curable compositions can be processed without water or organic solvents. Therefore, the process of radiation curing is suitable for paintwork that is carried out in medium or small craft businesses or in the home. So far, however, the complex implementation of the method and the devices required for this, in particular the UV lamps, have prevented the use of radiation curing in these areas. The object of the invention was therefore a simple method of radiation curing which can also be used in small craft businesses or in the home and is generally suitable for curing three-dimensionally coated objects.
Die Aufgabe wurde gelöst durch das eingangs definierte Verfahren.The task was solved by the method defined at the beginning.
Durch das erfindungsgemäße Verfahren können Beschichtungen auf planaren Flächen (zweidimensionales Härtungsverfahren) oder auch Beschichtungen auf dreidimensionale Formkörpern mehrseitig oder allseitig gehärtet werden (dreidimensionales Härtungsverfahren) ) .With the method according to the invention, coatings on planar surfaces (two-dimensional hardening method) or also coatings on three-dimensional shaped bodies can be hardened on several sides or on all sides (three-dimensional hardening method).
Bei dem Verfahren wird ein Schutzgas verwendet, welches schwerer ist als Luft. Das Molgewicht des Gases ist daher größer als 28,8 g/mol (entspricht dem Molgewicht eines Gasgemisches von 20 % Sauerstoff und 80 % Stickstoff), vorzugsweise größer 32, insbesondere größer 35 g/mol. In Betracht kommen z.B. Edelgase wie Argon, Kohlenwasserstoffe und halogenierte Kohlenwasserstoffe. Besonders bevorzugt ist Kohlendioxid.A protective gas that is heavier than air is used in the process. The molecular weight of the gas is therefore greater than 28.8 g / mol (corresponds to the molecular weight of a gas mixture of 20% oxygen and 80% nitrogen), preferably greater than 32, in particular greater than 35 g / mol. For example, Noble gases such as argon, hydrocarbons and halogenated hydrocarbons. Carbon dioxide is particularly preferred.
Die Versorgung mit Kohlendioxid kann aus Druckbehältern, gefilterten Verbrennungsgasen z.B. von Erdgas oder als Trockeneis erfolgen. Als vorteilhaft, insbesondere für Anwendungen im nicht industriellen oder im kleinindustriellen Bereich wird die Versor- gung mit Trockeneis gesehen. Da Trockeneis als Feststoff in einfachen mit Schaumstoffen isolierten Behältern transportiert und gelagert werden kann. Das Trockeneis kann als solches verwendet werden, bei den üblichen Verwendungstemperaturen liegt es dann gasförmig vor.The supply of carbon dioxide can be obtained from pressure vessels, filtered combustion gases e.g. of natural gas or as dry ice. The supply with dry ice is seen as advantageous, in particular for applications in the non-industrial or in the small industrial area. Because dry ice can be transported and stored as a solid in simple containers insulated with foam. The dry ice can be used as such, it is then gaseous at the usual use temperatures.
Das Schutzgas ist schwerer als Luft, Luft wird daher nach oben verdrängt. Verhindert werden muß das seitliche Entweichen des Gases .The protective gas is heavier than air, so air is displaced upwards. The lateral escape of the gas must be prevented.
Dazu können unterschiedlichste Vorrichtungen oder Maßnahmen geeignet sein.Various devices or measures can be suitable for this.
Eine Möglichkeit ist die Verwendung eines Behälters als Tauchbek- ken. Dieses Verfahren ist insbesondere geeignet für das dreidi- mensionale Beschichtungsverf hren.One possibility is to use a container as a diving pool. This process is particularly suitable for the three-dimensional coating process.
Das Schutzgas wird in den Behälter eingefüllt und die Luft daraus verdrängt .The protective gas is filled into the container and the air is displaced from it.
Der Behälter enthält nun eine Schutzgasatmosphäre in die das Substrat, welches mit der strahlungshärtbaren Masse beschichtet ist, oder der Formkörper eingetaucht werden kann. Anschließend kann die Strahlungshärtung erfolgen, z.B. durch Sonnenlicht oder durch in geeigneter Weise angebrachte Lampen.The container now contains a protective gas atmosphere in which the substrate, which is coated with the radiation-curable composition, or the molded body can be immersed. Then can radiation curing is carried out, for example by sunlight or by means of suitable lamps.
Bei der Strahlungshärtung von beschichteten Flächen, insbesondere Bodenflächen, kann die jeweilig zu härtende Fläche durch geeigne¬ te Vorrichtungen, insbesondere Stellwände abgegrenzt werden, so daß das Schutzgas während der Bestrahlungsdauer nicht entweichen kann.In the radiation curing of coated surfaces, in particular floor surfaces, respectively, the area to be hardened by te geeigne ¬ devices, in particular partition walls are deferred, so that the protective gas during the irradiation time can not escape.
Durch das Verfahren können weiterhin bedruckbare oder bedruckte Substrate beschichtet und strahlengehärtet werden. Als Substrate in Betracht kommen z.B. Papier, Karton, Folien oder Textilien. Bei der strahlungshärtbaren Beschichtung kann es sich um die Druckfarbe oder einen Überdrucklack handeln. Die Strahlungshär- tung kann unmittelbar beim Druckverfahren, z.B. in der Druckmaschine erfolgen. Als Druckverfahren genannt seine Offset-, Tief-, Hoch-, Flexo- oder Tampondruckverfahren.The method can also be used to coat printable or printed substrates and radiation-cure them. Suitable substrates are e.g. Paper, cardboard, foils or textiles. The radiation-curable coating can be the printing ink or an overprint varnish. Radiation curing can be used directly in the printing process, e.g. done in the printing press. His printing, offset, gravure, portrait, flexo or pad printing processes are mentioned as printing processes.
Während der Strahlungshärtung beträgt der Sauerstoffgehalt in der Schutzgasatmosphäre vorzugsweise weniger als 15 Gew.-%, besonders bevorzugt weniger als 10 Gew.-%, ganz besonders bevorzugt weniger als 5 Gew.-%, bezogen auf die gesamte Gasmenge in der Schutzgasatmosphäre; insbesondere können mit dem erfindungsgemäßen Verfahren leicht Sauerstoffgehalte unter 1 % auch unter 0,1 % und sogar unter 0,01 Gew. -% eingestellt werden.During radiation curing, the oxygen content in the protective gas atmosphere is preferably less than 15% by weight, particularly preferably less than 10% by weight, very particularly preferably less than 5% by weight, based on the total amount of gas in the protective gas atmosphere; in particular, the method according to the invention can easily be used to set oxygen contents below 1%, below 0.1% and even below 0.01% by weight.
Unter Schutzgasatmosphäre wird dabei das Gasvolumen verstanden, welches das Substrat in einem Abstand von bis zu 10 cm von seiner Oberfläche umgibt.A protective gas atmosphere is understood to mean the gas volume which surrounds the substrate at a distance of up to 10 cm from its surface.
Im Falle der Verwendung von Trockeneis als Schutzgas kann z.B. eine Beschickung der Tauchbecken, die unter Umständen gleichzeitig Lagerbehälter für Trockeneis sind, einfach erfolgen. Die Überwachung des Kohlendioxidverbrauchs ist unmittelbar am Ver- brauch des Trockeneisfeststoffes zu bestimmten. Trockeneis verdampft bei -78,5°C direkt zu gasförmigem Kohlendioxid. In einem Becken wird dadurch verwirbelungsarm Luftsauerstoff nach oben aus dem Becken verdrängt.If dry ice is used as protective gas, e.g. the plunge pools, which may also be storage containers for dry ice, can be easily loaded. Monitoring of carbon dioxide consumption must be determined directly from the consumption of dry ice solids. Dry ice evaporates directly to gaseous carbon dioxide at -78.5 ° C. In a pool, this causes air oxygen with little swirl to be displaced upwards out of the pool.
Der Restsauerstoff kann mit handelsüblichen Luftsauerstoffmeßgeräten bestimmt werden. Das Becken kann zur Minimierung von Gasverlusten und evtl. auch gegen Erwärmung bei Nichtbetriebszeiten abgedeckt werden. Wegen der Sauerstoffreduzierten Atmosphäre im Tauch- und Vorratsbecken und der damit verbundenen Erstickungsge- fahr sollten geeignete Sicherheitsmaßnahmen getroffen werden. Ebenso sollte in angrenzenden Arbeitsbereichen eine ausreichende Belüftung und Kohlendioxidabfluß sichergestellt werden.The residual oxygen can be determined using commercially available atmospheric oxygen measuring devices. The basin can be covered to minimize gas losses and possibly also against heating during non-operating times. Appropriate safety measures should be taken due to the oxygen-reduced atmosphere in the immersion and storage basin and the associated choking hazard. Adequate ventilation and carbon dioxide drainage should also be ensured in adjacent work areas.
Die lackierten Gegenstände können einzeln mit Hebe- und Senkvor- richtungen oder über fließbandähnliche Vorrichtungen bei Serien- lackierungen in das Tauchbecken zur Belichtung abgesenkt werden. Um ein möglichst vollständiges Fluten des Gegenstandes zu gewähr¬ leisten ohne zuviel Luft mit in die Bestrahlungszone zu reißen, ist entweder ein langsames Absenken bzw. Heben oder die Verwendung von Vor- und Nachflutern geeignet. Die Vor- bzw. Nach- fluter sind eine Erweiterung der Inertgasbecken, um Luftwirbe- lungszonen von der Bestrahlungszone zu trennen. Dazu kann das Inertgasbecken von der Belichtungszone ausgehend sowohl in die Höhe als auch beidseitig in die Breite erweitert werden. Die Ausmaße der Vorfluter sind in erster Linie abhängig von Ein- und Aus- tauchgeschwindigkeit und von der Geometrie des Gegenstandes.The painted objects can be lowered into the plunge pool for exposure individually using lifting and lowering devices or using assembly line-like devices in the case of series painting. To perform a complete as possible flooding of the object to be granted ¬ without providing too much air with tearing in the irradiation zone, either a slow lowering or lifting or the use of pre- and Nachflutern is suitable. The upstream and downstream flooders are an extension of the inert gas basin to separate air turbulence zones from the radiation zone. For this purpose, the inert gas basin can be expanded from the exposure zone both in height and in width on both sides. The dimensions of the receiving water are primarily dependent on the speed of immersion and immersion and the geometry of the object.
Die Dauer der Bestrahlung hängt vom gewünschten Härtungsgrad der Beschichtung oder des Formkörpers ab. Der Härtungsgrad läßt sich im einfachsten Fall an der Entklebung oder an der Kratzfestigkeit z.B. gegenüber dem Fingernagel oder gegenüber anderen Gegenständen wie Bleistift-, Metall- oder Kunststoffspitzen bestimmen. Ebenso sind im Lackbereich übliche Beständigkeitsprüfungen gegenüber Chemikalien, z.B. Lösemittel, Tinten etc. geeignet. Ohne Be- Schädigung der Lackflächen sind vor allem spektroskopische Methoden, insbesondere die Raman- und Infrarotspektroskopie, oder Messungen der dielektrischen oder akustischen Eigenschaften usw. geeignet. Die Strahlungshärtung kann durch Sonnenlicht erfolgen oder durch Lampen, welche vorzugsweise im Tauchbecken so ange- bracht sind, dass die gewünschte mehrseitige oder allseitige Härtung der beschichteten Substrate erfolgt.The duration of the irradiation depends on the desired degree of hardening of the coating or of the shaped body. In the simplest case, the degree of hardening can be determined from the detackification or the scratch resistance, e.g. against the fingernail or against other objects such as pencil, metal or plastic tips. Likewise, resistance tests against chemicals, e.g. Suitable solvents, inks, etc. Spectroscopic methods, in particular Raman and infrared spectroscopy, or measurements of the dielectric or acoustic properties, etc., are particularly suitable without damaging the paint surfaces. Radiation curing can be carried out by sunlight or by lamps, which are preferably installed in the immersion pool in such a way that the desired multi-sided or all-round curing of the coated substrates takes place.
Für flächige immobile Substrate z.B. Fußböden oder am Boden fixierte Gegenstände können einfache Eindämmvorrichtungen zur Vermeidung des Abflusses von Kohlendioxid angebracht werden. Beispiele sind das Abdichten des Türbereichs in Räumen z.B. bis zu 40 cm Höhe ab Fußboden z.B. mit verklebten Folien, oder aus aufstellen von Wänden aus Holz, Kunststoff, aufgespannten Folien oder Papierbahnen. Das Kohlendioxidgas kann durch Einfüllen aus Gasflaschen oder als Trockeneis erfolgen. Weiterhin können Behälter mit Trockeneis hängend abgebracht werden, aus denen Kohlendioxid auf das zu härtende Material ausströmen kann.For flat immobile substrates e.g. Floors or objects fixed to the floor can be attached to simple containment devices to prevent the outflow of carbon dioxide. Examples include sealing the door area in rooms e.g. up to 40 cm height from the floor e.g. with glued foils, or from setting up walls made of wood, plastic, stretched foils or paper webs. The carbon dioxide gas can be made from gas cylinders or as dry ice. Furthermore, containers with dry ice can be removed hanging, from which carbon dioxide can flow onto the material to be hardened.
Die strahlungshärtbare Masse enthält strahlungshärtbare Verbindungen als Bindemittel. Dies sind Verbindungen mit radikalisch oder kationisch polymerisierbaren und daher strahlungshärt- baren ethylenisch ungesättigten Gruppen. Vorzugsweise enthält die strahlungshärtbare Masse 0,001 bis 12, besonders bevorzugt 0,1 bis 8 und ganz besonders bevorzugt 0,5 bis 7 Mol, strahlungshärt- bare ethylenisch ungesättigte Gruppen auf 1000 g strahlungshärtbare Verbindungen.The radiation-curable composition contains radiation-curable compounds as binders. These are compounds with free-radically or cationically polymerizable and therefore radiation-curable ethylenically unsaturated groups. Preferably, the radiation-curable composition 0.001 to 12, particularly preferably 0.1 to 8 and very particularly preferably 0.5 to 7 mol, radiation-curable ethylenically unsaturated groups per 1000 g of radiation-curable compounds.
Als strahlungshärtbare Verbindungen kommen z. B. (Meth)acryl- verbindungen, Vinylether, Vinylamide, ungesättigte Polyester z.B. auf Basis von Maleinsäure oder Fumarsäure gegebenenfalls mit Styrol als Reaktivverdünner oder Maleinimid/Vinylether- Systemen in Betracht.As radiation-curable compounds such. B. (meth) acrylic compounds, vinyl ethers, vinyl amides, unsaturated polyesters e.g. based on maleic acid or fumaric acid, if appropriate with styrene as reactive diluent or maleimide / vinyl ether systems.
Bevorzugt sind (Meth) acrylatverbindungen wie Polyester (meth) - acrylate, Polyether (meth) acrylate, Urethan (meth) acrylate, Epoxi (meth) acreylate, Silikon (meth) acrylate, acrylierte Poly- acrylate.Preferred are (meth) acrylate compounds such as polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acylates, silicone (meth) acrylates, acrylated polyacrylates.
Vorzugsweise handelt es sich bei mindestens 40 Mol-% besonders bevorzugt bei mindestens 60 Mol-% der strahlungshärtbaren ethylenisch ungesättigten Gruppen um (Meth) acrylgruppen.Preferably at least 40 mol%, particularly preferably at least 60 mol%, of the radiation-curable ethylenically unsaturated groups are (meth) acrylic groups.
Die strahlungshärtbaren Verbindungen können weitere reaktive Gruppen, z.B. Melamin-, Isocyanat-, Epoxid- , Anhydrid-, Alkohol-, Carbonsäuregruppen für eine zusätzliche thermische Härtung, z. B. durch chemische Reaktion von Alkohol-, Carbonsäure- , Amin-, Epoxid-, Anhydrid-, Isocyanat- oder Melamingruppen, enthalten (dual eure) .The radiation curable compounds can contain other reactive groups, e.g. Melamine, isocyanate, epoxy, anhydride, alcohol, carboxylic acid groups for additional thermal curing, e.g. B. by chemical reaction of alcohol, carboxylic acid, amine, epoxy, anhydride, isocyanate or melamine groups, contain (dual your).
Die strahlungshärtbaren Verbindungen können z.B. als Lösung, z.B. in einem organischen Lösungsmittel oder Wasser, als wäßrige Dis- persion, als Pulver vorliegen.The radiation curable compounds can e.g. as a solution, e.g. in an organic solvent or water, as an aqueous dispersion, as a powder.
Bevorzugt sind die strahlungshärtbaren Verbindungen und somit auch die strahlungshärtbaren Massen bei Raumtemperatur fließ - fähig. Die strahlungshärtbaren Massen enthalten vorzugsweise weniger als 20 Gew. -%, insbesondere weniger als 10 Gew. -% organische Lösemittel und/oder Wasser. Bevorzugt sind sie lösungsmittelfrei und wasserfrei (100 % Feststoff) .The radiation-curable compounds and thus also the radiation-curable compositions are preferably flowable at room temperature. The radiation-curable compositions preferably contain less than 20% by weight, in particular less than 10% by weight, of organic solvents and / or water. They are preferably solvent-free and anhydrous (100% solids).
Die strahlungshärtbaren Massen können neben den strahlungshärt- baren Verbindungen als Bindemittel weitere Bestandteile enthalten. In Betracht kommen z.B. Pigmente, Verlaufsmittel, Farbstoffe, Stabilisatoren etc.In addition to the radiation-curable compounds, the radiation-curable compositions can contain further constituents as binders. For example, Pigments, leveling agents, dyes, stabilizers etc.
Für die Härtung mit UV- icht werden im allgemeinen Photo - initiatoren verwendet. Als Photoinitiatoren in Betracht kommen z.B. Benzophenon, Alkyl- benzophenone, halogenmethylierte Benzophenone, Michlers Keton, Anthron und halogenierte Benzophenone. Ferner eignen sich Benzoin und seine Derivate. Ebenfalls wirksame Photoinitiatoren sind Anthrachinon und zahlreiche seiner Derivate, beispielsweise ß-Methylanthrachinon, tert. -Butylanthrachinon und Anthrachinon- carbonsäureester und, besonders wirksam, Photoinitiatoren mit einer Acylphosphinoxidgruppe wie Acylphosphinoxide oder Bisacyl- phosphinoxide, z.B. 2 , , 6 -Trimethylbenzoyldiphenylphosphinoxid (Lucirin® TPO) .Photoinitiators are generally used for curing with UV light. Examples of suitable photoinitiators are benzophenone, alkylbenzophenones, halogen-methylated benzophenones, Michler's ketone, anthrone and halogenated benzophenones. Benzoin and its derivatives are also suitable. Also effective photoinitiators are anthraquinone and many of its derivatives, for example β-methylanthraquinone, tert. -Butylanthraquinone and anthraquinone-carboxylic acid esters and, particularly effective, photoinitiators with an acylphosphine oxide group such as acylphosphine oxides or bisacylphosphine oxides, for example 2,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO).
Soweit die strahlungshärtbaren Massen Photoinitiatoren enthalten, sollten diese Photoinitiatoren Absorbtionswellenlängen im Bereich des emittierten Lichts haben. Geeignete Photoinitiatoren für sichtbares Licht, welches keine UV-Anteile enthält, sind insbesondere die obengenannten Photoinitiatoren mit Acylphosphino- xidgruppen.As far as the radiation-curable compositions contain photoinitiators, these photoinitiators should have absorption wavelengths in the range of the emitted light. Suitable photoinitiators for visible light, which contains no UV components, are in particular the above-mentioned photoinitiators with acylphosphino oxide groups.
Es ist ein Vorteil der Erfindung, daß der Gehalt der Photo- initiatoren in der strahlungshärtbaren Masse gering sein kann oder auf Photoinitiatoren ganz verzichtet werden kann.It is an advantage of the invention that the content of the photoinitiators in the radiation-curable composition can be low or that photoinitiators can be dispensed with entirely.
Vorzugsweise enthalten die strahlungshärtbaren Massen weniger als 10 Gew. -Teile, insbesondere weniger als 4 Gew. -Teile, besonders bevorzugt weniger als 1,5 Gew. -Teile Photoinitiator auf 100 Gew. - Teile strahlungshärtbare Verbindungen.The radiation-curable compositions preferably contain less than 10 parts by weight, in particular less than 4 parts by weight, particularly preferably less than 1.5 parts by weight of photoinitiator per 100 parts by weight of radiation-curable compounds.
Ausreichend ist insbesondere eine Menge von 0 Gew. -Teilen bis 1,5 Gew. -Teilen, insbesondere 0,01 bis 1 Gew. -Teil Photo- initiator.A quantity of 0 parts by weight to 1.5 parts by weight, in particular 0.01 to 1 part by weight of photoinitiator, is in particular sufficient.
Die strahlungshärtbare Masse kann nach üblichen Verfahren auf das zu beschichtende Substrat aufgebracht werden oder in die entsprechende Form gebracht werden.The radiation-curable composition can be applied to the substrate to be coated by conventional methods or can be shaped accordingly.
Die Strahlungshärtung kann dann erfolgen, sobald das Substrat von dem Schutzgas umgeben ist.Radiation curing can take place as soon as the substrate is surrounded by the protective gas.
Die Strahlungshärtung kann mit allen Lampen, welche auch bisher für die Strahlungshartung eingesetzt wurden, erfolgen. Die Strahlungshärtung kann mit Elektronenstrahlen, Röntgen- oder Gammastrahlen, UV-Strahlung oder sichtbarem Licht erfolgen. Es ist ein Vorteil des erfindungsgemäßen Verfahrens, daß die Strahlungshartung mit sichtbarem Licht, welches nur geringe oder auch keine (Wellenlängen unter 300 nm enthält, erfolgen kann. Die Strahlungshartung beim erfindungsgemäßen Verfahren kann daher mit Sonnenlicht erfolgen oder mit Lampen, welche als Sonnenlichtersatz dienen. Diese La.mpen strahlen im sichtbaren Bereich oberhalb 400 nm ab und haben keine oder kaum UV-Lichtanteile unter 5 300 nm) .Radiation curing can be carried out with all lamps that have previously been used for radiation curing. Radiation curing can be carried out using electron beams, X-rays or gamma rays, UV radiation or visible light. It is an advantage of the method according to the invention that radiation curing can be carried out with visible light which contains only little or no (wavelengths below 300 nm). The radiation curing in the method according to the invention can therefore be carried out with sunlight or with lamps which serve as a substitute for sunlight. These lamps radiate in the visible range above 400 nm and have no or hardly any UV light components below 5300 nm).
Insbesondere beträgt beim erfindungsgemäßen Verfahren der Anteil von Strahlung im Wellenlängenbereich unter 300 nm weniger als 20 %, vorzugsweise weniger als 10 %, besonders bevorzugt weniger 0 als 5 %, insbesondere weniger als 1 bzw. 0,5 % oder weniger als 0,1 % des Integrals der abgestrahlten Intensität über den gesamten Wellenlängenbereich unterhalb 1000 nm.In particular, in the method according to the invention, the proportion of radiation in the wavelength range below 300 nm is less than 20%, preferably less than 10%, particularly preferably less than 0%, in particular less than 1 or 0.5% or less than 0.1% of the integral of the emitted intensity over the entire wavelength range below 1000 nm.
Bei der vorstehenden Strahlung handelt es sich um die tatsächlich 5 für die Härtung zur Verfügung stehende Strahlung, also bei Verwendung von Filtern um die Strahlung nach Filterdurchgang.The above radiation is the 5 radiation actually available for curing, that is, when filters are used, the radiation after filter passage.
In Betracht kommen Lampen, die ein Linienspektrum aufweisen, daß heißt nur bei bestimmten Wellenlängen abstrahlen, z. B. Leucht- 0 dioden oder Laser.Lamps that have a line spectrum come into consideration, that is to say emit only at certain wavelengths, e.g. B. LEDs 0 or lasers.
In Betracht kommen ebenfalls Lampen mit Breitbandspektrum, daß heißt, einer Verteilung des emittierten Lichts über einen Wellenlängenbereich. Das Intensitätsmaximum liegt dabei vorzugsweise im 5 sichtbaren Bereich oberhalb 400 nm.Lamps with a broadband spectrum, that is to say a distribution of the emitted light over a wavelength range, are also suitable. The intensity maximum is preferably in the visible range above 400 nm.
Genannt seien z.B. Glühlampen, Halogenlampen, Xenonlampen. Genannt seien auch Quecksilberdampflampen mit Filtern zur Vermeidung oder Verringerung von Strahlung unter 300 nm. 0For example, Incandescent lamps, halogen lamps, xenon lamps. Mercury vapor lamps with filters to avoid or reduce radiation below 300 nm may also be mentioned. 0
Ebenso geeignet sind gepulste Lampen z.B. Fotoblitzlampen oder Hochleistungsblitzlampen (Fa. VISIT) . Ein besonderer Vorteil des Verfahrens ist die Einsetzbarkeit von Lampen mit niedrigem Energiebedarf und niedrigem UV-Anteil, z.B. von 500 Watt Halogen-Lam- 5 pen, wie sie zu allgemeinen Beleuchtungszwecken eingesetzt werden. Dadurch kann sowohl auf eine Hochspannungseinheit zur Stromversorgung (bei Quecksilberdampflampen) sowie gegebenenfalls auf Lichtschutzmaßnahmen verzichtet werden, auch besteht mit Halogenlampen auch an Luft keine Gefährdung durch Ozonentwicklung wie 0 bei kurzwelligen UV-Lampen. Dadurch wird die Strahlungshartung mit transportablen Bestrahlungsgeräten erleichtert und Anwendungen „vor Ort", also unabhängig von feststehenden industriellen Härtungsanlagen sind möglich.Pulsed lamps are also suitable, e.g. Photo flash lamps or high-performance flash lamps (from VISIT). A particular advantage of the process is the ability to use lamps with low energy requirements and a low UV component, e.g. of 500 watt halogen lamps as used for general lighting purposes. This means that there is no need for a high-voltage unit for the power supply (for mercury vapor lamps) and, if necessary, for light protection measures, and halogen lamps also pose no risk in air due to ozone development, such as 0 with short-wave UV lamps. This makes radiation hardening easier with portable radiation devices and applications "on site", ie independent of fixed industrial hardening systems, are possible.
5 Für den mobilen Einsatz und für Anwendungen, die eine Vielzahl von Lampen zur Ausleuchtung des Substrates benötigen sind besonders Lampen, beinhaltend Lampengehäuse mit Reflektor, evtl. vor- handenen Kühleinrichtungen, Strahlungsfiltern und Stromquellenanschluß geeignet, die ein geringes Gewicht z.B. unter 20 kg vorzugsweise unter 8 kg, haben.5 For mobile use and for applications that require a large number of lamps to illuminate the substrate, lamps in particular, including lamp housings with reflectors, may be required. existing cooling devices, radiation filters and power source connection suitable, which have a low weight, for example less than 20 kg, preferably less than 8 kg.
Besonders leichte Lampen sind z.B. Halogenlampen, Glühlampen, Leuchtdioden, tragbare Laser, Fotoblitzlampen etc. Diese Lampen zeichnen sich auch durch besonders leichte Einbaumöglichkeit in Behälterinnenräume oder Behälterwandungen aus. Ebenso wird der technische Aufwand zur Stromversorgung vor allem im Vergleich zu bisher industrieüblichen QuecksilberdampfStrahlern im Mittel- und Hochdruckbereich verringert. Als bevorzugte Stromquellen der Lampen dienen neben Netzkraftstrom vor allem haushaltsübliche Wechselspannung, z.B. 220 V/50 Hz oder die Versorgung mit transportablen Generatoren, Batterien, Akkumulatoren, Solarzellen, etc.Particularly light lamps are e.g. Halogen lamps, incandescent lamps, light-emitting diodes, portable lasers, photo flash lamps etc. These lamps are also characterized by their particularly easy installation in container interiors or container walls. Likewise, the technical effort for power supply is reduced, especially in comparison to mercury vapor lamps in the medium and high pressure range that have been customary in the industry to date. In addition to mains power, the preferred current sources for the lamps are household AC, e.g. 220 V / 50 Hz or the supply of portable generators, batteries, accumulators, solar cells, etc.
Das erfindungsgemäße Verfahren eignet sich zur Herstellung von Beschichtungen auf Substraten und zur Herstellung von Formkörpern.The method according to the invention is suitable for the production of coatings on substrates and for the production of moldings.
Als Substrate in Betracht kommen z. B. solche aus Holz, Kunststoffe, Metall, mineralische oder keramische Materialien.Suitable substrates include z. B. those made of wood, plastics, metal, mineral or ceramic materials.
Als Formkörper genannt seien z. B. Verbundwerkstoffe, die z. B. mit strahlungshärtbarer Masse getränkte Fasermaterialien oder Gewebe enthalten, oder Formkörper für die Stereolithographie.As molded articles such. B. composites, the z. B. contain radiation-curable mass impregnated fiber materials or fabrics, or moldings for stereolithography.
Ein weiterer Vorteil des Verfahrens ist, daß die Abstände zwischen Lampen und strahlungshärtbarer Masse gegenüber der Härtung an Luft vergrößerbar sind. Insgesamt können geringere Strah- lungsdosen eingesetzt werden und eine Strahlereinheit kann zur Aushärtung größerer Flächen verwendet werden.Another advantage of the method is that the distances between lamps and radiation-curable mass can be increased compared to curing in air. Overall, lower radiation doses can be used and a radiator unit can be used to harden larger areas.
Damit ermöglicht das Verfahren zusätzlich zu üblichen Anwendungen der Strahlungshartung neue Anwendungen im Bereich der Härtung von Beschichtungen und Formmassen komplizierter dreidimensional geformter Gegenstände z.B. Möbel, Fahrzeugkarosserien, Gehäuse- und Gerätebau, bei mobilen Einsätzen wie Fuß- und Hallenbodenlackie- rung . Wegen des geringen technischen und materiellen Aufwandes ist das Verfahren auch geeignet für mittlere und kleine Hand- werksbetriebe, den Heimarbeits- und do it your seif -Bereich.Thus, in addition to the usual applications of radiation curing, the process enables new applications in the field of curing coatings and molding compounds of complicated three-dimensionally shaped objects, e.g. Furniture, vehicle bodies, housing and equipment construction, for mobile applications such as floor and hall floor painting. Because of the low technical and material expenditure, the process is also suitable for medium and small craft businesses, the home work and do it your soap area.
BeispieleExamples
Beispiel 1 Es wurde eine strahlungshärtbare Masse durch Mischen folgender Bestandteile hergestellt.example 1 A radiation-curable composition was produced by mixing the following components.
35 Gew.-% Laromer® LR 8987 (BASF Aktiengesellschaft), ein Urethanacrylat35% by weight Laromer® LR 8987 (BASF Aktiengesellschaft), a urethane acrylate
20 Gew. -% Hexandioldiacrylat,20% by weight hexanediol diacrylate,
38,5 Gew. -% Laromer® LR 8863, ein Polyetheracrylat 3,5 Gew.-% Iragucure® 184 (Ciba Spezialitätenchemie), ein Photoinitiator 0,5 Gew. -% Lucirin® TPO (BASF) ein Photoinitiator38.5% by weight Laromer® LR 8863, a polyether acrylate 3.5% by weight Iragucure® 184 (Ciba Specialty Chemicals), a photoinitiator 0.5% by weight Lucirin® TPO (BASF) a photoinitiator
2 Gew.-% Tinuvin®400 (Ciba Spezialitätenchemie), ein UV-Absorber 1,5 Gew.-% Tinuvin® 292, ein UV Absorber2% by weight of Tinuvin®400 (Ciba Specialty Chemicals), a UV absorber 1.5% by weight of Tinuvin® 292, a UV absorber
Mit dieser Masse wurde eine Glasscheibe lackiert (Schichtdicke 50 μm) .A glass pane was coated with this material (layer thickness 50 μm).
In einen Behälter der Tiefe 60 cm mit Durchmesser 40 cm werden 500 g Trockeneis eingefüllt. Nach ca. 60 min beträgt der Restsau- erstoffanteil ca. 10 cm unterhalb des oberen Behälterrandes500 g of dry ice are poured into a 60 cm deep, 40 cm diameter container. After approx. 60 minutes, the residual oxygen content is approx. 10 cm below the upper edge of the container
3 Gew. -% und bei 45 cm Tiefe 0,01 Gew.-%. Auf die 45 cm Ebene wird die Glasscheibe eingelegt und 2 min mit einer 500 Watt Halogenlampe im Abstand von 50 cm zur Halogenlampe bestrahlt. Die Lackierung ist hochkratzfest und kann mit einem Holzspatel sowie einem weißen Schreibmaschinenpapier unter manuellem Druck und Reiben nicht angekratzt werden.3% by weight and at 45 cm depth 0.01% by weight. The glass pane is placed on the 45 cm level and irradiated for 2 min with a 500 watt halogen lamp at a distance of 50 cm from the halogen lamp. The paint is highly scratch-resistant and cannot be scratched with a wooden spatula and white typewriter paper under manual pressure and rubbing.
Im Vergleich dazu wird unter gleichen Bedingungen an Luft bestrahlt. Die Lackierung blieb flüssig. Im Vergleich dazu wird auf einem Transportband bei 10 m/min Bandgeschwindigkeit unter einer Quecksilberhochdrucklampe mit 120 W/cm (Fa. IST) mit Lampenabstand 15 cm zweimal belichtet... Die Lackierung konnte nicht kratzfest ausgehärtet werden.In comparison, air is irradiated under the same conditions. The paint remained fluid. In comparison, exposure is carried out twice on a conveyor belt at a belt speed of 10 m / min under a high-pressure mercury lamp with 120 W / cm (IST) with a lamp spacing of 15 cm ... The coating could not be cured scratch-resistant.
Beispiel 2Example 2
Die strahlungshärtbare Masse entsprach Beispiel 1.The radiation-curable composition corresponded to Example 1.
Die strahlungshärtbare Masse wurde als Klarlack auf das Gehäuse eines Autoaußenspiegel aufgetragen und erfindungsgemäß wie in Beispiel 1 beschrieben gehärtet. Die erhaltene Lackierung war hochkratzfest. The radiation-curable composition was applied as a clear lacquer to the housing of an exterior car mirror and cured according to the invention as described in Example 1. The paint obtained was highly scratch-resistant.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Formmassen und Beschichtungen auf Substraten durch Härtung von strahlungshärtbaren Massen unter Schutzgas durch Bestrahlen mit Licht dadurch gekennzeichnet, daß es sich bei dem Schutzgas um ein Gas handelt, das schwerer ist als Luft, und das seitliche Wegfließen des Schutzgases während der Strahlungshartung durch eine geeig- nete Vorrichtung oder Maßnahmen verhindert wird.1. A process for the production of molding compositions and coatings on substrates by curing radiation-curable compositions under protective gas by irradiation with light, characterized in that the protective gas is a gas which is heavier than air, and the side flow of the protective gas during the Radiation hardening is prevented by a suitable device or measures.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß es sich um ein dreidimensionales Härtungsverfahren handelt.2. The method according to claim 1, characterized in that it is a three-dimensional curing process.
3. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Substrat oder die Formmasse in ein Tauchbecken, welches das Schutzgas enthält, eingetaucht wird.3. The method according to claim 1 or 2, characterized in that the substrate or the molding compound is immersed in a plunge pool which contains the protective gas.
4. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Substrat um eine Bodenfläche oder bedruckbare oder bedruckte Substrate handelt und das seitliche Wegfließen des Schutzgases durch seitliche Begrenzungen verhindert wird.4. The method according to claim 1, characterized in that the substrate is a floor surface or printable or printed substrates and the lateral flow of the protective gas is prevented by side boundaries.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekenn- zeichnet, daß es sich bei dem Schutzgas um Kohlendioxid handelt.5. The method according to any one of claims 1 to 4, characterized in that the protective gas is carbon dioxide.
6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Schutzgas durch Verdampfen von Trockeneis hergestellt wird.6. The method according to any one of claims 1 to 5, characterized in that the protective gas is produced by evaporating dry ice.
7. Verfahren gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Sauerstoffgehalt in der Schutzgas - atmosphäre, welche das Substrat in einem Abstand von bis zu 10 cm von seiner Oberfläche umgibt, kleiner 15 Gew. -%, bezogen auf die gesamte Gasmenge, beträgt.7. The method according to any one of claims 1 to 6, characterized in that the oxygen content in the protective gas atmosphere, which surrounds the substrate at a distance of up to 10 cm from its surface, less than 15 wt .-%, based on the total Amount of gas.
8. Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die strahlungshärtbare Masse 0,001 bis 12 Mol strahlungshärtbare ethylenisch ungesättigte Gruppen auf 1000 g strahlungshärtbare Verbindungen enthält.8. The method according to any one of claims 1 to 7, characterized in that the radiation-curable composition contains 0.001 to 12 mol of radiation-curable ethylenically unsaturated groups per 1000 g of radiation-curable compounds.
9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es sich bei mindestens 60 mol-% der strahlungs- härtbaren ethylenisch ungesättigten Gruppen um (Meth)acryl- gruppen handelt. 9. The method according to any one of claims 1 to 8, characterized in that at least 60 mol% of the radiation-curable ethylenically unsaturated groups are (meth) acrylic groups.
10. Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die strahlungshärtbaren Massen weniger als10. The method according to any one of claims 1 to 9, characterized in that the radiation-curable compositions less than
10 Gew. -Teile Photoinitiator, bezogen auf 100 Gew. -Teile der Gesamtmenge an strahlungshärtbaren Verbindungen enthalten. 510 parts by weight of photoinitiator, based on 100 parts by weight of the total amount of radiation-curable compounds. 5
11. Verfahren gemäß einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Bestrahlung mit einer Lichtquelle erfolgt, die Licht im sichtbaren Bereich oberhalb 300 nm abstrahlt und üblicherweise als Ersatz für Sonnenlicht verwendet wird.11. The method according to any one of claims 1 to 10, characterized in that the irradiation is carried out with a light source which emits light in the visible range above 300 nm and is usually used as a replacement for sunlight.
1010
12. Verfahren gemäß Anspruch 11, dadurch gekennzeichnet, daß die Bestrahlung mit Sonnenlicht, Halogenlampen oder Glühlampen Leuchtdioden oder Laser erfolgt.12. The method according to claim 11, characterized in that the irradiation with sunlight, halogen lamps or incandescent light-emitting diodes or lasers.
15 13. Verfahren gemäß einem der Ansprüche 1 bis 12 zur Beschichtung von Kraftfahrzeugen, z.B. Straßen-, Schienen- und Luftfahrzeugen, insbesondere Kraftfahrzeugkarosserien und Kraftfahrzeugteilen.15. The method according to any one of claims 1 to 12 for coating motor vehicles, e.g. Road, rail and aircraft, in particular motor vehicle bodies and motor vehicle parts.
20 14. Verfahren gemäß einem der Ansprüche 1 bis 13 zur Beschichtung von Formteilen aus Holz, Kunststoffen, Metall, mineralischen und keramischen Materialien.20 14. The method according to any one of claims 1 to 13 for coating moldings made of wood, plastics, metal, mineral and ceramic materials.
15. Verfahren gemäß einem der Ansprüche 1 bis 11 zur Beschichtung 25 von Bodenbelägen.15. The method according to any one of claims 1 to 11 for coating 25 of floor coverings.
16. Verfahren gemäß einem der Ansprüche 1 bis 11 zur Herstellung von Formkörpern, z.B. Verbundwerkstoffen oder Formkörpern für die Stereolithographie.16. The method according to any one of claims 1 to 11 for the production of moldings, e.g. Composites or moldings for stereolithography.
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EP00981286A 1999-12-01 2000-11-21 Light curing of radiation curable materials under a protective gas Expired - Lifetime EP1235652B1 (en)

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US20060115602A1 (en) 2006-06-01
JP2003515445A (en) 2003-05-07
US7105206B1 (en) 2006-09-12
DE50015609D1 (en) 2009-05-14
WO2001039897A3 (en) 2002-03-14
EP2047916A3 (en) 2009-04-29
EP1235652B1 (en) 2009-04-01
WO2001039897A2 (en) 2001-06-07
ES2321799T3 (en) 2009-06-12
EP2047916A2 (en) 2009-04-15
ATE427167T1 (en) 2009-04-15

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