CA2606100A1 - Method for producing scratch-resistant cured materials - Google Patents
Method for producing scratch-resistant cured materials Download PDFInfo
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- CA2606100A1 CA2606100A1 CA002606100A CA2606100A CA2606100A1 CA 2606100 A1 CA2606100 A1 CA 2606100A1 CA 002606100 A CA002606100 A CA 002606100A CA 2606100 A CA2606100 A CA 2606100A CA 2606100 A1 CA2606100 A1 CA 2606100A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- B05D2201/00—Polymeric substrate or laminate
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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
- B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
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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
- B05D3/04—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
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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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer
Abstract
The invention relates to a method for producing cured material consisting of material mixtures that can be cured by actinic radiation, by irradiation with UV-radiation. The invention is characterised in that it uses UV-radiation of the following spectral distribution and dose: wavelength lambda = 400 to 320 nm; dose = 500 to 2,500 mJ/cm2; wavelength lambda = 320 to 290 nm; dose = 700 to 3,000 mJ/cm2; wavelength lambda = 290 to 180 nm; dose = 100 to 500 mJ/cm2.
Description
~
METHOD FOR. PRODUUNG SC RATC H RESISTANT CURED MATERIALS
Field of the 9nvenltaon!
The present invention relates to a new process for producing cured materials.
The present invention further relates to the use of the cured materials produced by means of the new process for the coating, adhesive bonding, sealing, wrapping, and packaging of bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, freight containers, packaging, small parts, optical, mechanical, and electrical components, and components for white goods.
Prior Art The cured materials are preferably thermoset materials. For the purposes of the present invention, thermoset materials are three-dimensionally crosslinked substances which in contrast to thermoplastic materials are deformable only to a small extent or not at all on heating.
A process for producing cured materials is known from German patent application DE 102 02 565 Al. In the known process the cured materials are produced from a composition, curable thermally and with actinic radiation, by heating and exposure to UV
radiation, for which (1) a composition curable thermally and with actinic radiation is used which, after it has cured, has a storage modulus E' in the rubber-elastic range of at least 10' S Pa and a loss factor tan6 at 20 C of not more than 0.10, the storage modu lus E.' arld the loss factor having been measured by means of dynamic mechanical thermoanalysis (DMTA) on free films with a thickness of 40 10 m, and (2) exposure is carried out with UV radiation whose spectrum comprises, in addition to UV-A and UV-B, a UV-C fraction which in the wavelength range from 200 to 280 nm has from 2 to 80% of the relative spectral radiance of the spectrum of a medium-pressure mercury vapor lamp within this wavelength range, the relative spectral radiance of the UV-C fraction in the wavelength range from 200 to 240 nm BASF Coatings AG 2 May 04, 2006 always being smaller than the relative spectral radiance of the spectrum of a medium-pressure mercury vapor lamp within this wavelength range, and (3) the radiation dose is from 100 to 6000 mJ cm,2.
For the purposes of the present invention actinic radiation means electromagnetic radiation, examples being near infrared (NIR), visible light, UV radiation, X-rays or gamma radiation, preferably UV radiation, and also corpuscular radiation, examples being electron beams, beta radiation, neutron beams, proton beams, and alpha radiation, preferably electron beams. Actinic radiation means, in particular, UV radiation.
The spectrum of UV radiation is known to be divided into three regions:
UV-A: 320 to 400 nm UV-B: 320 to 290 nm UV-C: 290 to 100 nm In general the UV spectrum of UV radiation sources is available only down to a wavelength of 180 - 200 nm, since the lower-wavelength radiation is absorbed by the hollow quartz bodies of the radiation sources (cf. R. Stephen Davidson, "Exploring the Science, Technology and Applications of U.V. and E.S. Curing", Sita Technology Ltd., London, 1999, Chapter I, "An Overview", pages 3 to 34).
The yellowing of the resultant known cured materials is low. They are scratch-resistant and, after being scratched, display minor loss of gloss. At the same time their hardness and chemical resistance are high.
The continually growing demands of the market, however, call for further improvement in the scratch resistance of cured materials, particularly their scratch resistance when exposed to automatic wash lines. In addition it is necessary to achieve further improvement in the adhesion of the cured materials to substrates, particularly those of metals, plastics, and other cured materials. A particular need is to further improve the intercoat adhesion between coats of cured materials which differ in physical composition and/or functions, particularly in multicoat paint systems.
BASF Coatings AG 3 May 04, 2006 Problem It is an object of the present invention to provide a new process for producing cured materials that no longer has the disadvantages of the prior art but instead, in a particularly simple and particularly reliable way, affords cured materials which meet the advantageous profile of requirements set out above and, furthermore, exhibit improved scratch resistance, particularly on exposure in wash lines, and also improved adhesion to substrates, particularly those of metals, plastics, and other cured materials.
The new process ought in particular to afford cured materials which have improved intercoat adhesion between coats of cured materials which differ in physical composition and/or function, particularly in multicoat paint systems, and particularly on exposure to a steam jet.
Solution Found accordingly has been the new process for producing cured materials from compositions curable with actinic radiation ("compositions") by exposure to UV
radiation, using UV radiation of the following spectral distribution and dose:
- wavelength lambda = 400 to 320 nm; dose = 500 to 2500 mJ/cm2;
- wavelength lambda = 320 to 290 nm; dose = 700 to 3000 mJ/cm2;
- wavelength lambda = 290 to 180 nm; dose = 100 to 500 mJ/cm2.
The new process for producing cured materials is referred to below as the "process of the invention".
Further subject matter of the invention will emerge from the description.
Advantages of the inventiion In the light of the prior art it was surprising and unforeseeable for the skilled worker that the object on which the present invention was based could be achieved by means of the process of the invention.
In particular it was surprising that the process of the invention, in a particularly simple and reliable way, using conventional UV radiation sources, using conventional electronic, optical, and mechanical components, and using conventional irradiation units, afforded, in BASF Coatings AG 4 May 04, 2006 a particularly simple and particularly reliable way, cured materials, especially thermoset materials, which not only exhibited low yellowing, high hardness, and high chemical resistance but also, furthermore, had improved scratch resistance, particularly on exposure in wash lines, and also had improved adhesion to substrates, particularly those of metals and plastics and other cured materials. In particular, the process of the invention afforded cured materials which exhibited improved intercoat adhesion between coats of cured materials differing in physical composition and/or function, particularly in multicoat paint systems, and particularly on exposure to a steam jet.
Even more surprising was that the process of the invention could be carried out with UV-curable compositions differing very widely in constitution. As a result, in an unexpectedly advantageous way, it was possible to tailor the compositions optimally to a very wide variety of end uses, so that they could be used with advantage as coating materials, adhesives, sealants, and starting materials for moldings and films. In particular it was surprising that the coating materials could be used with particular advantage as electrocoat materials, surfacers, antistonechip primers, solid-color topcoat, basecoat, and clearcoat materials.
A surprise not least was the extraordinarily broad usefulness of the cured materials as coatings, adhesive layers, seals, moldings, and films, preferably as coatings, especially electrocoats, surfacer coats, antistonechip primer coats, solid-color topcoats, basecoats, and clearcoats. They were especially suitable outstandingly for the coating, adhesive bonding, sealing, and packaging of bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, freight containers, packaging, small parts, such as nuts, bolts, wheel rims or hub caps, optical components, mechanical components, electrical components, such as windings (coils, stators, rotors), and components for white goods, such as radiators, household appliances, refrigerator casings or washing-machine casings.
etai8ed description of the invention The process of the invention serves for producing cured materials, especially thermoset materials, from compositions curable with actinic radiation (referred to for the sake of brevity below as "compositions") by exposure to UV radiation.
BASF Coatings AG 5 May 04, 2006 In accordance with the invention the UV radiation used is of the following spectral distribution and dose:
wavelength lambda = 400 to 320 nm; dose = 500 to 2500 and preferably 750 to 2000 mJ/cmz;
- wavelength lambda = 320 to 290 nm; dose = 700 to 3000 and preferably 1000 to 2200 mJ/cm2;
wavelength lambda = 290 to 180 nm; dose = 100 to 500 and preferably 200 to 450 mJ/cmz.
The power may vary widely. The UV radiation used is preferably of the following spectral distribution and power:
wavelength lambda = 400 to 320 nm; power = 100 to 600 and preferably 120 to 550 mVr!/cm2;
wavelength lambda = 320 to 290 nm; power = 100 to 600 and preferably 140 to 550 mVi//cm2;
wavelength lambda = 290 to 180 nm; power = 20 to 120 and preferably 30 to 100 mVV/cm2.
For irradiation in the context of the process of the invention, broad variation is possible in the distance of the UV radiation source from the surface of the composition.
The distance is preferably 20 to 250 mm and in particular 40 to 100 mm.
For a given dose, the irradiation period is guided by the belt speed or rate of advance of the substrates in the irradiation unit, and vice versa.
As radiation sources for the UV radiation for inventive use it is possible to use any conventional UV lamps which as such emit the relevant spectrum. Use may also be made, however, of combinations of at least two UV lamps which, although not emitting the UV
radiation for inventive use, have spectra which nevertheless add to give the UV radiation for inventive use. In addition it is possible to use UV lamps where the desired spectrum is set by means of filters and/or reflectors. Flash lamps are also suitable.
Examples of suitable flash lamps are flash lamps from the company VISIT.
BASF Coatings AG 6 May 04, 2006 As UV lamps it is preferred to use mercury vapor lamps, more preferably low-, medium-and high-pressure mercury vapor lamps, especially medium-pressure mercury vapor lamps. Particular preference is given to using unmodified mercury vapor lamps plus appropriate filters and/or reflectors, or mercury vapor lamps which have been modified, in particular by doping.
Examples of suitable modified mercury vapor lamps are gallium-doped and/or iron-doped lamps, especially iron-doped mercury vapor lamps, as described, for example, in R. Stephen Davidson, "Exploring the Science, Technology and Applications of U.V. and E.S. vuring", Sita Technology Ltd., London, 1999, Chapter I, "An Overview", page 16, Figure 10, or in ipl.-Ing. Peter Klamann, "eltosch System-Kompetenz, UV-Technik, Leitfaden fur Anwender", page 2, October 1998.
Examples of suitable unmodified mercury vapor lamps plus appropriate filters and/or reflectors are the UV lamps from Arccure. These lamps are constructed so that the compositions for curing are not struck directly by any UV radiation but only indirectly reflected radiation in two bundled streaks. For both reflected streaks it is possible to use different reflectors, which reflect the entire UV spectrum ("broad"), reflect the long-wave component of the UV spectrum more extensively onto the plastic moldings ("A+B"), or reflect the short-wave component of the UV spectrum more extensively onto the sample ( 9))_ The arrangement of the radiation sources may be adapted to the spatial circumstances of the compositions and/or of the substrates to which they have been applied, and also the process parameters. In the case of substrates of complex shape, such as are envisaged, for example, for automobile bodies, those regions not accessible to direct radiation (shadow regions), such as cavities, folds, and other structural undercuts, can be cured using pointwise, small-area or all-round sources, in conjunction with an automatic movement means for the irradiation of cavities or edges.
In the context of the process of the invention it is preferred to carry out irradiation under an oxygen-depleted atmosphere.
"Oxygen-depleted" means that the oxygen content of the atmosphere at the surface of the compositions is lower than the oxygen content of air (20.95% by volume). The maximum oxygen content of the oxygen-depleted atmosphere is preferably 18%, more preferably BASF Coatings AG 7 May 04, 2006 16%, very preferably 14%, with particular preference 10%, and in particular 6.0% by volume.
The atmosphere may in principle by oxygen-free; that is, it comprises an inert gas. The complete or substantial absence of oxygen may also be obtained, however, by masking the surface of the compositions with an oxygen-impermeable film.
The absence of the inhibitory effect of oxygen, however, may in such cases produce a sharp acceleration in radiation curing, as a result of which inhomogeneities and stresses may arise in the coatings of the invention. It is therefore not advantageous in all cases to lower the oxygen content of the atmosphere to a volume percentage of zero.
The minimum oxygen content is preferably 0.1 % and in particular 0.5% by volume.
The oxygen-depleted atmosphere may be provided in a variety of ways. It is preferred to produce an appropriate gas mixture and to make it available in pressurized cannisters.
More preferably the depletion is brought about by introducing at least one inert gas in the respective amounts required into the cushion of air situated over the surface of the layers that are to be cured. The oxygen content of the atmosphere situated over the surface in question can be measured continuously by means of conventional methods and devices for determining elemental oxygen, and where appropriate can be adjusted automatically to the desired level.
By inert gas is meant a gas which under the curing conditions employed is not broken down by the actinic radiation, does not inhibit curing and/or does not react with the compositions. Preference is given to using nitrogen, carbon dioxide, helium, neon or argon, especially nitrogen and/or carbon dioxide.
The compositions used for the process of the invention are curable with actinic radiation, especially UV radiation. This means that they comprise or consist of constituents which can be activated with actinic radiation and so undergo free-radical or ionic polymerization, especially including free-radical polymerization. This results in three-dimensional crosslinking of the compositions to give the cured materials, particularly the thermoset materials.
The compositions may additionally be curable physically and/or thermally.
BASF Coatings AG 8 May 04, 2006 For the purposes of the present invention the term "physical curing" denotes the curing of the compositions, in particular in the form of a film of a coating material, by filming as a result of solvent emission from the compositions, with linking within the coating taking place via looping of the polymer molecules of the binders (regarding the term cf. Rompp Lexikon Lacke und Druckfarben, Georg Thieme Veriag, Stuttgart, New York, 1998, "Binders", pages 73 and 74). Or else filming takes place via the coalescence of binder particles (cf. R mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Curing", pages 274 and 275). Normally no crosslinking agents are needed for this purpose.
For the purposes of the present invention the term "thermal curing" denotes the heat-initiated curing of a composition, in particular of a film of a coating material, in which normally a binder and a separate crosslinking agent are employed. This is normally referred to by those in the art as external crosslinking. Where the crosslinking agents are already incorporated in the binders, the term "self-crosslinking" is also used. In accordance with the invention, external crosslinking is of advantage and is therefore employed with preference (cf. R mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, I~_!ew York, 1998, "Curing", pages 274 to 276, especially page 275, bottom).
Those in the art also refer to compositions curable with actinic radiation and thermally as dual-cure compositions.
In the process of the invention it is preferred to use compositions which, after they have been cured, have a storage modulus E' in the rubber-elastic range of at least 10' 5, preferably at least 10' 6, more preferably at least 108 , and in particular at least 108.3 Pa and a loss factor tanS at 20 C of not more than 0.10, preferably not more than 0.06, the storage modulus E and the loss factor having been measured by means of dynamic mechanical thermoanalysis (DMTA) on free films having a thickness of 40 10 m.
The recoverable energy component (elastic component) in the deformation of a viscoelastic material such as a polymer, for example, is determined by the parameter of the storage modulus E, whereas the energy component consumed (dissipated) in this process is described by the parameter of the loss modulus E". The moduli E' and E" are dependent on deformation rate and temperature. The loss factor tan8 is defined as the ratio of the loss modulus E" to the storage modulus E'. tan8 can be determined by means BASF Coatings AG 9 May 04, 2006 of dynamic mechanical thermoanalysis (DMTA) and constitutes a measure of the relationship between the elastic and plastic properties of the film. DMTA is a widely known measurement method for determining the viscoelastic properties of coatings and is described, for example, in Murayama, T., Dynamic Mechanical Analysis of Polymeric Materials, Elsevier, New York, 1978 and Loren W. Hill, Journal of Coatings Technology, Vol. 64, No. 808, May 1992, pages 31 to 33. The method conditions relating to the measurement of tanb by means of DMTA are described in detail by Th. Frey, K.-H. Grof3e Brinkhaus, and U. R ckrath in Cure Monitoring of Thermoset Coatings, Progress In Organic Coatings 27 (1996), 59-66, or in German patent application DE 44 09 715 Al or German patent DE 197 09 467 C2. Preference is given to employing the following conditions: tensile mode; amplitude: 0.2%; frequency: 1 Hz; temperature ramp:
1 C/min from room temperature to 200 C.
The storage modulus E' can be adjusted by the skilled worker through the selection of particular actinic radiation-curable and also, where appropriate, physically and/or thermally curable constituents, the functionality of the constituents, and their proportion as a fraction of the composition for inventive use.
The storage modulus E' can generally be adjusted, by means of constituents curable with actinic radiation, by selecting the nature and amount of the constituents preferably such that for each gram of composition soiids there are 0.5 to 6.0, preferably 1.0 to 4.0, and more preferably 2.0 to 3.0 meq of bonds which can be activated with actinic radiation.
For the purposes of the present invention the "solids" means the sum of those constituents of a composition that build up the cured material produced from said composition.
For the purposes of the present invention a bond which can be activated with actinic radiation is a bond which when exposed to actinic radiation becomes reactive and, together with other activated bonds of its kind, enters into polymerization reactions and/or crosslinking reactions which proceed in accordance with free-radical and/or ionic mechanisms. Examples of suitable bonds are single carbon-hydrogen bonds or single or double carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon bonds. Of these, the double carbon-carbon bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention.
For the sake of brevity they are referred to below as "double bonds".
BASF Coatings AG 10 May 04, 2006 Particularly preferred compounds containing double bonds are compounds containing acrylate groups.
The compositions may contain acid groups. Where the latter are used they are present in an amount of more than 0.05, preferably more than 0.08, very preferably more than 0.15, and in particular more than 0.2 meq/g solids. The amount of acid groups present should not exceed 15, preferably 10, more preferably 8, and in particular 5 meq/g solids.
Where acid groups are used they are selected preferably from the group consisting of carboxyl groups, phosphonic acid groups, sulfonic acid groups, acidic phosphate ester groups, and acidic sulfate ester groups, especially carboxyl groups.
The physical constitution of the compositions for use in the process of the invention is not critical; instead, all conventional compositions curable with actinic radiation, especially UV
radiation, and also, if desired, curable physically and/or thermally, can be used.
Suitable constituents of such compositions, the suitable compositions themselves, and the processes for preparing them are known, for example, from German patent application DE
102 02 565 Al, page 4, paragraph [0029], to page 8, paragraph [0079], or from German patent DE 197 09 467 C2.
The process of the invention affords particular advantages if carried out with compositions comprising at least one free-radically crosslinkable or curable component which (i) contains one or more oligourethane and/or one or more polyurethane (meth)acrylates and which has (ii) on average more than one olefinically unsaturated double bond per molecule, (iii) a number-average molecular weight of 1000 to 10 000 daltons, (iv) a double bond content of 1.0 to 5.0 double bonds per 1000 g of free-radically crosslinkable component, (v) on average per molecule > 1 branch point, (vi) 5 to 50% by weight, based in each case on the weight of the component, of cyclic structural elements, and (vii) at least one aliphatic structural element having at least 6 carbon atoms in the chain, BASF coag6ngs AG 11 PAT 01275 PC'f May 04, 2006 the free-radically crosslinkable component containing carbamate and/or biuret and/or allophanate and/or urea and/or amide groups.
The free-radically crosslinkable component preferably contains at least 50% by weight, more preferably contains at least 70% by weight, and very preferably contains at least 80% by weight, based in each case on the solids content of the free-radically crosslinkable component, of one or more oligourethane (meth)acrylates and/or one or more polyurethane (meth)acrylates. In particular, the free-radically crosslinkable component is composed of 100% of one or more oligourethane (meth)acrylates and/or one or more polyurethane (meth)acrylates.
The free-radically crosslinkable component also contains preferably not more than 50% by weight, more preferably not more than 30% by weight, and very preferably not more than 20% by weight, of further monomers, but preferably oligomers and/or polymers, especially polyester (meth)acrylates, epoxy (meth)acrylates, (meth)acryloyl-functional (meth)acrylic copolymers, polyether (meth)acrylates, unsaturated polyesters, amino (meth)acrylates, melamine (meth)acrylates and/or silicone (meth)acrylates, preferably polyester (meth)acrylates and/or epoxy (meth)acrylates and/or polyether (meth)acrylates.
Preference is given here to polymers which in addition to the double bonds also contain hydroxyl, carboxyl, amino and/or thiol groups. In the great majority of cases the use of further free-radically crosslinkable constituents is superfluous.
The free-radically crosslinkable component contains preferably less than 5% by weight, more preferably less than 1% by weight, based in each case on the weight of the free-radically crosslinkable component, and in particular contains substantially no detectable free isocyanate groups.
Additionally it is preferred for the free-radically crosslinkable component to comprise a mixture of different oligourethane and/or polyurethane (meth)acrylates, which may also have different double bond contents, molecular weights, double bond equivalent weights, branch point contents and levels of cyclic and also relatively long-chain aliphatic structural elements, and different amounts of carbamate, biuret, allophanate, amide and/or urea groups.
This mixture may be obtained by mixing different oligourethane or polyurethane (meth)acrylates or by the preparation of different products simultaneously during the preparation of a corresponding oligourethane and/or polyurethane (meth)acrylate.
BASF Coatings AG 12 May 04, 2006 In order to obtain effective crosslinking it is preferred to use free-radically crosslinkable components whose functional groups are of high reactivity, more preferably free-radically crosslinkable components containing acrylic double bonds as functional groups.
The urethane (meth)acrylates can be prepared in a way which is known to the skilled worker, from a compound containing isocyanate groups and from at least one compound containing groups that are reactive toward isocyanate groups, preparation then taking place by mixing of the components in any order, where appropriate at an elevated temperature.
It is preferred to add the compound containing groups that are reactive toward isocyanate groups to the compound containing isocyanate groups, preferably in two or more steps.
In particular the urethane (meth)acrylates are obtained by initially introducing the diisocyanate or polyisocyanate and subsequently adding at least one hydroxyalkyl (meth)acrylate or hydroxyalkyl ester of other olefinically unsaturated carboxylic acids, so ;giving rise to reaction initially of some of the isocyanate groups.
Subsequently a chain extender from the group of the diols/polyols and/or diamines/polyamines and/or dithiols/polythiols and/or alkanolamines is added and in this way the remaining isocyanate groups are reacted with the chain extender.
A further possibility is to prepare the urethane (meth)acrylates by reacting a di- or polyisocyanate with a chain extender and subsequently reacting the remaining free isocyanate groups with at least one olefinically unsaturated hydroxyalkyl ester.
It will be appreciated that all forms intermediate between these two techniques are also possible. For example, some of the isocyanate groups of a diisocyanate can first be reacted with a diol, subsequently a further portion of the isocyanate groups can be reacted with the olefinically unsaturated hydroxyalkyl ester, and thereafter the remaining isocyanate groups can be reacted with a diamine.
In general the reaction is carried out at temperatures between 5 and 100 C, preferably between 20 to 90 C, and more preferably between 40 and 80 C, and in particular between 60 and 80 C.
It is preferred here to operate under anhydrous conditions. "Anhydrous" means here that BASF Coatings AG 13 May 04, 2006 the water content of the reaction system is not more than 5% by weight, preferably not more than 3% by weight, and more preferably not more than 1% by weight. In particular the water content is below the detection limit.
In order to suppress polymerization of the polymerizable double bonds it is preferred to operate under an oxygen-containing gas, more preferably air or air/nitrogen mixtures.
As an oxygen-containing gas it is possible with preference to use air or a mixture of oxygen or of air and a gas which is inert under the conditions of use. As the inert gas use may be made of nitrogen, helium, argon, carbon monoxide, carbon dioxide, steam, lower hydrocarbons, or mixtures thereof.
The oxygen content of the oxygen-containing gas can be, for example, between 0.1% and 22% by volume, preferably from 0.5% to 20%, more preferably 1% to 15%, very preferably 2% to 10%, and in particular 4% to 10% by volume. It will be appreciated that, if desired, higher oxygen contents can also be used.
The reaction can also be carried out in the presence of an inert solvent, examples being acetone, isobutyl methyl ketone, methyl ethyl ketone, toluene, xylene, butyl acetate or ethoxyethyl acetate.
Through the selection of the nature and amount of di- and/or polyisocyanate, chain extender, and hydroxyalkyl ester employed, control is exerted over the further variables of the urethane (meth)acrylates, such as, for example, double bond content, double bond equivalent weight, amount of branch points, amount of cyclic structural elements, amount of aliphatic structural elements having at least 6 carbon atoms, and amount of biuret, allophanate, carbamate, urea and/or amide groups, and the like.
Through the selection of the particular amounts of di- or polyisocyanate and chain extender that are employed and also through the functionality of the chain extender it is also possible, furthermore, to prepare urethane (meth)acrylates which as well as the ethylenically unsaturated double bonds also contain other functional groups, examples being hydroxyl groups, carboxyl groups, amino groups and/or thiol groups or the like.
Especially if the urethane (meth)acrylate is to be used in aqueous compositions, some of the free isocyanate groups present in the reaction mixtures are also reacted with compounds which contain an isocyanate-reactive group, selected preferably from the BASF Coatings AG 14 May 04, 2006 group consisting of hydroxyl, thiol, and primary and secondary amino groups, especially hydroxyl groups, and also at least one, especially one, acid group, selected preferably from the group consisting of carboxyl groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups, especially carboxyl groups. Examples of suitable compounds of this kind are hydroxyacetic acid, hydroxypropionic acid or gamma-hydroxybutyric acid, especially hydroxyacetic acid (glycolic acid).
For the process of the invention the compositions may be present in any of a very wide variety of physical states and three-dimensional forms.
For instance, at room temperature, the compositions may be solid or liquid or fluid. They may also, however, be solid at room temperature and fluid at higher temperatures, with preferably a thermoplastic behavior being displayed. In particular they may be conventional compositions comprising organic solvents, aqueous compositions, substantially or entirely solvent-free and water-free liquid compositions (100% systems), substantially or entirely solvent-free and water-free solid powders, or substantially or entirely solvent-free powder suspensions (powder slurries). The dual-cure compositions may additionally be one-component systems, where the binders and crosslinking agents are present alongside one another, or two-component or multicomponent systems, where the binders and crosslinking agents are separate from one another until shortly before application.
In terms of method the preparation of the compositions for inventive use has no peculiarities but instead takes place by the mixing and homogenization of the above-described constituents by means of conventional mixing techniques and apparatus such as stirred tanks, agitator mills, extruders, compounders, Ultraturrax devices, inline dissolvers, static mixers, micromixers, toothed-wheel dispersers, pressure release nozzles and/or microfluidizers, preferably in the absence of actinic radiation. The selection of the method that is optimum for a given individual case is guided in particular by the physical state and the three-dimensional form which the composition is to have. Where, for example, a thermoplastic composition is present in the preferred form of a film or a laminate, extrusion through a slot die is particularly appropriate for producing the composition and shaping it.
For the purposes of the process of the invention the compositions are used for producing cured materials, especially thermoset materials, which serve a very wide variety of end uses.
BASF coattregs AG 15 PAT 01275 PcT
May 04, 2006 The compositions are preferably starting products for moldings and films or are coating materials, adhesives, and sealants.
The cured materials are preferably moldings, films, coatings, adhesive layers, and seals.
The coating materials are employed in particular as electrocoat materials, surfacers, antistonechip primers, solid-color topcoat materials, aqueous basecoat materials and/or clearcoat materials, especially clearcoat materials, for producing single-coat or multicoat color and/or effect, electrically conductive, magnetically shielding or fluorescent paint systems, especially multicoat color and/or effect paint systems. The multicoat paint systems can be produced using the conventional wet-on-wet techniques and/or extrusion techniques and also the conventional paint or film construction systems.
To produce the cured materials, in the process of the invention, the compositions for inventive use are applied to conventional temporary or permanent substrates.
For producing films and moldings it is preferred to use conventional temporary substrates, such as metallic and plastic belts and sheets or hollow bodies of metal, glass, plastic, wood or ceramic, which can be easily removed without damaging the moldings and films that are produced from the compositions.
Where the compositions are used for producing coatings, adhesives, and seals, permanent substrates are used, such as bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, containers, packaging, small parts, optical, mechanical, and electrical components, and components for white goods.
The films and moldings produced by means of the process of the invention may likewise serve as permanent substrates.
In terms of method the application of the compositions for use in the process of the invention has no peculiarities but can instead take place by all conventional application methods suitable for the composition in question, such as, for example, extrusion, electrocoating, injecting, spraying, including powder spraying, knifecoating, brushing, pouring, dipping, trickling or rolling. Preference is given to employing extrusion methods and spray application methods. During application it is advisable to operate in the absence of actinic radiation, in order to prevent premature crosslinking of the compositions.
BASF Coatings AG 16 May 04, 2006 In one preferred embodiment of the process of the invention the compositions are used in the form of films, particularly in the form of planar laminates, comprising at least one film of a composition and also, where appropriate, at least one backing film, preferably of a thermoplastic.
In one particularly preferred embodiment of the process of the invention the films or laminates are shaped before being cured.
Shaping takes place preferably by thermoforming and/or by injection backmolding with thermoplastics or reactive precursors of plastics (reaction injection molding) in conventional injection molding machines. This results in shaped films or laminates, still curable, on correspondingly shaped plastic substrates.
Where the curable films or laminates comprise at least one thermoplastic backing film, the films or laminates are preferably connected with the substrates or precursors thereof in such a way that the backing films are facing away from the UV radiation sources.
Following their application the compositions are cured in the manner described at the outset.
The resultant cured materials, particularly the resulting films, moldings, coatings, adhesive layers, and seals, are outstandingly suitable for the coating, adhesive bonding, sealing, wrapping, and packaging of bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, containers, packaging, small parts, such as nuts, bolts, vvheel rims or hub caps, optical components, mechanical components, electrical components, such as windings (coils, stators, rotors), and also components for white goods, such as radiators, household appliances, refrigerator casings or washing-machine casings.
The process of the invention affords very particular advantages when used for producing clearcoats.
The clearcoats are normally the outermost coats of multicoat paint systems or of films and/or laminates, substantially determining the overall visual appearance and protecting the substrates and/or the color and/or effect coats of multicoat paint systems or films BASF Coatings AG 17 May 04, 2006 and/or laminates from mechanical and chemical damage and from damage by radiation.
Consequently, deficiencies in the hardness, scratch resistance, chemical resistance, and yellowing stability in the clearcoat are manifested to a particularly marked extent.
However, the clearcoats produced by the procedure of the invention exhibit no more than a low level of yellowing. They are highly scratch-resistant and, after being scratched, exhibit only very low levels of loss of gloss. In particular the loss of gloss in the Amtec/Kistler carwash simulation test is very low. At the same time they have a high level of hardness and a particu-arly high chemical resistance. Not least, they exhibit outstanding substrate adhesion and intercoat adhesion, particularly in connection with exposure to a steam jet.
Examples Preparation example 1 The preparation of a free rad ecafly curable or crosslinkable urethane acrylate A urethane acrylate was prepared from the synthesis components specified below, by coarsely dispersing hydrogenated bisphenol A in 2-hydroxyethyl acrylate at 60 C with stirring. Added to this suspension were the isocyanates, hydroquinone monomethyl ether, 1,6-di-tert-butyl-para-cresol, and methyl ethyl ketone. Following the addition of dibutyltin dilaurate there was an increase in the temperature of the batch. It was stirred at an internal temperature of 75 C for a number of hours until there was virtually no longer any change in the NCO value of the reaction mixture. Any free isocyanate groups still present after the reaction were converted by adding a small amount of methanol.
Synthesis components:
104.214 g of hydrogenated bisphenol A (corresponding to 0.87 equivalent of hydroxyl groups);
147.422 g (corresponding to 0.77 equivalent of isocyanate groups) of Basonat from BASF AG = commercial isocyanurate of hexamethylene diisocyanate having an NCO
content of 21.5%-22.5 / (DIN EN ISO 11909);
147.422 g (corresponding to 0.77 equivalent of isocyanate groups) of Sasonat from BASF AG = commercial biuret of hexamethylene diisocyanate having an NCO
BASF Coatings AG 18 May 04, 2006 content of 22%-23% (DIN EN ISO 11909);
124.994 g (corresponding to 0.51 equivalent of isocyanate groups) of Vestanat from Degussa = commercial isocyanurate of isophorone diisocyanate having an NCO
content of 11.7%-12.3% (DIN EN ISO 11909);
131.378 g of 2-hydroxyethyl acrylate (corresponding to 1.13 equivalents of hydroxyl groups);
0.328 g of hydroquinone monomethyl ether (0.05% on solids);
0.655 g of 1,6-di-tert-butyl-para-cresol (0.1 % on solids);
methyl ethyl ketone (70% solids);
0.066 g of dibutyltin dilaurate (0.01% on solids);
METHOD FOR. PRODUUNG SC RATC H RESISTANT CURED MATERIALS
Field of the 9nvenltaon!
The present invention relates to a new process for producing cured materials.
The present invention further relates to the use of the cured materials produced by means of the new process for the coating, adhesive bonding, sealing, wrapping, and packaging of bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, freight containers, packaging, small parts, optical, mechanical, and electrical components, and components for white goods.
Prior Art The cured materials are preferably thermoset materials. For the purposes of the present invention, thermoset materials are three-dimensionally crosslinked substances which in contrast to thermoplastic materials are deformable only to a small extent or not at all on heating.
A process for producing cured materials is known from German patent application DE 102 02 565 Al. In the known process the cured materials are produced from a composition, curable thermally and with actinic radiation, by heating and exposure to UV
radiation, for which (1) a composition curable thermally and with actinic radiation is used which, after it has cured, has a storage modulus E' in the rubber-elastic range of at least 10' S Pa and a loss factor tan6 at 20 C of not more than 0.10, the storage modu lus E.' arld the loss factor having been measured by means of dynamic mechanical thermoanalysis (DMTA) on free films with a thickness of 40 10 m, and (2) exposure is carried out with UV radiation whose spectrum comprises, in addition to UV-A and UV-B, a UV-C fraction which in the wavelength range from 200 to 280 nm has from 2 to 80% of the relative spectral radiance of the spectrum of a medium-pressure mercury vapor lamp within this wavelength range, the relative spectral radiance of the UV-C fraction in the wavelength range from 200 to 240 nm BASF Coatings AG 2 May 04, 2006 always being smaller than the relative spectral radiance of the spectrum of a medium-pressure mercury vapor lamp within this wavelength range, and (3) the radiation dose is from 100 to 6000 mJ cm,2.
For the purposes of the present invention actinic radiation means electromagnetic radiation, examples being near infrared (NIR), visible light, UV radiation, X-rays or gamma radiation, preferably UV radiation, and also corpuscular radiation, examples being electron beams, beta radiation, neutron beams, proton beams, and alpha radiation, preferably electron beams. Actinic radiation means, in particular, UV radiation.
The spectrum of UV radiation is known to be divided into three regions:
UV-A: 320 to 400 nm UV-B: 320 to 290 nm UV-C: 290 to 100 nm In general the UV spectrum of UV radiation sources is available only down to a wavelength of 180 - 200 nm, since the lower-wavelength radiation is absorbed by the hollow quartz bodies of the radiation sources (cf. R. Stephen Davidson, "Exploring the Science, Technology and Applications of U.V. and E.S. Curing", Sita Technology Ltd., London, 1999, Chapter I, "An Overview", pages 3 to 34).
The yellowing of the resultant known cured materials is low. They are scratch-resistant and, after being scratched, display minor loss of gloss. At the same time their hardness and chemical resistance are high.
The continually growing demands of the market, however, call for further improvement in the scratch resistance of cured materials, particularly their scratch resistance when exposed to automatic wash lines. In addition it is necessary to achieve further improvement in the adhesion of the cured materials to substrates, particularly those of metals, plastics, and other cured materials. A particular need is to further improve the intercoat adhesion between coats of cured materials which differ in physical composition and/or functions, particularly in multicoat paint systems.
BASF Coatings AG 3 May 04, 2006 Problem It is an object of the present invention to provide a new process for producing cured materials that no longer has the disadvantages of the prior art but instead, in a particularly simple and particularly reliable way, affords cured materials which meet the advantageous profile of requirements set out above and, furthermore, exhibit improved scratch resistance, particularly on exposure in wash lines, and also improved adhesion to substrates, particularly those of metals, plastics, and other cured materials.
The new process ought in particular to afford cured materials which have improved intercoat adhesion between coats of cured materials which differ in physical composition and/or function, particularly in multicoat paint systems, and particularly on exposure to a steam jet.
Solution Found accordingly has been the new process for producing cured materials from compositions curable with actinic radiation ("compositions") by exposure to UV
radiation, using UV radiation of the following spectral distribution and dose:
- wavelength lambda = 400 to 320 nm; dose = 500 to 2500 mJ/cm2;
- wavelength lambda = 320 to 290 nm; dose = 700 to 3000 mJ/cm2;
- wavelength lambda = 290 to 180 nm; dose = 100 to 500 mJ/cm2.
The new process for producing cured materials is referred to below as the "process of the invention".
Further subject matter of the invention will emerge from the description.
Advantages of the inventiion In the light of the prior art it was surprising and unforeseeable for the skilled worker that the object on which the present invention was based could be achieved by means of the process of the invention.
In particular it was surprising that the process of the invention, in a particularly simple and reliable way, using conventional UV radiation sources, using conventional electronic, optical, and mechanical components, and using conventional irradiation units, afforded, in BASF Coatings AG 4 May 04, 2006 a particularly simple and particularly reliable way, cured materials, especially thermoset materials, which not only exhibited low yellowing, high hardness, and high chemical resistance but also, furthermore, had improved scratch resistance, particularly on exposure in wash lines, and also had improved adhesion to substrates, particularly those of metals and plastics and other cured materials. In particular, the process of the invention afforded cured materials which exhibited improved intercoat adhesion between coats of cured materials differing in physical composition and/or function, particularly in multicoat paint systems, and particularly on exposure to a steam jet.
Even more surprising was that the process of the invention could be carried out with UV-curable compositions differing very widely in constitution. As a result, in an unexpectedly advantageous way, it was possible to tailor the compositions optimally to a very wide variety of end uses, so that they could be used with advantage as coating materials, adhesives, sealants, and starting materials for moldings and films. In particular it was surprising that the coating materials could be used with particular advantage as electrocoat materials, surfacers, antistonechip primers, solid-color topcoat, basecoat, and clearcoat materials.
A surprise not least was the extraordinarily broad usefulness of the cured materials as coatings, adhesive layers, seals, moldings, and films, preferably as coatings, especially electrocoats, surfacer coats, antistonechip primer coats, solid-color topcoats, basecoats, and clearcoats. They were especially suitable outstandingly for the coating, adhesive bonding, sealing, and packaging of bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, freight containers, packaging, small parts, such as nuts, bolts, wheel rims or hub caps, optical components, mechanical components, electrical components, such as windings (coils, stators, rotors), and components for white goods, such as radiators, household appliances, refrigerator casings or washing-machine casings.
etai8ed description of the invention The process of the invention serves for producing cured materials, especially thermoset materials, from compositions curable with actinic radiation (referred to for the sake of brevity below as "compositions") by exposure to UV radiation.
BASF Coatings AG 5 May 04, 2006 In accordance with the invention the UV radiation used is of the following spectral distribution and dose:
wavelength lambda = 400 to 320 nm; dose = 500 to 2500 and preferably 750 to 2000 mJ/cmz;
- wavelength lambda = 320 to 290 nm; dose = 700 to 3000 and preferably 1000 to 2200 mJ/cm2;
wavelength lambda = 290 to 180 nm; dose = 100 to 500 and preferably 200 to 450 mJ/cmz.
The power may vary widely. The UV radiation used is preferably of the following spectral distribution and power:
wavelength lambda = 400 to 320 nm; power = 100 to 600 and preferably 120 to 550 mVr!/cm2;
wavelength lambda = 320 to 290 nm; power = 100 to 600 and preferably 140 to 550 mVi//cm2;
wavelength lambda = 290 to 180 nm; power = 20 to 120 and preferably 30 to 100 mVV/cm2.
For irradiation in the context of the process of the invention, broad variation is possible in the distance of the UV radiation source from the surface of the composition.
The distance is preferably 20 to 250 mm and in particular 40 to 100 mm.
For a given dose, the irradiation period is guided by the belt speed or rate of advance of the substrates in the irradiation unit, and vice versa.
As radiation sources for the UV radiation for inventive use it is possible to use any conventional UV lamps which as such emit the relevant spectrum. Use may also be made, however, of combinations of at least two UV lamps which, although not emitting the UV
radiation for inventive use, have spectra which nevertheless add to give the UV radiation for inventive use. In addition it is possible to use UV lamps where the desired spectrum is set by means of filters and/or reflectors. Flash lamps are also suitable.
Examples of suitable flash lamps are flash lamps from the company VISIT.
BASF Coatings AG 6 May 04, 2006 As UV lamps it is preferred to use mercury vapor lamps, more preferably low-, medium-and high-pressure mercury vapor lamps, especially medium-pressure mercury vapor lamps. Particular preference is given to using unmodified mercury vapor lamps plus appropriate filters and/or reflectors, or mercury vapor lamps which have been modified, in particular by doping.
Examples of suitable modified mercury vapor lamps are gallium-doped and/or iron-doped lamps, especially iron-doped mercury vapor lamps, as described, for example, in R. Stephen Davidson, "Exploring the Science, Technology and Applications of U.V. and E.S. vuring", Sita Technology Ltd., London, 1999, Chapter I, "An Overview", page 16, Figure 10, or in ipl.-Ing. Peter Klamann, "eltosch System-Kompetenz, UV-Technik, Leitfaden fur Anwender", page 2, October 1998.
Examples of suitable unmodified mercury vapor lamps plus appropriate filters and/or reflectors are the UV lamps from Arccure. These lamps are constructed so that the compositions for curing are not struck directly by any UV radiation but only indirectly reflected radiation in two bundled streaks. For both reflected streaks it is possible to use different reflectors, which reflect the entire UV spectrum ("broad"), reflect the long-wave component of the UV spectrum more extensively onto the plastic moldings ("A+B"), or reflect the short-wave component of the UV spectrum more extensively onto the sample ( 9))_ The arrangement of the radiation sources may be adapted to the spatial circumstances of the compositions and/or of the substrates to which they have been applied, and also the process parameters. In the case of substrates of complex shape, such as are envisaged, for example, for automobile bodies, those regions not accessible to direct radiation (shadow regions), such as cavities, folds, and other structural undercuts, can be cured using pointwise, small-area or all-round sources, in conjunction with an automatic movement means for the irradiation of cavities or edges.
In the context of the process of the invention it is preferred to carry out irradiation under an oxygen-depleted atmosphere.
"Oxygen-depleted" means that the oxygen content of the atmosphere at the surface of the compositions is lower than the oxygen content of air (20.95% by volume). The maximum oxygen content of the oxygen-depleted atmosphere is preferably 18%, more preferably BASF Coatings AG 7 May 04, 2006 16%, very preferably 14%, with particular preference 10%, and in particular 6.0% by volume.
The atmosphere may in principle by oxygen-free; that is, it comprises an inert gas. The complete or substantial absence of oxygen may also be obtained, however, by masking the surface of the compositions with an oxygen-impermeable film.
The absence of the inhibitory effect of oxygen, however, may in such cases produce a sharp acceleration in radiation curing, as a result of which inhomogeneities and stresses may arise in the coatings of the invention. It is therefore not advantageous in all cases to lower the oxygen content of the atmosphere to a volume percentage of zero.
The minimum oxygen content is preferably 0.1 % and in particular 0.5% by volume.
The oxygen-depleted atmosphere may be provided in a variety of ways. It is preferred to produce an appropriate gas mixture and to make it available in pressurized cannisters.
More preferably the depletion is brought about by introducing at least one inert gas in the respective amounts required into the cushion of air situated over the surface of the layers that are to be cured. The oxygen content of the atmosphere situated over the surface in question can be measured continuously by means of conventional methods and devices for determining elemental oxygen, and where appropriate can be adjusted automatically to the desired level.
By inert gas is meant a gas which under the curing conditions employed is not broken down by the actinic radiation, does not inhibit curing and/or does not react with the compositions. Preference is given to using nitrogen, carbon dioxide, helium, neon or argon, especially nitrogen and/or carbon dioxide.
The compositions used for the process of the invention are curable with actinic radiation, especially UV radiation. This means that they comprise or consist of constituents which can be activated with actinic radiation and so undergo free-radical or ionic polymerization, especially including free-radical polymerization. This results in three-dimensional crosslinking of the compositions to give the cured materials, particularly the thermoset materials.
The compositions may additionally be curable physically and/or thermally.
BASF Coatings AG 8 May 04, 2006 For the purposes of the present invention the term "physical curing" denotes the curing of the compositions, in particular in the form of a film of a coating material, by filming as a result of solvent emission from the compositions, with linking within the coating taking place via looping of the polymer molecules of the binders (regarding the term cf. Rompp Lexikon Lacke und Druckfarben, Georg Thieme Veriag, Stuttgart, New York, 1998, "Binders", pages 73 and 74). Or else filming takes place via the coalescence of binder particles (cf. R mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Curing", pages 274 and 275). Normally no crosslinking agents are needed for this purpose.
For the purposes of the present invention the term "thermal curing" denotes the heat-initiated curing of a composition, in particular of a film of a coating material, in which normally a binder and a separate crosslinking agent are employed. This is normally referred to by those in the art as external crosslinking. Where the crosslinking agents are already incorporated in the binders, the term "self-crosslinking" is also used. In accordance with the invention, external crosslinking is of advantage and is therefore employed with preference (cf. R mpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, I~_!ew York, 1998, "Curing", pages 274 to 276, especially page 275, bottom).
Those in the art also refer to compositions curable with actinic radiation and thermally as dual-cure compositions.
In the process of the invention it is preferred to use compositions which, after they have been cured, have a storage modulus E' in the rubber-elastic range of at least 10' 5, preferably at least 10' 6, more preferably at least 108 , and in particular at least 108.3 Pa and a loss factor tanS at 20 C of not more than 0.10, preferably not more than 0.06, the storage modulus E and the loss factor having been measured by means of dynamic mechanical thermoanalysis (DMTA) on free films having a thickness of 40 10 m.
The recoverable energy component (elastic component) in the deformation of a viscoelastic material such as a polymer, for example, is determined by the parameter of the storage modulus E, whereas the energy component consumed (dissipated) in this process is described by the parameter of the loss modulus E". The moduli E' and E" are dependent on deformation rate and temperature. The loss factor tan8 is defined as the ratio of the loss modulus E" to the storage modulus E'. tan8 can be determined by means BASF Coatings AG 9 May 04, 2006 of dynamic mechanical thermoanalysis (DMTA) and constitutes a measure of the relationship between the elastic and plastic properties of the film. DMTA is a widely known measurement method for determining the viscoelastic properties of coatings and is described, for example, in Murayama, T., Dynamic Mechanical Analysis of Polymeric Materials, Elsevier, New York, 1978 and Loren W. Hill, Journal of Coatings Technology, Vol. 64, No. 808, May 1992, pages 31 to 33. The method conditions relating to the measurement of tanb by means of DMTA are described in detail by Th. Frey, K.-H. Grof3e Brinkhaus, and U. R ckrath in Cure Monitoring of Thermoset Coatings, Progress In Organic Coatings 27 (1996), 59-66, or in German patent application DE 44 09 715 Al or German patent DE 197 09 467 C2. Preference is given to employing the following conditions: tensile mode; amplitude: 0.2%; frequency: 1 Hz; temperature ramp:
1 C/min from room temperature to 200 C.
The storage modulus E' can be adjusted by the skilled worker through the selection of particular actinic radiation-curable and also, where appropriate, physically and/or thermally curable constituents, the functionality of the constituents, and their proportion as a fraction of the composition for inventive use.
The storage modulus E' can generally be adjusted, by means of constituents curable with actinic radiation, by selecting the nature and amount of the constituents preferably such that for each gram of composition soiids there are 0.5 to 6.0, preferably 1.0 to 4.0, and more preferably 2.0 to 3.0 meq of bonds which can be activated with actinic radiation.
For the purposes of the present invention the "solids" means the sum of those constituents of a composition that build up the cured material produced from said composition.
For the purposes of the present invention a bond which can be activated with actinic radiation is a bond which when exposed to actinic radiation becomes reactive and, together with other activated bonds of its kind, enters into polymerization reactions and/or crosslinking reactions which proceed in accordance with free-radical and/or ionic mechanisms. Examples of suitable bonds are single carbon-hydrogen bonds or single or double carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon bonds. Of these, the double carbon-carbon bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention.
For the sake of brevity they are referred to below as "double bonds".
BASF Coatings AG 10 May 04, 2006 Particularly preferred compounds containing double bonds are compounds containing acrylate groups.
The compositions may contain acid groups. Where the latter are used they are present in an amount of more than 0.05, preferably more than 0.08, very preferably more than 0.15, and in particular more than 0.2 meq/g solids. The amount of acid groups present should not exceed 15, preferably 10, more preferably 8, and in particular 5 meq/g solids.
Where acid groups are used they are selected preferably from the group consisting of carboxyl groups, phosphonic acid groups, sulfonic acid groups, acidic phosphate ester groups, and acidic sulfate ester groups, especially carboxyl groups.
The physical constitution of the compositions for use in the process of the invention is not critical; instead, all conventional compositions curable with actinic radiation, especially UV
radiation, and also, if desired, curable physically and/or thermally, can be used.
Suitable constituents of such compositions, the suitable compositions themselves, and the processes for preparing them are known, for example, from German patent application DE
102 02 565 Al, page 4, paragraph [0029], to page 8, paragraph [0079], or from German patent DE 197 09 467 C2.
The process of the invention affords particular advantages if carried out with compositions comprising at least one free-radically crosslinkable or curable component which (i) contains one or more oligourethane and/or one or more polyurethane (meth)acrylates and which has (ii) on average more than one olefinically unsaturated double bond per molecule, (iii) a number-average molecular weight of 1000 to 10 000 daltons, (iv) a double bond content of 1.0 to 5.0 double bonds per 1000 g of free-radically crosslinkable component, (v) on average per molecule > 1 branch point, (vi) 5 to 50% by weight, based in each case on the weight of the component, of cyclic structural elements, and (vii) at least one aliphatic structural element having at least 6 carbon atoms in the chain, BASF coag6ngs AG 11 PAT 01275 PC'f May 04, 2006 the free-radically crosslinkable component containing carbamate and/or biuret and/or allophanate and/or urea and/or amide groups.
The free-radically crosslinkable component preferably contains at least 50% by weight, more preferably contains at least 70% by weight, and very preferably contains at least 80% by weight, based in each case on the solids content of the free-radically crosslinkable component, of one or more oligourethane (meth)acrylates and/or one or more polyurethane (meth)acrylates. In particular, the free-radically crosslinkable component is composed of 100% of one or more oligourethane (meth)acrylates and/or one or more polyurethane (meth)acrylates.
The free-radically crosslinkable component also contains preferably not more than 50% by weight, more preferably not more than 30% by weight, and very preferably not more than 20% by weight, of further monomers, but preferably oligomers and/or polymers, especially polyester (meth)acrylates, epoxy (meth)acrylates, (meth)acryloyl-functional (meth)acrylic copolymers, polyether (meth)acrylates, unsaturated polyesters, amino (meth)acrylates, melamine (meth)acrylates and/or silicone (meth)acrylates, preferably polyester (meth)acrylates and/or epoxy (meth)acrylates and/or polyether (meth)acrylates.
Preference is given here to polymers which in addition to the double bonds also contain hydroxyl, carboxyl, amino and/or thiol groups. In the great majority of cases the use of further free-radically crosslinkable constituents is superfluous.
The free-radically crosslinkable component contains preferably less than 5% by weight, more preferably less than 1% by weight, based in each case on the weight of the free-radically crosslinkable component, and in particular contains substantially no detectable free isocyanate groups.
Additionally it is preferred for the free-radically crosslinkable component to comprise a mixture of different oligourethane and/or polyurethane (meth)acrylates, which may also have different double bond contents, molecular weights, double bond equivalent weights, branch point contents and levels of cyclic and also relatively long-chain aliphatic structural elements, and different amounts of carbamate, biuret, allophanate, amide and/or urea groups.
This mixture may be obtained by mixing different oligourethane or polyurethane (meth)acrylates or by the preparation of different products simultaneously during the preparation of a corresponding oligourethane and/or polyurethane (meth)acrylate.
BASF Coatings AG 12 May 04, 2006 In order to obtain effective crosslinking it is preferred to use free-radically crosslinkable components whose functional groups are of high reactivity, more preferably free-radically crosslinkable components containing acrylic double bonds as functional groups.
The urethane (meth)acrylates can be prepared in a way which is known to the skilled worker, from a compound containing isocyanate groups and from at least one compound containing groups that are reactive toward isocyanate groups, preparation then taking place by mixing of the components in any order, where appropriate at an elevated temperature.
It is preferred to add the compound containing groups that are reactive toward isocyanate groups to the compound containing isocyanate groups, preferably in two or more steps.
In particular the urethane (meth)acrylates are obtained by initially introducing the diisocyanate or polyisocyanate and subsequently adding at least one hydroxyalkyl (meth)acrylate or hydroxyalkyl ester of other olefinically unsaturated carboxylic acids, so ;giving rise to reaction initially of some of the isocyanate groups.
Subsequently a chain extender from the group of the diols/polyols and/or diamines/polyamines and/or dithiols/polythiols and/or alkanolamines is added and in this way the remaining isocyanate groups are reacted with the chain extender.
A further possibility is to prepare the urethane (meth)acrylates by reacting a di- or polyisocyanate with a chain extender and subsequently reacting the remaining free isocyanate groups with at least one olefinically unsaturated hydroxyalkyl ester.
It will be appreciated that all forms intermediate between these two techniques are also possible. For example, some of the isocyanate groups of a diisocyanate can first be reacted with a diol, subsequently a further portion of the isocyanate groups can be reacted with the olefinically unsaturated hydroxyalkyl ester, and thereafter the remaining isocyanate groups can be reacted with a diamine.
In general the reaction is carried out at temperatures between 5 and 100 C, preferably between 20 to 90 C, and more preferably between 40 and 80 C, and in particular between 60 and 80 C.
It is preferred here to operate under anhydrous conditions. "Anhydrous" means here that BASF Coatings AG 13 May 04, 2006 the water content of the reaction system is not more than 5% by weight, preferably not more than 3% by weight, and more preferably not more than 1% by weight. In particular the water content is below the detection limit.
In order to suppress polymerization of the polymerizable double bonds it is preferred to operate under an oxygen-containing gas, more preferably air or air/nitrogen mixtures.
As an oxygen-containing gas it is possible with preference to use air or a mixture of oxygen or of air and a gas which is inert under the conditions of use. As the inert gas use may be made of nitrogen, helium, argon, carbon monoxide, carbon dioxide, steam, lower hydrocarbons, or mixtures thereof.
The oxygen content of the oxygen-containing gas can be, for example, between 0.1% and 22% by volume, preferably from 0.5% to 20%, more preferably 1% to 15%, very preferably 2% to 10%, and in particular 4% to 10% by volume. It will be appreciated that, if desired, higher oxygen contents can also be used.
The reaction can also be carried out in the presence of an inert solvent, examples being acetone, isobutyl methyl ketone, methyl ethyl ketone, toluene, xylene, butyl acetate or ethoxyethyl acetate.
Through the selection of the nature and amount of di- and/or polyisocyanate, chain extender, and hydroxyalkyl ester employed, control is exerted over the further variables of the urethane (meth)acrylates, such as, for example, double bond content, double bond equivalent weight, amount of branch points, amount of cyclic structural elements, amount of aliphatic structural elements having at least 6 carbon atoms, and amount of biuret, allophanate, carbamate, urea and/or amide groups, and the like.
Through the selection of the particular amounts of di- or polyisocyanate and chain extender that are employed and also through the functionality of the chain extender it is also possible, furthermore, to prepare urethane (meth)acrylates which as well as the ethylenically unsaturated double bonds also contain other functional groups, examples being hydroxyl groups, carboxyl groups, amino groups and/or thiol groups or the like.
Especially if the urethane (meth)acrylate is to be used in aqueous compositions, some of the free isocyanate groups present in the reaction mixtures are also reacted with compounds which contain an isocyanate-reactive group, selected preferably from the BASF Coatings AG 14 May 04, 2006 group consisting of hydroxyl, thiol, and primary and secondary amino groups, especially hydroxyl groups, and also at least one, especially one, acid group, selected preferably from the group consisting of carboxyl groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups, especially carboxyl groups. Examples of suitable compounds of this kind are hydroxyacetic acid, hydroxypropionic acid or gamma-hydroxybutyric acid, especially hydroxyacetic acid (glycolic acid).
For the process of the invention the compositions may be present in any of a very wide variety of physical states and three-dimensional forms.
For instance, at room temperature, the compositions may be solid or liquid or fluid. They may also, however, be solid at room temperature and fluid at higher temperatures, with preferably a thermoplastic behavior being displayed. In particular they may be conventional compositions comprising organic solvents, aqueous compositions, substantially or entirely solvent-free and water-free liquid compositions (100% systems), substantially or entirely solvent-free and water-free solid powders, or substantially or entirely solvent-free powder suspensions (powder slurries). The dual-cure compositions may additionally be one-component systems, where the binders and crosslinking agents are present alongside one another, or two-component or multicomponent systems, where the binders and crosslinking agents are separate from one another until shortly before application.
In terms of method the preparation of the compositions for inventive use has no peculiarities but instead takes place by the mixing and homogenization of the above-described constituents by means of conventional mixing techniques and apparatus such as stirred tanks, agitator mills, extruders, compounders, Ultraturrax devices, inline dissolvers, static mixers, micromixers, toothed-wheel dispersers, pressure release nozzles and/or microfluidizers, preferably in the absence of actinic radiation. The selection of the method that is optimum for a given individual case is guided in particular by the physical state and the three-dimensional form which the composition is to have. Where, for example, a thermoplastic composition is present in the preferred form of a film or a laminate, extrusion through a slot die is particularly appropriate for producing the composition and shaping it.
For the purposes of the process of the invention the compositions are used for producing cured materials, especially thermoset materials, which serve a very wide variety of end uses.
BASF coattregs AG 15 PAT 01275 PcT
May 04, 2006 The compositions are preferably starting products for moldings and films or are coating materials, adhesives, and sealants.
The cured materials are preferably moldings, films, coatings, adhesive layers, and seals.
The coating materials are employed in particular as electrocoat materials, surfacers, antistonechip primers, solid-color topcoat materials, aqueous basecoat materials and/or clearcoat materials, especially clearcoat materials, for producing single-coat or multicoat color and/or effect, electrically conductive, magnetically shielding or fluorescent paint systems, especially multicoat color and/or effect paint systems. The multicoat paint systems can be produced using the conventional wet-on-wet techniques and/or extrusion techniques and also the conventional paint or film construction systems.
To produce the cured materials, in the process of the invention, the compositions for inventive use are applied to conventional temporary or permanent substrates.
For producing films and moldings it is preferred to use conventional temporary substrates, such as metallic and plastic belts and sheets or hollow bodies of metal, glass, plastic, wood or ceramic, which can be easily removed without damaging the moldings and films that are produced from the compositions.
Where the compositions are used for producing coatings, adhesives, and seals, permanent substrates are used, such as bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, containers, packaging, small parts, optical, mechanical, and electrical components, and components for white goods.
The films and moldings produced by means of the process of the invention may likewise serve as permanent substrates.
In terms of method the application of the compositions for use in the process of the invention has no peculiarities but can instead take place by all conventional application methods suitable for the composition in question, such as, for example, extrusion, electrocoating, injecting, spraying, including powder spraying, knifecoating, brushing, pouring, dipping, trickling or rolling. Preference is given to employing extrusion methods and spray application methods. During application it is advisable to operate in the absence of actinic radiation, in order to prevent premature crosslinking of the compositions.
BASF Coatings AG 16 May 04, 2006 In one preferred embodiment of the process of the invention the compositions are used in the form of films, particularly in the form of planar laminates, comprising at least one film of a composition and also, where appropriate, at least one backing film, preferably of a thermoplastic.
In one particularly preferred embodiment of the process of the invention the films or laminates are shaped before being cured.
Shaping takes place preferably by thermoforming and/or by injection backmolding with thermoplastics or reactive precursors of plastics (reaction injection molding) in conventional injection molding machines. This results in shaped films or laminates, still curable, on correspondingly shaped plastic substrates.
Where the curable films or laminates comprise at least one thermoplastic backing film, the films or laminates are preferably connected with the substrates or precursors thereof in such a way that the backing films are facing away from the UV radiation sources.
Following their application the compositions are cured in the manner described at the outset.
The resultant cured materials, particularly the resulting films, moldings, coatings, adhesive layers, and seals, are outstandingly suitable for the coating, adhesive bonding, sealing, wrapping, and packaging of bodies of means of transport, especially motor-vehicle bodies, and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, containers, packaging, small parts, such as nuts, bolts, vvheel rims or hub caps, optical components, mechanical components, electrical components, such as windings (coils, stators, rotors), and also components for white goods, such as radiators, household appliances, refrigerator casings or washing-machine casings.
The process of the invention affords very particular advantages when used for producing clearcoats.
The clearcoats are normally the outermost coats of multicoat paint systems or of films and/or laminates, substantially determining the overall visual appearance and protecting the substrates and/or the color and/or effect coats of multicoat paint systems or films BASF Coatings AG 17 May 04, 2006 and/or laminates from mechanical and chemical damage and from damage by radiation.
Consequently, deficiencies in the hardness, scratch resistance, chemical resistance, and yellowing stability in the clearcoat are manifested to a particularly marked extent.
However, the clearcoats produced by the procedure of the invention exhibit no more than a low level of yellowing. They are highly scratch-resistant and, after being scratched, exhibit only very low levels of loss of gloss. In particular the loss of gloss in the Amtec/Kistler carwash simulation test is very low. At the same time they have a high level of hardness and a particu-arly high chemical resistance. Not least, they exhibit outstanding substrate adhesion and intercoat adhesion, particularly in connection with exposure to a steam jet.
Examples Preparation example 1 The preparation of a free rad ecafly curable or crosslinkable urethane acrylate A urethane acrylate was prepared from the synthesis components specified below, by coarsely dispersing hydrogenated bisphenol A in 2-hydroxyethyl acrylate at 60 C with stirring. Added to this suspension were the isocyanates, hydroquinone monomethyl ether, 1,6-di-tert-butyl-para-cresol, and methyl ethyl ketone. Following the addition of dibutyltin dilaurate there was an increase in the temperature of the batch. It was stirred at an internal temperature of 75 C for a number of hours until there was virtually no longer any change in the NCO value of the reaction mixture. Any free isocyanate groups still present after the reaction were converted by adding a small amount of methanol.
Synthesis components:
104.214 g of hydrogenated bisphenol A (corresponding to 0.87 equivalent of hydroxyl groups);
147.422 g (corresponding to 0.77 equivalent of isocyanate groups) of Basonat from BASF AG = commercial isocyanurate of hexamethylene diisocyanate having an NCO
content of 21.5%-22.5 / (DIN EN ISO 11909);
147.422 g (corresponding to 0.77 equivalent of isocyanate groups) of Sasonat from BASF AG = commercial biuret of hexamethylene diisocyanate having an NCO
BASF Coatings AG 18 May 04, 2006 content of 22%-23% (DIN EN ISO 11909);
124.994 g (corresponding to 0.51 equivalent of isocyanate groups) of Vestanat from Degussa = commercial isocyanurate of isophorone diisocyanate having an NCO
content of 11.7%-12.3% (DIN EN ISO 11909);
131.378 g of 2-hydroxyethyl acrylate (corresponding to 1.13 equivalents of hydroxyl groups);
0.328 g of hydroquinone monomethyl ether (0.05% on solids);
0.655 g of 1,6-di-tert-butyl-para-cresol (0.1 % on solids);
methyl ethyl ketone (70% solids);
0.066 g of dibutyltin dilaurate (0.01% on solids);
4.500 g of methanol (corresponding to 0.14 equivalent of hydroxyl groups).
The characteristics of the resulting urethane acrylate (free-radically crosslinkable component) were as follows:
- on average 2.2 ethylenically unsaturated double bonds per molecule;
- a double bond content of 1.74 double bonds per 1000 g of urethane acrylate solids;
- on average 2.2 branch points per molecule;
- 25% by weight of cyclic structural elements, based on the solids content of the urethane acrylate.
Preparation example 2 The preparation of aW-curab@e clearcoat materba9 A suitable stirrer vessel was initially charged with 100.00 parts by weight of the above-described organic solution of the urethane acrylate from preparation example 1.
Added to the initial charge over the course of 30 minutes was a mixture of 1.0 part by BASF Coatings AG 19 May 04, 2006 weight of Tinuvin0 292 (commercial HALS light stabilizer from Ciba Specialty Chemicals, based on a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), 2.0 parts by weight of Tinuvin0 400 (commercial light stabilizer from Ciba Specialty Chemicals, based on a mixture of 2-(4-((2-hydroxy-3-dodecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(4-((2-hydroxy-3-tridecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine), 0.8 part by weight of Lucirin0 TPO-L
(commercial photoinitiator from BASF Aktiengesellschaft, based on 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide), 2.40 parts by weight of Irgacure0 184 (commercial photoinitiator from Ciba Specialty Chemicals, based on 1-hydroxycyclohexyl phenyl ketone) and 0.2 part by weight of SykO 306 (commercial additive from Byk Chemie, based on a polyether-modified polydimethylsiloxane) with continual stirring at room temperature, and the resulting mixture was dissolved in 3-butoxy-2-propanol and adjusted with 3-butoxy-2-propanol to a solids content of 48%. It was then stirred at room temperature for 30 minutes.
Preparation examp@e 3 The production of a coated thermoplastic backing film The backing film used was a thermoplastic film of LuranO S 778 TE from BASF
Aktiengesellschaft with a thickness of 800 pm. The surface of the backing film that was to be coated was subjected to a corona pretreatment at 0.5 kilowatt.
The film was coated on one side with a metallic aqueous basecoat material (color: "silver metallic"). The basecoat material was applied to the backing film using a box-type coating bar with a width of 37 cm at a belt speed of 0.5 m/min. Application was carried out with a gentle airflow of 0.2 m/s, at a constant temperature of 21 1 C, and at a constant relative humidity of 65 5%. The thickness of the resulting wet basecoat film (first basecoat film) was 100 pm. The wet first basecoat film was flashed off under these conditions for 3 minutes and then dried to a residual volatiles content of 4% by weight, based on the first basecoat film. The resulting conditioned first basecoat film, with a thickness of approximately 20 pm, was adjusted with chill rolls to a surface temperature <
30 C.
Applied to the conditioned and temperature-adjusted first basecoat film was the same basecoat material, under the following conditions, using a system for pneumatic spray application:
BASF C atsngs AG 20 May 04, 2006 - outflow rate: 100 ml/min;
- air pressures: atomizer air: 2.5 bar; horn air: 2.5 bar;
- rate of travel of the nozzles: high enough to result in a spray-jet overlap of 60%;
The characteristics of the resulting urethane acrylate (free-radically crosslinkable component) were as follows:
- on average 2.2 ethylenically unsaturated double bonds per molecule;
- a double bond content of 1.74 double bonds per 1000 g of urethane acrylate solids;
- on average 2.2 branch points per molecule;
- 25% by weight of cyclic structural elements, based on the solids content of the urethane acrylate.
Preparation example 2 The preparation of aW-curab@e clearcoat materba9 A suitable stirrer vessel was initially charged with 100.00 parts by weight of the above-described organic solution of the urethane acrylate from preparation example 1.
Added to the initial charge over the course of 30 minutes was a mixture of 1.0 part by BASF Coatings AG 19 May 04, 2006 weight of Tinuvin0 292 (commercial HALS light stabilizer from Ciba Specialty Chemicals, based on a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), 2.0 parts by weight of Tinuvin0 400 (commercial light stabilizer from Ciba Specialty Chemicals, based on a mixture of 2-(4-((2-hydroxy-3-dodecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(4-((2-hydroxy-3-tridecyloxypropyl)oxy)-2-hydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine), 0.8 part by weight of Lucirin0 TPO-L
(commercial photoinitiator from BASF Aktiengesellschaft, based on 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide), 2.40 parts by weight of Irgacure0 184 (commercial photoinitiator from Ciba Specialty Chemicals, based on 1-hydroxycyclohexyl phenyl ketone) and 0.2 part by weight of SykO 306 (commercial additive from Byk Chemie, based on a polyether-modified polydimethylsiloxane) with continual stirring at room temperature, and the resulting mixture was dissolved in 3-butoxy-2-propanol and adjusted with 3-butoxy-2-propanol to a solids content of 48%. It was then stirred at room temperature for 30 minutes.
Preparation examp@e 3 The production of a coated thermoplastic backing film The backing film used was a thermoplastic film of LuranO S 778 TE from BASF
Aktiengesellschaft with a thickness of 800 pm. The surface of the backing film that was to be coated was subjected to a corona pretreatment at 0.5 kilowatt.
The film was coated on one side with a metallic aqueous basecoat material (color: "silver metallic"). The basecoat material was applied to the backing film using a box-type coating bar with a width of 37 cm at a belt speed of 0.5 m/min. Application was carried out with a gentle airflow of 0.2 m/s, at a constant temperature of 21 1 C, and at a constant relative humidity of 65 5%. The thickness of the resulting wet basecoat film (first basecoat film) was 100 pm. The wet first basecoat film was flashed off under these conditions for 3 minutes and then dried to a residual volatiles content of 4% by weight, based on the first basecoat film. The resulting conditioned first basecoat film, with a thickness of approximately 20 pm, was adjusted with chill rolls to a surface temperature <
30 C.
Applied to the conditioned and temperature-adjusted first basecoat film was the same basecoat material, under the following conditions, using a system for pneumatic spray application:
BASF C atsngs AG 20 May 04, 2006 - outflow rate: 100 ml/min;
- air pressures: atomizer air: 2.5 bar; horn air: 2.5 bar;
- rate of travel of the nozzles: high enough to result in a spray-jet overlap of 60%;
5- nozzle/film distance: 30 cm.
Application was carried out under a gentle airflow of 0.5 m/s (impinging vertically on the film), at a constant temperature of 21 1 C, and at a constant relative humidity of 65 5%. The thickness of the resulting wet basecoat film (second basecoat film) was 50 2pm. The second basecoat film was flashed off under these conditions for 3 minutes and then dried to a residual volatiles content of 4% by weight, based on the second basecoat film. The air temperature was 90 C, the humidity 10 g/min, and the air speeds 10 m/s. The resulting conditioned second basecoat film, with a thickness of about 10 pm,, was adjusted with chill rolls to a surface temperature < 30 C.
Atop the conditioned and temperature-adjusted second basecoat film was applied the UV-curable clearcoat material of preparation example 2, using a box-type coating bar with a width of 37 cm. Application was carried out with a gentle airflow of 0.2 m/s, at a constant temperature of 21 1 C, and at a constant relative humidity of 65 5%. The thickness of the resulting wet clearcoat film was 120 pm. It was flashed off under the stated conditions for 6 minutes and then dried to a residual volatiles content of 2.5% by weight, based on the clearcoat film. The air temperature in the oven was 119 C for all drying stages. The resulting dried but not yet fully cured coating, with a coat thickness of 60 pm, was adjusted with chill rolls to a surface temperature < 30 C and coated with the polypropylene protective film described in DE 103 35 620 Al, example 1 (commercial product from Bischof + Klein, Lengerich).
The multilayer film which resulted was wound up into a roll and stored in this form until further use.
ExampBes 1 to 3 The production of plas4ac moldings Plastic moldings were produced in accordance with the following general instructions:
The multilayer film of preparation example 3 was preformed. Subsequently the transparent BASF Coatings AG 21 May 04, 2006 coating, as yet not fully cured, was stripped of its protective film and then crosslinked fully using UV radiation. The positive mold used was a cube. The resulting preformed part was inserted into a mold. The mold was closed and the cube was injection backmolded with a liquid plastic material.
Irradiation was carried out using a UV lamp from Arccure (undoped mercury tube). The construction of this lamp was such that there was no direct impingement of UV
radiation on the plastic moldings; instead, only indirectly reflected radiation impinged on the moldings, in two bundled streaks. Different reflectors could be used for both reflected streaks, which reflected the total UV spectrum ("broad"), which reflected the long-wave component of the UV spectrum more extensively onto the plastic moldings ("A+13"), or which reflected the short-wave component of the UV spectrum more extensively onto the sample ("C"). In the case of examples 1 and 3 to 6 the reflector arrangement selected, viewed in the direction of travel of the plastic moldings through the UV
exposure unit, was as follows: 1. "broad" and 2. "C". In the case of example 2 the reflector arrangement chosen was as follows: 1. "A+B" and 2. "A+B"
The plastic moldings were irradiated in an oxygen-depleted carbon dioxide atmosphere.
The table gives an overview of the shortest distances employed between the UV
radiation source and the surface of the clearcoat film on the plastic moldings, the oxygen content of the atmosphere over the clearcoat film, the spectral distribution, with the associated dose and power, and the scratch resistance and adhesion of the resulting clearcoats on the plastic moldings.
BASF Coatings AG 22 May 04, 2006 Table: Curing of the clearcoat films with UV radiation, and important properties of the clearcoats Example Dost,a) 02 b) se') Powerd) Amtece) sif) No. (mm) (% by v i,) (Mj/cM2) (MW/cMZ) (residual (index) gloss %) 0!!-A l0l9-B UF1-C UV-A UV-B U!1-C
1 40 0.5 782 1058 205 - - - 79.3 sat.
2 40 0.9 915 1240 251 474 467 77 81 sat.
3 40 0.8 854 1194 235 470 474 78 87.7 sat.
a) distance between UV radiation source and clearcoat film surface;
b) oxygen content of atmosphere above the clearcoat film;
c), d) measured using a PowerPuck from EIT;
e) residual gloss after exposure in the Amtec/Kistler carwash simulation test with cleaning (wiping with petroleum ether);
f) steamjet test;
In the case of the carwash simulation test a laboratory wash line from Amtec Kistler was used (cf. T. Klimmasch, T. Engbert, Technologietage, Cologne, DFO, report volume 32, pages 59 to 66, 1997). The stress induced was determined by measuring the residual gloss of the sample after the carwash simulation test and subsequent wiping with a wipe soaked with petroleum ether. Residual gloss levels of more than 80% were achieved.
For the steamjet test, in accordance with the Daimler-Benz steamjet testing instructions that are known in the art, a St. Andrew's cross was scored into the clearcoats of each of examples 1 to 6. The scored areas were subjected to a waterjet spray (Walter instrument model LTA2; pressure: 67 bar; water temperature: 60 C; nozzle tip/test specimen distance: 10 cm; exposure time: 60 seconds; instrument setting: F 1).
The degree of flaking and subfilm migration was assessed visually. In all cases the result was sat. (satisfactory).
BASF Coatings AG 23 May 04, 2006 The results in the table underline the fact that the clearcoats on the plastic moldings of examples 1 to 6 exhibited very good intercoat adhesion and high scratch resistance, especially under realistic conditions.
In other respects the clearcoats on the plastic moldings of examples 1 to 6 were bright and had a very high gloss (20 ) in accordance with IN 67530. They were hard, fiexible, chemical-resistant, and free from disruptive yellowing.
Application was carried out under a gentle airflow of 0.5 m/s (impinging vertically on the film), at a constant temperature of 21 1 C, and at a constant relative humidity of 65 5%. The thickness of the resulting wet basecoat film (second basecoat film) was 50 2pm. The second basecoat film was flashed off under these conditions for 3 minutes and then dried to a residual volatiles content of 4% by weight, based on the second basecoat film. The air temperature was 90 C, the humidity 10 g/min, and the air speeds 10 m/s. The resulting conditioned second basecoat film, with a thickness of about 10 pm,, was adjusted with chill rolls to a surface temperature < 30 C.
Atop the conditioned and temperature-adjusted second basecoat film was applied the UV-curable clearcoat material of preparation example 2, using a box-type coating bar with a width of 37 cm. Application was carried out with a gentle airflow of 0.2 m/s, at a constant temperature of 21 1 C, and at a constant relative humidity of 65 5%. The thickness of the resulting wet clearcoat film was 120 pm. It was flashed off under the stated conditions for 6 minutes and then dried to a residual volatiles content of 2.5% by weight, based on the clearcoat film. The air temperature in the oven was 119 C for all drying stages. The resulting dried but not yet fully cured coating, with a coat thickness of 60 pm, was adjusted with chill rolls to a surface temperature < 30 C and coated with the polypropylene protective film described in DE 103 35 620 Al, example 1 (commercial product from Bischof + Klein, Lengerich).
The multilayer film which resulted was wound up into a roll and stored in this form until further use.
ExampBes 1 to 3 The production of plas4ac moldings Plastic moldings were produced in accordance with the following general instructions:
The multilayer film of preparation example 3 was preformed. Subsequently the transparent BASF Coatings AG 21 May 04, 2006 coating, as yet not fully cured, was stripped of its protective film and then crosslinked fully using UV radiation. The positive mold used was a cube. The resulting preformed part was inserted into a mold. The mold was closed and the cube was injection backmolded with a liquid plastic material.
Irradiation was carried out using a UV lamp from Arccure (undoped mercury tube). The construction of this lamp was such that there was no direct impingement of UV
radiation on the plastic moldings; instead, only indirectly reflected radiation impinged on the moldings, in two bundled streaks. Different reflectors could be used for both reflected streaks, which reflected the total UV spectrum ("broad"), which reflected the long-wave component of the UV spectrum more extensively onto the plastic moldings ("A+13"), or which reflected the short-wave component of the UV spectrum more extensively onto the sample ("C"). In the case of examples 1 and 3 to 6 the reflector arrangement selected, viewed in the direction of travel of the plastic moldings through the UV
exposure unit, was as follows: 1. "broad" and 2. "C". In the case of example 2 the reflector arrangement chosen was as follows: 1. "A+B" and 2. "A+B"
The plastic moldings were irradiated in an oxygen-depleted carbon dioxide atmosphere.
The table gives an overview of the shortest distances employed between the UV
radiation source and the surface of the clearcoat film on the plastic moldings, the oxygen content of the atmosphere over the clearcoat film, the spectral distribution, with the associated dose and power, and the scratch resistance and adhesion of the resulting clearcoats on the plastic moldings.
BASF Coatings AG 22 May 04, 2006 Table: Curing of the clearcoat films with UV radiation, and important properties of the clearcoats Example Dost,a) 02 b) se') Powerd) Amtece) sif) No. (mm) (% by v i,) (Mj/cM2) (MW/cMZ) (residual (index) gloss %) 0!!-A l0l9-B UF1-C UV-A UV-B U!1-C
1 40 0.5 782 1058 205 - - - 79.3 sat.
2 40 0.9 915 1240 251 474 467 77 81 sat.
3 40 0.8 854 1194 235 470 474 78 87.7 sat.
a) distance between UV radiation source and clearcoat film surface;
b) oxygen content of atmosphere above the clearcoat film;
c), d) measured using a PowerPuck from EIT;
e) residual gloss after exposure in the Amtec/Kistler carwash simulation test with cleaning (wiping with petroleum ether);
f) steamjet test;
In the case of the carwash simulation test a laboratory wash line from Amtec Kistler was used (cf. T. Klimmasch, T. Engbert, Technologietage, Cologne, DFO, report volume 32, pages 59 to 66, 1997). The stress induced was determined by measuring the residual gloss of the sample after the carwash simulation test and subsequent wiping with a wipe soaked with petroleum ether. Residual gloss levels of more than 80% were achieved.
For the steamjet test, in accordance with the Daimler-Benz steamjet testing instructions that are known in the art, a St. Andrew's cross was scored into the clearcoats of each of examples 1 to 6. The scored areas were subjected to a waterjet spray (Walter instrument model LTA2; pressure: 67 bar; water temperature: 60 C; nozzle tip/test specimen distance: 10 cm; exposure time: 60 seconds; instrument setting: F 1).
The degree of flaking and subfilm migration was assessed visually. In all cases the result was sat. (satisfactory).
BASF Coatings AG 23 May 04, 2006 The results in the table underline the fact that the clearcoats on the plastic moldings of examples 1 to 6 exhibited very good intercoat adhesion and high scratch resistance, especially under realistic conditions.
In other respects the clearcoats on the plastic moldings of examples 1 to 6 were bright and had a very high gloss (20 ) in accordance with IN 67530. They were hard, fiexible, chemical-resistant, and free from disruptive yellowing.
Claims (24)
1. A process for producing cured materials from compositions curable with actinic radiation ("compositions") by exposure to UV radiation, which comprises using UV
radiation of the following spectral distribution and dose:
- wavelength lambda = 400 to 320 nm, dose = 500 to 2500 mJ/cm2;
- wavelength lambda = 320 to 290 nm; dose = 700 to 3000 mJ/cm2;
- wavelength lambda = 290 to 180 nm; dose = 100 to 500 mJ/cm2.
radiation of the following spectral distribution and dose:
- wavelength lambda = 400 to 320 nm, dose = 500 to 2500 mJ/cm2;
- wavelength lambda = 320 to 290 nm; dose = 700 to 3000 mJ/cm2;
- wavelength lambda = 290 to 180 nm; dose = 100 to 500 mJ/cm2.
2. The process as claimed in claim 1, wherein UV radiation of the following spectral distribution and power is used:
- wavelength lambda = 400 to 320 nm; dose = 750 to 2000 mJ/cm2;
- wavelength lambda = 320 to 290 nm; dose = 1000 to 2200 mJ/cm2, - wavelength lambda = 290 to 180 nm, dose = 200 to 450 mJ/cm2.
- wavelength lambda = 400 to 320 nm; dose = 750 to 2000 mJ/cm2;
- wavelength lambda = 320 to 290 nm; dose = 1000 to 2200 mJ/cm2, - wavelength lambda = 290 to 180 nm, dose = 200 to 450 mJ/cm2.
3. The process as claimed in claim 1 or 2, wherein UV radiation of the following spectral distribution and power is used:
- wavelength lambda = 400 to 320 nm; power = 100 to 600 mW/cm2, - wavelength lambda = 320 to 290 nm, power = 100 to 600 mW/cm2;
- wavelength lambda = 290 to 180 nm, power = 20 to 120 mW/cm2.
- wavelength lambda = 400 to 320 nm; power = 100 to 600 mW/cm2, - wavelength lambda = 320 to 290 nm, power = 100 to 600 mW/cm2;
- wavelength lambda = 290 to 180 nm, power = 20 to 120 mW/cm2.
4. The process as claimed in claim 3, wherein UV radiation of the following spectral distribution and power is used:
- wavelength lambda = 400 to 320 nm; power = 120 to 550 mW/cm2, - wavelength lambda = 320 to 290 nm, power = 140 to 550 mW/cm2, - wavelength lambda = 290 to 180 nm; power = 30 to 100 mW/cm2.
- wavelength lambda = 400 to 320 nm; power = 120 to 550 mW/cm2, - wavelength lambda = 320 to 290 nm, power = 140 to 550 mW/cm2, - wavelength lambda = 290 to 180 nm; power = 30 to 100 mW/cm2.
5. The process as claimed in any one of claims 1 to 4, wherein during the irradiation the distance between the UV radiation source and the surface of the composition is 20 to 250 mm.
6. The process as claimed in claim 5, wherein the distance is 40 to 100 mm.
7. The process as claimed in any one of claims 1 to 6, wherein during irradiation the oxygen content of the atmosphere at the surface of the compositions is depleted
8. The process as claimed in claim 7, wherein the oxygen content of the atmosphere is < 18% by volume
9. The process as claimed in any one of claims 1 to 8, wherein the compositions are additionally curable physically and/or thermally
10. The process as claimed in any one of claims 1 to 9, wherein the compositions are in the form of films or constituents of laminates.
11. The process as claimed in any one of claims 1 to 10, wherein after they have been cured the compositions have a storage modulus E' in the rubber-elastic region of at least 10 7 5 Pa and a loss factor tan.delta. at 20°C of not more than 0 10, the storage modulus E' and the loss factor tan6 having been measured by means of dynamic mechanical thermoanalysis (DMTA) on free films having a thickness of 40 ~ 10 µm.
12. The process as claimed in any one of claims 1 to 11, wherein the amount of bonds which can be activated with UV radiation in the compositions is 0 5 to 6 meq/g solids.
13. The process as claimed in claim 12, wherein the amount of bonds which can be activated with UV radiation is 1 to 4 meq/g solids.
14. The process as claimed in claim 12 or 13, wherein the bonds which can be activated with UV radiation are double carbon-carbon bonds.
15. The process as claimed in any one of claims 1 to 14, wherein the compositions comprise at least one free-radically crosslinkable component which (i) contains one or more oligourethane and/or one or more polyurethane (meth)acrylates and which has (ii) on average more than one olefinically unsaturated double bond per molecule, (iii) a number-average molecular weight of 1000 to 10 000 daltons, (iv) a double bond content of 1.0 to 5.0 double bonds per 1000 g of free-radically crosslinkable component, (v) on average per molecule > 1 branch point, (vi) 5 to 50% by weight, based in each case on the weight of the component, of cyclic structural elements, and (vii) at least one aliphatic structural element having at least 6 carbon atoms in the chain, the free-radically crosslinkable component containing carbamate and/or biuret and/or allophanate and/or urea and/or amide groups.
16. The process as claimed in any one of claims 1 to 15, wherein the compositions are coating materials, adhesives, sealants, and starting products for moldings and films.
17. The process as claimed in claim 16, wherein the cured materials are coatings, adhesive layers, seals, moldings, and films.
18. The process as claimed in claim 16, wherein the coating materials are electrocoat materials, surfacers or antistonechip primers, solid-color topcoat materials, basecoat materials or clearcoat materials that serve to produce coatings.
19. The process as claimed in claim 17 or 18, wherein the coatings are electrocoats, surfacer coats, antistonechip primer coats, solid-color topcoats, basecoats or clearcoats.
20. The process as claimed in claim 18 or 19, wherein the coatings are multicoat color and/or effect paint systems or films and/or laminates.
21. The process for producing cured materials as claimed in any one of claims 1 to 19, wherein the compositions are applied to permanent or temporary substrates and exposed to UV radiation.
22. The process as claimed in claim 21, wherein the substrates are composed of metal, plastic, glass, wood, textile, leather, natural stone, artificial stone, concrete, cement or assemblies of these materials.
23. The process as claimed in claim 21 or 22, wherein the moldings and films are removed from the temporary substrates.
24. The process as claimed in any one of claims 21 to 23, wherein the permanent substrates are bodies of means of transport and parts thereof, the interior and exterior of constructions and parts thereof, doors, windows, furniture, hollow glassware, coils, containers, packaging, small parts, optical, mechanical and electrical components, and components for white goods.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005024362.2 | 2005-05-27 | ||
| DE102005024362A DE102005024362A1 (en) | 2005-05-27 | 2005-05-27 | Process for producing scratch-resistant hardened materials |
| PCT/EP2006/062139 WO2006125723A1 (en) | 2005-05-27 | 2006-05-09 | Method for producing scratch-resistant cured materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2606100A1 true CA2606100A1 (en) | 2006-11-30 |
Family
ID=36778319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002606100A Abandoned CA2606100A1 (en) | 2005-05-27 | 2006-05-09 | Method for producing scratch-resistant cured materials |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1885773A1 (en) |
| JP (1) | JP2008545829A (en) |
| KR (1) | KR20080015417A (en) |
| CN (1) | CN101184793A (en) |
| CA (1) | CA2606100A1 (en) |
| DE (1) | DE102005024362A1 (en) |
| MX (1) | MX2007010949A (en) |
| WO (1) | WO2006125723A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008060906A1 (en) * | 2008-12-09 | 2010-06-10 | Innovative Oberflächentechnologie GmbH | High network density polymer surface and method of making the same |
| DE102008061244A1 (en) * | 2008-12-10 | 2010-06-17 | Innovative Oberflächentechnologie GmbH | Process and apparatus for direct radiation-induced polymerization and crosslinking of acrylates and methacrylates |
| DE102009047755A1 (en) * | 2009-12-09 | 2011-06-16 | DESIGNquadrat GbR (vertretungsberechtigte Gesellschafter Alexander Christ, 50679 Köln, Guido Endert, 42799 Leichlingen, Horst Wergen, 42105 Wuppertal) | Solid surface |
| EP2374547A1 (en) * | 2010-04-08 | 2011-10-12 | Co-Energy Engineering B.V. | Method and device for curing a coating |
| CN103210438A (en) * | 2010-11-17 | 2013-07-17 | 旭硝子株式会社 | Transparent protective plate, flat panel display, and method for producing flat panel display |
| CN102218858A (en) * | 2011-03-28 | 2011-10-19 | 无锡市瑞莺合成革有限公司 | Multifunctional composite textile processing method |
| CN103877826A (en) * | 2014-02-26 | 2014-06-25 | 金甲化工企业(中山)有限公司 | Method for removing formaldehyde in air |
| JP2017155182A (en) * | 2016-03-04 | 2017-09-07 | 信越化学工業株式会社 | Photo-hardening method of silicone rubber surface, and silicone rubber molded body |
| WO2020022855A1 (en) * | 2018-07-27 | 2020-01-30 | 주식회사 엘지화학 | Infrared ray reflective film |
| CN111413245B (en) * | 2020-04-07 | 2022-11-22 | 佛山市儒林化工有限公司 | Method for measuring solid content of UV irradiation metal printing coating |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2442879C3 (en) * | 1973-09-17 | 1978-12-14 | Nippon Paint Co., Ltd., Osaka (Japan) | Process for curing light-curable paints and coating compounds |
| CH660489A5 (en) * | 1984-08-31 | 1987-04-30 | Bernhard Glaus | METHOD AND DEVICE FOR CURING POLYMERIZABLE COATING MEASURES ON NON-TEXTILE SUBSTRATES. |
| DE3527404C1 (en) * | 1985-07-31 | 1987-01-02 | Kurz Leonhard Fa | Process for producing a film having a textured lacquer layer |
| DE3600577A1 (en) * | 1986-01-10 | 1987-07-16 | Wangner Gmbh Co Kg Hermann | METHOD FOR MENDING DAMAGES IN PAPER MACHINE COVERS |
| DE4336748C3 (en) * | 1992-11-17 | 2001-09-06 | Ciba Sc Holding Ag | Process for flash drying and curing, use of the process and suitable devices |
| DE19754621C2 (en) * | 1997-12-09 | 2002-03-21 | Mze Engineering Fuer Verfahren | Process for hardening and increasing the scratch resistance of radiation-hardened lacquer layers |
| DE19818735A1 (en) * | 1998-04-27 | 1999-10-28 | Herberts Gmbh | Coating material cured using radiation used for repairing paint damage |
| DE10044374A1 (en) * | 2000-09-08 | 2002-08-08 | Tesa Ag | Process for crosslinking polyacrylates |
| DE10202565A1 (en) * | 2002-01-24 | 2003-08-07 | Basf Coatings Ag | Hardened materials, processes for their manufacture and their use |
| DE10237950A1 (en) * | 2002-08-20 | 2004-03-11 | Tesa Ag | Polyacrylate contact adhesive useful for making adhesive tape comprises a base-reactive polyacrylate thermally crosslinked with a photochemically generated base |
| DE10336426A1 (en) * | 2003-08-08 | 2005-03-10 | Basf Coatings Ag | Method and device for coating colored and unsupported substrates with a transparent coating |
-
2005
- 2005-05-27 DE DE102005024362A patent/DE102005024362A1/en not_active Ceased
-
2006
- 2006-05-09 EP EP06755083A patent/EP1885773A1/en not_active Withdrawn
- 2006-05-09 CN CNA200680018536XA patent/CN101184793A/en active Pending
- 2006-05-09 CA CA002606100A patent/CA2606100A1/en not_active Abandoned
- 2006-05-09 KR KR1020077027849A patent/KR20080015417A/en not_active Application Discontinuation
- 2006-05-09 MX MX2007010949A patent/MX2007010949A/en unknown
- 2006-05-09 JP JP2008512797A patent/JP2008545829A/en active Pending
- 2006-05-09 WO PCT/EP2006/062139 patent/WO2006125723A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008545829A (en) | 2008-12-18 |
| MX2007010949A (en) | 2007-11-07 |
| WO2006125723A1 (en) | 2006-11-30 |
| KR20080015417A (en) | 2008-02-19 |
| EP1885773A1 (en) | 2008-02-13 |
| DE102005024362A1 (en) | 2006-11-30 |
| CN101184793A (en) | 2008-05-21 |
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