EP0693002B2 - Verfahren zur herstellung von hoch-glänzend, strahlunghärtbaren beschichtungen - Google Patents
Verfahren zur herstellung von hoch-glänzend, strahlunghärtbaren beschichtungen Download PDFInfo
- Publication number
- EP0693002B2 EP0693002B2 EP94912806A EP94912806A EP0693002B2 EP 0693002 B2 EP0693002 B2 EP 0693002B2 EP 94912806 A EP94912806 A EP 94912806A EP 94912806 A EP94912806 A EP 94912806A EP 0693002 B2 EP0693002 B2 EP 0693002B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- weight
- radiation
- oxygen
- high gloss
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- 238000000034 method Methods 0.000 title claims abstract description 28
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- 239000008199 coating composition Substances 0.000 claims abstract description 40
- 230000005855 radiation Effects 0.000 claims abstract description 35
- 239000012298 atmosphere Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- -1 acrylyloxy groups Chemical group 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 23
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- 230000005865 ionizing radiation Effects 0.000 claims description 6
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- 239000010410 layer Substances 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
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- 239000002245 particle Substances 0.000 description 2
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- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MRUJVILJKBDVQK-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C=C MRUJVILJKBDVQK-UHFFFAOYSA-N 0.000 description 1
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- BRBMYNGGGPTKKL-UHFFFAOYSA-N 1,9-decanediol Chemical compound CC(O)CCCCCCCCO BRBMYNGGGPTKKL-UHFFFAOYSA-N 0.000 description 1
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- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
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- 239000004386 Erythritol Substances 0.000 description 1
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- 239000004606 Fillers/Extenders Substances 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001279 poly(ester amides) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B05D3/068—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 ionising radiations (gamma, X, electrons)
Definitions
- Radiation curable coatings are highly desirable because they can be cured without the need to evaporate substantial amounts of solvent. Therefore, curing can be accomplished rapidly and with less release of volatile organic compounds into the atmosphere. Also, radiation curing can be carried out at relatively low temperatures, thereby lending itself to use with temperature sensitive substrates such as wood and plastic. The use of electron beam radiation is particularly favored for curing thick coatings and coatings that are heavily pigmented.
- accelerator compounds e.g., tertiary amino compounds
- coating compositions to at least partially overcome the inhibition of curing due to oxygen, thereby increasing the amount of oxygen that can be permitted in the radiation curing chamber.
- accelerators provide processing advantages, they generally have deleterious effects on the coating, such as yellowing and/or surface roughness.
- the accelerators can sometimes also have a negative effect on the ease of applying the coating composition onto the substrate.
- Multi-step radiation curing processes which may include a combination of electron beam and ultraviolet radiation, have been employed to produce low gloss coatings.
- oxygen air
- Shrinkage of underlying layers during the first step caused pigment particles to be driven into the surface portions, whereby the surface contained a larger amount of pigment than the body of the film which reduced the gloss of the film without sacrificing film strength or rheology properties of the coating composition.
- U.S. Patent Nos. 3,918,393 (Hahn) and 4,048,036 (Prucnal) illustrate this approach.
- Multi-step radiation curing techniques have also been proposed for producing textured finishes in U.S. Patent Nos. 4,421,784 (Troue), 3,840,448 (Osbome et al.), and 4,411,931 (Duong) wherein surface wrinkling of the coating is induced by the staged curing process.
- Those of skill in the art would have considered two stage radiation cure processes inappropriate for producing high gloss finishes.
- the first step of the process of the present invention involves irradiation with an electron beam, followed by a subsequent step of exposure to ultraviolet radiation.
- the electron beam step may take place in air or in a partially inert atmosphere including at least 1000 ppm oxygen, preferably at least 2 percent oxygen by volume, whereby the surface of the coating remains wet or uncured.
- the ultraviolet radiation step takes place in a substantially inert atmosphere (less than 1000 parts per million oxygen) whereby curing of the coating is substantially completed. Although an inert atmosphere is required in the ultraviolet step, it may be noted that the conditions need not be controlled as rigorously as in prior art electron beam processes.
- the present invention is defined by the use of a radiation curable composition comprising :
- the present invention is furthermore defined by the method for producing a high gloss, radiation cured coating comprising: applying to a substrate a coating composition comprising:
- the binder or vehicle in the coating composition used in the present invention comprises at least one resin (monomer, oligomer, or polymer) which is curable by exposure to radiation in the presence of one or more of the photoinitiators disclosed herein. Binder constitutes 10 to 99, preferably 50 to 99, percent by weight of the total coating composition. Many such resins are known in the art and may be used in the present invention.
- the resins suitable for use in the present invention as defined above are characterized by inhibition of curing by the presence of oxygen (such as in air). Oxygen inhibition permits maintaining an at least partially uncured surface layer during the initial curing step with the electron beam.
- a particular category of useful radiation curable compounds are characterized by a plurality of acrylyloxy groups and the ability to free radically addition polymerize upon being initiated by a photoinitiator or ionizing radiation.
- acrylic unsaturation is used in its broad sense to mean the unsaturation provided by unsubstituted acrylyl groups or a-substituted acrylyl groups such as methacrylyl, ethacrylyl and a-chloroacrylyl.
- Examples of these compounds are the diacrylates and dimethacrylates of ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-diethylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 3-methylpentane-1,4-diol, 2,2-diethylbutane-1,3-dio
- polyacrylyloxy functional polyesters polyacrylyloxy functional polyesters, polamides, polyacrylates, polyethers, polycarbonates or polyurethanes as well as polyacrylyloxy functional compounds of mixed functionality such as polyacrylyloxy functional poly(ester-urethanes), poly(ester-amides) and poly(ether-urethanes). Mixtures of compounds having a plurality of acrylyloxy groups may be used, if desired.
- the amount of polymerizable compound having a plurality of acrylyloxy groups present in the coating composition is subject to wide variation.
- the compound is present in an amount in the range of from 10 to 99 percent by weight based on the weight of the binder of the coating composition.
- An amount in the range of from about 20 to 97 percent is typical. From about 30 to 95 percent by weight of the binder is preferred.
- Monomers having monoacrylic functionality which crosslinks with the compound having polyacrylyloxy functionality may optionally be present in the coating composition.
- monoacrylic functional monomers which may be used are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, hexyl ethyl acrylate, hexyl butyl acrylate, 2-ethyl hydroxy acrylate, octyl acrylate, hydroxy ethyl acrylate, hydroxy butyl acrylate, caprclactone-hydroxyl alkyl acrylate reaction products, and 2-ethyl hydroxy acrylate.
- the preferred monoacrylic functional monomers are liquid compounds miscible with the polyacrylyloxy compound.
- a benefit from the use of one or more monoacrylic functional monomers is that the monoacrylic functional monomer may act as a reactive solvent for the polyacrylyloxy functional compound, thereby providing coating compositions having a satisfactory low viscosity while using relatively small amounts or no volatile, nonreactive solvent.
- the monoacrylic functional monomer, or mixtures of monoacrylic functional monomers may be employed over a broad range, although none is required.
- the amount of such monomer when used should be sufficient to provide a liquid, flowable, interpolymerizable mixture.
- the monomer will ordinarily be present in the coating composition in the range of from about 0 to about 80 percent by weight of the binder of the coating composition.
- the monoacrylic functional monomer will be present in the range of from about 0 to about 30 percent by weight of the binder.
- monovalent functional monomers may be employed as known in the radiation curing art, including N-vinyl-2-pyrolidone, vinyl neodecanoate, and other ethylenic unsaturated monomers known to be suitable for radiation curable coatings.
- the present invention employs a coating composition containing a photoinitiator.
- Photoinitiators absorb radiation and thereby obtain energy to form free radicals that initiate polymerization of the binder resin.
- the photoinitiator in the present invention is one which forms free radicals upon exposure to actinic radiation, viz., ultraviolet light.
- photoinitiators are selected that are non-volatile, which is generally related to the molecular weight of the photoinitiator. Therefore, for the purpose of the present invention, the non-volatile photoinitiator is characterized by a molecular weight of at least 1000.
- photoinitiators one of skill in the art would consider it expedient to select compounds that are soluble and stabile in the particular composition.
- photoinitiators which may be used in the coating compositions.
- One class of compounds useful as photoinitiators in the present invention are acetophenone derivatives meeting the definition of non-volatile set forth above, in particular substituted acetophenone derivatives.
- Many acetophenone derivatives are known as photoinitiators, a large number of which are disclosed in U.S. Patent No. 4,229,274 (Carlblom).
- the amount of photoinitiator present in the coating composition is at least 0.01 weight percent based on total solids content of the coating composition. Although larger amounts could be used, it is usually uneconomical to use more than 5 percent of the photoinitiator. According to the present invention, the amount of photoinitiator does not exceed 4 weight percent. Typically, the photoinitiator may be present in an amount of at least 0.1 percent, most often in the range of from 0.5 percent to 2 percent. Mixtures of more than one photoinitiator compound may be used.
- the coating compositions employed in the present invention include a surfactant of the type that serves as a flow control agent or leveling agent selected from siloxane compounds and fluorocarbon compounds. Suitable products are commercially available for this purpose.
- the preferred class of flow control agents are siloxane compounds, examples of which are "BYK®-310, a polyester modified dimethylpolysiloxane” from Byk Chemie, Wallingford, Connecticut, and "Versaflow 102", a modified methyl siloxane from Shamrock Technologies, Inc., Newark, New Jersey.
- fluorocarbon flow control agents are the "Zonyl®” surfactants from DuPont and the “Fluororad®” surfactants, particularly "FC430,” from 3M.
- the flow control agents for use in the present invention are characterized by the property of assisting leveling of the coatings used in the present invention after application onto a substrate, without substantial interference with the application process itself.
- the flow control agent should have relatively low volatility.
- the flow control agent is present in the compcsition in amounts ranging from 0.01 to 1.0 percent by weight based on total solids content of the composition.
- Pigments may be included in the coating composition.
- opacifying pigments include titanium dioxide (rutile or anatase), zinc oxide, zirconium oxide, zinc sulfide and lithopone.
- coloring pigments include iron oxides, cadmium sulfide, carbon black, phthalocyanine blue, phthalocyanine green, indanthrone blue, ultramarine blue, chromium oxide, burnt umber, benzidine yellow, toluidine red, aluminum powder and aluminum flakes.
- extender pigments include silica, barytes, calcium carbonate, barium sulfate, talc, aluminum silicates, sodium aluminum silicates, potassium aluminum silicates and magnesium silicate.
- a single pigment may be used or mixtures of pigments may be employed.
- the pigment When the pigment is ultraviolet light absorbing, it should be used in amounts which do not preclude curing of the interior of the coating. The maximum amount is therefore related to the thickness of the coating to be cured. Thin coatings may tolerate more ultraviolet light absorbing pigment than thick coatings. When the pigment does not significantly absorb ultraviolet light, there is usually greater latitude in the amounts which may be employed.
- pigment When pigment is used, it is generally present in an amount in the range of from about 0.1 to about 70 percent by weight of the coating composition. Often it is present in an amount in the range of from about 0.5 to about 50 percent. Usually it is present in an amount in the range of from about 1 to about 35 percent by weight of the coating composition. Dyes and tints may optionally be included in the coating composition as replacements for all or some of the pigment content.
- resinous pigment dispersants e.g., cellulose acetate butyrate or resinous acrylics
- plasticizers e.g., cellulose acetate butyrate or resinous acrylics
- grinding vehicles such as non-reactive acrylics.
- resinous additives which are commercially available which may be used for these purposes. These additives are used in the manner and in amounts known to the art, such as 0 to 20 weight percent of the total composition.
- non-reactive, volatile organic solvent Another ingredient which is often included in coating compositions of this type is a non-reactive, volatile organic solvent.
- solvent may be present, but in lesser amounts than conventional. It is generally advantageous to minimize the amount of organic solvent, but if reduction of viscosity is desired for a particular application, the present invention does not preclude adding larger amounts of a non-reactive solvent or mixtures of several solvents.
- non-reactive organic solvents examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, secutyl alcohol, isobutyl alcohol, tert-butyl alcohol, amyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, cellosolve, ethyl cellosolve, cellosolve acetate, 2-ethylhexyl acetate, tetrahydrofuran, and aliphatic naphtha.
- solvent of this type it is ordinarily present in the coating composition in the range of from about 0.1 to about 40 percent by weight of the vehicle of the coating composition. From about 0 to about 15 percent is typical.
- the preferred compositions are solvent-free.
- the coating compositions used in the invention are usually prepared by simply admixing the various ingredients.
- the compounds comprising the photocatalyst system may be premixed and then admixed with the other ingredients of the coating composition or they may be added separately. Although mixing is usually accomplished at room temperature, elevated temperatures are sometimes used. The maximum temperature which is usable depends upon the heat stability of the ingredients. Temperatures above about 200°F (93°C) are only rarely employed.
- the radiation curable coating compositions employed in the invention are generally used to form cured adherent coatings on substrates.
- the substrate is coated with the coating composition using substantially any technique known to the art. These include spraying, curtain coating, dipping, roller application, printing, brushing, drawing and extrusion.
- Wet, uncured coatings, as applied to a substrate have thicknesses of at least 1.0 mil (0.025 millimeter), preferably at least 2.5 mils (0.06 millimeters), in order to achieve the high gloss effect of the present invention.
- Cured coatings of the ultraviolet light curable coating composition employed in the invention usually have thicknesses in the range of from 1 to 5 mils (0.025 to 0.13 millimeter). More often they have thicknesses in the range of from 2 to 4 mils (0.05 to 0.1 millimeter).
- Substrates which may be coated with the compositions may vary widely in their properties.
- Organic substrates such as wood, fiberboard, particle board, composition board, paper, cardboard and various polymers such as polyesters, polyamides, cured phenolic resins, cured aminoplasts, acrylics, polyurethanes and rubber may be used.
- Inorganic substrates are exemplified by glass, quartz and ceramic materials.
- Many metallic substrates may be coated. Exemplary metallic substrates are iron, steel, stainless steel, copper, brass, bronze, aluminum, magnesium, titanium, nickel, chromium, zinc and alloys.
- the method of curing the coating composition involves a two step radiation exposure wherein the applied coating layer is cured in a subsurface portion in a first step by exposure to ionizing radiation (e.g., electron beam radiation or laser) in the presence of oxygen (i.e., greater than 1000 ppm) whereby curing at the surface is inhibited.
- ionizing radiation e.g., electron beam radiation or laser
- oxygen i.e., greater than 1000 ppm
- the curing is completed throughout the remainder of the coating thickness by means of ultraviolet radiation in an at least partially inert atmosphere (i.e., less than 1000 ppm oxygen).
- Suitable electron beam radiation for use in the first curing step may constitute a dose of 2 to 10 megarads, preferably 3 to 7 megarads, at 150 to 300 kiloelectron volts, preferably about 250 kiloelectron volts. Line speeds of 50 to 120 feet per minute (15 to 36 meters per minute) are suitable.
- the exposure in the first ste is chosen so as to substantially cure the portion of the coating closest to the substrate. A portion of the coating thickness nearest to the surface will remain at least partially uncured due to oxygen inhibition.
- the atmosphere in the vicinity of the coating during the electron beam exposure should include at least 1000 ppm oxygen, preferably at least 2 percent oxygen by volume.
- Any suitable source which emits ultraviolet light viz., electromagnetic radiation having a wavelength in the range of from about 180 to about 400 nanometers, may be used in the practice of the second curing step.
- Suitable sources are mercury arcs, carbon arcs, medium pressure mercury lamps, high pressure mercury lamps, swirl-flow plasma arc, ultraviolet light-emitting diodes and ultraviolet light emitting lasers.
- Particularly preferred are ultraviolet light emitting lamps of the medium or high pressure mercury vapor type. Such lamps usually have fused quartz envelopes to withstand the heat and transmit the ultraviolet radiation and are ordinarily in the form of long tubes having an electrode at either end.
- the time of exposure to ultraviolet light and the intensity of the ultraviolet light to which the coating composition is exposed may vary greatly. For practical commercial line speeds, lamps rated at 200 watts per inch (7900 watts per meter) or greater are preferred. Generally the exposure to ultraviolet light should continue until either the film is thermoset throughout or at least cured to the point where subsequent reactions cause the film to become thermoset throughout. Exposure of the coating to ultraviolet light may be accomplished in the presence of an inert atmosphere, viz., an atmosphere either containing no oxygen or only a concentration of oxygen which insignificantly inhibits polymerization of the coating surface (less than 1000 parts per million oxygen). Gases such as nitrogen, argon, carbon dioxide or mixtures thereof are typically the major components of inert atmospheres, although other unreactive gases may be used. Nitrogen is generally employed for this purpose.
- Coatings produced in accordance with the present invention exhibit gloss and distinctness of image comparable to that of coatings produced with full inerting (less than 200 parts oxygen per million). Gloss may conveniently be determined by the Standard Method of Test for Specular Gloss, ASTM Designation D-523-67 (Reapproval 1971). Using a Gardner 60° glossmeter, the gloss of cured coatings may exceed 70 percent reflected light, preferably greater than 80 percent, and with specific examples being in the range of 83 to 86 percent.
- a portion of the diacrylate together with the dispersant and the lampblack pigment were ground in a pigment mill with ceramic media. The grind was then flushed out of the mill with an additional portion of the diacrylate. The composition was then let down with the remainder of the diacrylate premixed with the cellulose acetate butyrate, the photoinitiator, and the siloxane flow control agent.
- composition above was applied at a wet film thickness of 2.5 mils (0.06 millimeters) with a curtain coater onto medium density fiberboard that has been filled, sealed, and sanded smooth.
- the coated substrate was cured by at a line speed of 100 feet per minute (30.5 meters per minute), first with an electron beam manufactured by Energy Sciences, Inc., of Woburn, Massachusetts, USA, set at 250 kilovolts terminal voltage and 23 milliamperes beam current, yielding 5 megarads of energy, in an atmosphere containing 10% oxygen by volume.
- the coated substrate was subjected to ultraviolet exposure from four medium pressure mercury vapor lamps of 200 watts per inch (80 watts per centimeter) manufactured by Aetek International, Plainfield, Illinois, USA, at a line speed of 80 feet per minute (24 meters per minute) in a fully inerted atmosphere (nitrogen with less than 200 parts per million oxygen).
- a highly glossy finish was produced as reported in Table 1.
- This example employs the same two stage curing process with electron beam and ultraviolet stages as used in Example 1, but uses a conventional radiation curable coating composition. Therefore, a polymeric surfactant was not included in the composition of this example. Also, a lower molecular weight photoinitiator was used ("Irgacure 651" from Ciba-Geigy Corp., Hawthorne, New York, having a molecular weight of 256). Substantially lower gloss was produced in this example as can be seen in Table 1.
- Example 2 employs the same prior art coating composition as in Example 2, but curing was carried out in a single stage process using only the electron beam described in Example 1. The electron beam stage was fully inerted. Even though curing was carried out in a fully inerted atmosphere, the results as reported in Table 1 were not as good as Example 1.
- Example 1 This example is the same as Example 4, with the exception that no photoinitiator was included in the coating composition in view of the use of a single stage electron beam curing process.
- Table 1 The results as reported in Table 1 are the same as Example 3, indicating that the presence of photoinitiator was not the cause of the inferior gloss of Example 3 relative to the present invention as represented by Example 1.
- Gloss D.O.I. Example 1 The invention 85 90
- Example 2 Prior art composition
- Example 3 Single stage
- Example 4 Single stage 85 80
- Example 1 the particular method of the present invention
- Example 2 when cured by a two stage process that does not employ full inerting in the electron beam stage, can yield finishes having gloss subtantially superior to that attained by a typical prior art compositions cured by the same process (Example 2). That this result can be attained without the need to fully inert the electron beam stage is highly advantageous and surprising. Also surprising is finding that the gloss attained by Example 1 (the invention) is better even than that produced by a fully inerted electron beam (Examples 3 and 4).
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- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paper (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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- Macromonomer-Based Addition Polymer (AREA)
Claims (10)
- Verwendung einer strahlungshärtbaren Zusammensetzung, die folgendes umfaßt:(a) 10-99 Gew-% eines Harzbinders, der in Anwesenheit von zumindest einer Photoinitiatorverbindung durch Strahlungsexposition härtbar ist, wobei das Harz aus solchen Harzen gewählt ist, die Acryloxygruppen enthalten und deren Härtung durch Strahlungsexposition durch die Anwesenheit von Sauerstoff im wesentlichen gehemmt wird;(b) 0,01-4 Gew-% eines nicht-flüchtigen Photoinitiators mit einem Molekulargewicht von wenigstens 1000 und(c) 0,01-1 Gew-% eines Verlaufmittels, gewählt aus der Gruppe bestehend aus Siloxanverbindungen und Fluorkohlenwasserstoffverbindungen,
in einem ersten Aussetzungsschritt Aussetzen der Beschichtung an ionisierende Strahlung in einer Atmosphäre, die mehr als 1000 parts per million Sauerstoff enthält, so daß eine unterhalb der Oberfläche liegende Schicht der Beschichtung zumindest teilweise gehärtet wird, während eine zumindest teilweise ungehärtete Oberflächenschicht zurückbleibt; und
in einem nachfolgenden Aussetzungsschritt Aussetzen der zumindest teilweise gehärteten Beschichtung in einer Atmosphäre, die weniger als 1000 parts per million Sauerstoff enthält, an ultraviolette Strahlung, die zur Härtung der Oberfläche der Beschichtung und zur Erzeugung einer Beschichtung mit einer hochglänzenden Oberfläche ausreichend ist. - Verwendung nach Anspruch 1, worin der Photoinitiator ein substituiertes Acetophenonderivat umfaßt.
- Verwendung nach Anspruch 1, worin das Verlaufmittel ein Polysiloxan ist.
- Verwendung nach Anspruch 1, worin wenigstens 10 Gewichtsprozent des Binders aus einer Polyacryloxyverbindung bestehen.
- Verwendung nach Anspruch 1, worin wenigstens 30 Gewichtsprozent des Binders aus einer Polyacryloxyverbindung bestehen.
- Verfahren zur Herstellung einer hochglänzenden, strahlungsgehärteten Beschichtung, das folgendes umfaßt:
Aufbringen einer Beschichtungszusammensetzung auf ein Substrat, die folgendes umfaßt:10-99 Gew-% eines strahlungshärtbaren Harzbinders, der Acryloxygruppen enthält und dessen Härtung durch Strahlungsexposition im wesentlichen durch die Anwesenheit von Sauerstoff gehemmt wird;0,01-4 Gew-% eines nicht-flüchtigen Photoinitiators mit einem Molekulargewicht von wenigstens 1000 und0,01-1 Gew-% eines Verlaufmittels, gewählt aus der Gruppe bestehend aus Siloxanverbindungen und Fluorkohlenwasserstoffverbindungen;
in einem nachfolgenden Aussetzungsschritt Aussetzen der zumindest teilweise gehärteten Beschichtung in einer Atmosphäre, die weniger als 1000 parts per million Sauerstoff enthält, an ultraviolette Strahlung, die zur Härtung der Oberfläche der Beschichtung und zur Erzeugung einer Beschichtung mit einer hochglänzenden Oberfläche ausreichend ist. - Verfahren nach Anspruch 6, worin der Photoinitiator ein substituiertes Acetophenonderivat umfaßt.
- Verfahren nach Anspruch 6, worin das Verlaufmittel Polysiloxan ist.
- Verfahren nach Anspruch 6, worin wenigstens 10 Gewichtsprozent des Binders aus einer Polyacryloxyverbindung bestehen.
- Verfahren nach Anspruch 6, worin wenigstens 30 Gewichtsprozent des Binders aus einer Polyacryloxyverbindung bestehen.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US4109393A | 1993-04-01 | 1993-04-01 | |
US41093 | 1993-04-01 | ||
PCT/US1994/002939 WO1994022596A1 (en) | 1993-04-01 | 1994-03-18 | Compositions and methods for producing high gloss radiaton curable coatings |
Publications (3)
Publication Number | Publication Date |
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EP0693002A1 EP0693002A1 (de) | 1996-01-24 |
EP0693002B1 EP0693002B1 (de) | 1997-10-15 |
EP0693002B2 true EP0693002B2 (de) | 2001-05-02 |
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94912806A Expired - Lifetime EP0693002B2 (de) | 1993-04-01 | 1994-03-18 | Verfahren zur herstellung von hoch-glänzend, strahlunghärtbaren beschichtungen |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0693002B2 (de) |
AT (1) | ATE159276T1 (de) |
CA (1) | CA2156293C (de) |
DE (1) | DE69406278T3 (de) |
DK (1) | DK0693002T3 (de) |
ES (1) | ES2109687T5 (de) |
GR (1) | GR3025646T3 (de) |
WO (1) | WO1994022596A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06172471A (ja) * | 1992-10-09 | 1994-06-21 | Henkel Hakusui Kk | 重合硬化性組成物とこれを用いて成形または被覆する方法 |
SE504783C2 (sv) | 1995-08-10 | 1997-04-21 | Triline Ab | Förfarande och anläggning för pulverlackering |
SE504784C2 (sv) * | 1995-08-10 | 1997-04-21 | Herberts Powder Coatings Ab | Förfarande för pulverlackering samt pulver för genomförande av förfarandet |
GB2327892B (en) | 1997-07-31 | 2001-11-14 | Perstorp Ltd | Improvements in or relating to curable coating |
DE10321812B4 (de) * | 2003-05-15 | 2009-10-08 | Daimler Ag | Verfahren zur Herstellung von Lackschichten mittels Härtung durch UV-Licht sowie dessen Verwendung |
US7661387B2 (en) | 2004-01-30 | 2010-02-16 | Dunfries Investment Limited | Dual laser coating apparatus and process |
CA2589150C (en) | 2004-11-29 | 2013-05-28 | Dsm Ip Assets B.V. | Method for reducing the amount of migrateables of polymer coatings |
EP4011988B1 (de) | 2016-04-11 | 2024-09-18 | Sun Chemical B.V. | Verfahren für elektronenstrahlhärtbare tintenstrahlformulierungen |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3918393A (en) † | 1971-09-10 | 1975-11-11 | Ppg Industries Inc | Method of producing flat (non-glossy) films |
EP0003002A2 (de) † | 1977-12-22 | 1979-07-11 | Ciba-Geigy Ag | Verwendung von aromatisch-aliphatischen Ketonen als Photoinitiatoren, photopolymerisierbare Systeme enthaltend solche Ketone und neue aromatisch-aliphatische Ketone |
EP0281941A2 (de) † | 1987-03-12 | 1988-09-14 | Ciba-Geigy Ag | Coreaktive Fotoinitiatoren |
EP0324483A2 (de) † | 1988-01-12 | 1989-07-19 | Mitsubishi Petrochemical Co., Ltd. | Verfahren zur Beschichtung eines Polyolefins mit einer harten Beschichtung |
DE4031732A1 (de) † | 1990-10-06 | 1992-04-09 | Basf Ag | Strahlenhaertbare, waessrige bindemitteldispersionen |
GB2259704A (en) † | 1991-09-23 | 1993-03-24 | Ciba Geigy Ag | Alkylbisacylphosphine oxides |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4048036A (en) * | 1974-10-24 | 1977-09-13 | Ppg Industries, Inc. | Process for producing films of low gloss by exposure to ultraviolet light |
EP0030213A1 (de) * | 1979-11-29 | 1981-06-10 | Ciba-Geigy Ag | Durch Licht vernetzbare Schicht auf Druckformen und Verfahren zur Herstellung von Offset-Druckplatten |
US4317858A (en) * | 1980-06-27 | 1982-03-02 | Westinghouse Electric Corp. | Ultraviolet curable solvent-free wire enamel blends |
US4309452A (en) * | 1980-10-01 | 1982-01-05 | Gaf Corporation | Dual gloss coating and process therefor |
US4326001A (en) * | 1980-10-01 | 1982-04-20 | Gaf Corporation | Radiation cured coating and process therefor |
JPS5897132A (ja) * | 1981-12-07 | 1983-06-09 | Fuji Photo Film Co Ltd | 磁気記録材料の製造方法 |
EP0311288A3 (de) * | 1987-09-30 | 1992-01-08 | Westinghouse Electric Corporation | Mit UV härtbare Harzzusammensetzungen |
AU615563B2 (en) * | 1988-07-29 | 1991-10-03 | Nippon Kayaku Kabushiki Kaisha | Polyurrethane (meth)acrylate resin/n-vinyl- pyrrolidone/acryloylmorpholine resin composition |
US4999136A (en) * | 1988-08-23 | 1991-03-12 | Westinghouse Electric Corp. | Ultraviolet curable conductive resin |
-
1994
- 1994-03-18 EP EP94912806A patent/EP0693002B2/de not_active Expired - Lifetime
- 1994-03-18 AT AT94912806T patent/ATE159276T1/de not_active IP Right Cessation
- 1994-03-18 WO PCT/US1994/002939 patent/WO1994022596A1/en active IP Right Grant
- 1994-03-18 DK DK94912806.0T patent/DK0693002T3/da active
- 1994-03-18 CA CA002156293A patent/CA2156293C/en not_active Expired - Fee Related
- 1994-03-18 ES ES94912806T patent/ES2109687T5/es not_active Expired - Lifetime
- 1994-03-18 DE DE69406278T patent/DE69406278T3/de not_active Expired - Fee Related
-
1997
- 1997-12-10 GR GR970403298T patent/GR3025646T3/el unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3918393A (en) † | 1971-09-10 | 1975-11-11 | Ppg Industries Inc | Method of producing flat (non-glossy) films |
EP0003002A2 (de) † | 1977-12-22 | 1979-07-11 | Ciba-Geigy Ag | Verwendung von aromatisch-aliphatischen Ketonen als Photoinitiatoren, photopolymerisierbare Systeme enthaltend solche Ketone und neue aromatisch-aliphatische Ketone |
EP0281941A2 (de) † | 1987-03-12 | 1988-09-14 | Ciba-Geigy Ag | Coreaktive Fotoinitiatoren |
EP0324483A2 (de) † | 1988-01-12 | 1989-07-19 | Mitsubishi Petrochemical Co., Ltd. | Verfahren zur Beschichtung eines Polyolefins mit einer harten Beschichtung |
DE4031732A1 (de) † | 1990-10-06 | 1992-04-09 | Basf Ag | Strahlenhaertbare, waessrige bindemitteldispersionen |
GB2259704A (en) † | 1991-09-23 | 1993-03-24 | Ciba Geigy Ag | Alkylbisacylphosphine oxides |
Also Published As
Publication number | Publication date |
---|---|
ES2109687T5 (es) | 2001-09-01 |
WO1994022596A1 (en) | 1994-10-13 |
DE69406278D1 (de) | 1997-11-20 |
CA2156293A1 (en) | 1994-10-13 |
GR3025646T3 (en) | 1998-03-31 |
DK0693002T3 (da) | 1998-06-02 |
EP0693002B1 (de) | 1997-10-15 |
CA2156293C (en) | 1998-12-01 |
DE69406278T2 (de) | 1998-04-30 |
ES2109687T3 (es) | 1998-01-16 |
DE69406278T3 (de) | 2001-09-27 |
ATE159276T1 (de) | 1997-11-15 |
EP0693002A1 (de) | 1996-01-24 |
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