EP0693002B2 - Procedes d'obtention de revetements durcis par rayonnement d'une haute brillance - Google Patents

Procedes d'obtention de revetements durcis par rayonnement d'une haute brillance Download PDF

Info

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
Application number
EP94912806A
Other languages
German (de)
English (en)
Other versions
EP0693002A1 (fr
EP0693002B1 (fr
Inventor
Joseph Randall Friebele
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=21914697&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0693002(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of EP0693002A1 publication Critical patent/EP0693002A1/fr
Application granted granted Critical
Publication of EP0693002B1 publication Critical patent/EP0693002B1/fr
Publication of EP0693002B2 publication Critical patent/EP0693002B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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).

Claims (10)

  1. Utilisation d'une composition durcissable par rayonnement comprenant :
    (a) 10-99% en poids d'un liant de résine durcissable par exposition à un rayonnement en présence d'au moins un composé photo-initiateur, la résine étant choisie parmi celles contenant des groupes acrylyloxy et dont le durcissement par exposition au rayonnement est sensiblement inhibé par la présence d'oxygène;
    (b) 0,01-4% en poids d'un photo-initiateur non volatil ayant un poids moléculaire d'au moins 1.000; et
    (c) 0,01-1% en poids d'un régulateur de fluidité choisi dans le groupe comprenant les composés de siloxane et les composés fluorocarbonés,
       dans un procédé de production d'un revêtement durci par rayonnement, d'un brillant élevé comprenant l'application à un substrat de ladite composition pour former un revêtement;
       dans une première étape d'exposition, l'exposition du revêtement, dans une atmosphère contenant plus de 1.000 parties par million d'oxygène, à un rayonnement ionisant de manière à au moins durcir partiellement une couche sous-superficlelle du revêtement tout en laissant au moins une couche en surface partiellement non durcie; et,
       dans une étape d'exposition ultérieure, l'exposition du revêtement au moins partiellement durci, dans une atmosphère contenant moins de 1.000 parties par million d'oxygène, à un rayonnement ultraviolet suffisant pour durcir la surface du revêtement et produire un revêtement ayant une surface d'un brillant élevé.
  2. Utilisation suivant la revendication 1, dans laquelle le photo-initiateur comprend un dérivé d'acétophénone substitué.
  3. Utilisation suivant la revendication 1, dans laquelle le régulateur de viscosité est un polysiloxane.
  4. Utilisation suivant la revendication 1, dans laquelle au moins 10% en poids du liant sont un composé polyacryloxy.
  5. Utilisation suivant la revendication 1, dans laquelle au moins 30% en poids du liant sont un composé polyacryloxy.
  6. Procédé de production d'un revêtement durci par rayonnement, d'un brillant élevé comprenant :
       l'application à un substrat d'une composition de revêtement comprenant :
    10-99% en poids d'un liant de résine durcissable par rayonnement qui contient des groupes acryloxy et dont le durcissement par exposition au rayonnement est sensiblement inhibé par la présence d'oxygène,
    0,01-4% en poids d'un photo-initiateur non volatil ayant un poids moléculaire d'au moins 1.000, et
    0,01-1% en poids d'un régulateur de fluidité choisi dans le groupe comprenant les composés de siloxane et les composés fluorocarbonés;
    dans une première étape d'exposition, l'exposition du revêtement, dans une atmosphère contenant plus de 1.000 parties par million d'oxygène, à un rayonnement ionisant de manière à au moins durcir partiellement une couche sous-superficielle du revêtement tout en laissant au moins une couche en surface partiellement non durcie; et,
    dans une étape d'exposition ultérieure, l'exposition du revêtement au moins partiellement durci, dans une atmosphère contenant moins de 1.000 parties par million d'oxygène, à un rayonnement ultraviolet suffisant pour durcir la surface du revêtement et produire un revêtement ayant une surface d'un brillant élevé.
  7. Procédé suivant la revendication 6, dans lequel le photo-initiateur comprend un dérivé d'acétophénone substitué.
  8. Procédé suivant la revendication 6, dans lequel le régulateur de fluidité est du polysiloxane.
  9. Procédé suivant la revendication 6, dans lequel au moins 10% en poids du liant sont un composé polyacryloxy.
  10. Procédé suivant la revandication 6, dans lequel au moins 30% en poids du liant sont un composé polyacryloxy.
EP94912806A 1993-04-01 1994-03-18 Procedes d'obtention de revetements durcis par rayonnement d'une haute brillance Expired - Lifetime EP0693002B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US4109393A 1993-04-01 1993-04-01
US41093 1993-04-01
PCT/US1994/002939 WO1994022596A1 (fr) 1993-04-01 1994-03-18 Compositions et procedes d'obtention de revetements durcis par rayonnement d'une haute brillance

Publications (3)

Publication Number Publication Date
EP0693002A1 EP0693002A1 (fr) 1996-01-24
EP0693002B1 EP0693002B1 (fr) 1997-10-15
EP0693002B2 true EP0693002B2 (fr) 2001-05-02

Family

ID=21914697

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94912806A Expired - Lifetime EP0693002B2 (fr) 1993-04-01 1994-03-18 Procedes d'obtention de revetements durcis par rayonnement d'une haute brillance

Country Status (8)

Country Link
EP (1) EP0693002B2 (fr)
AT (1) ATE159276T1 (fr)
CA (1) CA2156293C (fr)
DE (1) DE69406278T3 (fr)
DK (1) DK0693002T3 (fr)
ES (1) ES2109687T5 (fr)
GR (1) GR3025646T3 (fr)
WO (1) WO1994022596A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
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
AU2005308920B2 (en) 2004-11-29 2010-04-15 Dsm Ip Assets B.V. Method for reducing the amount of migrateables of polymer coatings
EP3442720B1 (fr) * 2016-04-11 2022-02-23 Sun Chemical Corporation Procédé destiné à des formulations de jet d'encre durcissables par faisceau d'électrons

Citations (6)

* Cited by examiner, † Cited by third party
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 (fr) † 1977-12-22 1979-07-11 Ciba-Geigy Ag Utilisation de cétones aromatiques-aliphatiques comme photoinitiateurs, systèmes photopolymérisables contenant de telles cétones et cétones aromatiques-aliphatiques
EP0281941A2 (fr) † 1987-03-12 1988-09-14 Ciba-Geigy Ag Photo-initiateurs coréactifs
EP0324483A2 (fr) † 1988-01-12 1989-07-19 Mitsubishi Petrochemical Co., Ltd. Procédé pour appliquer un revêtement dur sur une polyoléfine
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)

* Cited by examiner, † Cited by third party
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 (fr) * 1979-11-29 1981-06-10 Ciba-Geigy Ag Couche photo-réticulable sur des surfaces d'impression et procédé de fabrication de plaques d'impression offset
US4317858A (en) * 1980-06-27 1982-03-02 Westinghouse Electric Corp. Ultraviolet curable solvent-free wire enamel blends
US4326001A (en) * 1980-10-01 1982-04-20 Gaf Corporation Radiation cured coating and process therefor
US4309452A (en) * 1980-10-01 1982-01-05 Gaf Corporation Dual gloss 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 (fr) * 1987-09-30 1992-01-08 Westinghouse Electric Corporation Compositions de résine durcissables par ultraviolet
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
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 (fr) † 1977-12-22 1979-07-11 Ciba-Geigy Ag Utilisation de cétones aromatiques-aliphatiques comme photoinitiateurs, systèmes photopolymérisables contenant de telles cétones et cétones aromatiques-aliphatiques
EP0281941A2 (fr) † 1987-03-12 1988-09-14 Ciba-Geigy Ag Photo-initiateurs coréactifs
EP0324483A2 (fr) † 1988-01-12 1989-07-19 Mitsubishi Petrochemical Co., Ltd. Procédé pour appliquer un revêtement dur sur une polyoléfine
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
DE69406278T2 (de) 1998-04-30
ATE159276T1 (de) 1997-11-15
WO1994022596A1 (fr) 1994-10-13
EP0693002A1 (fr) 1996-01-24
ES2109687T5 (es) 2001-09-01
CA2156293A1 (fr) 1994-10-13
EP0693002B1 (fr) 1997-10-15
DE69406278D1 (de) 1997-11-20
DK0693002T3 (da) 1998-06-02
DE69406278T3 (de) 2001-09-27
CA2156293C (fr) 1998-12-01
GR3025646T3 (en) 1998-03-31
ES2109687T3 (es) 1998-01-16

Similar Documents

Publication Publication Date Title
US5585415A (en) Pigmented compositions and methods for producing radiation curable coatings of very low gloss
US4048036A (en) Process for producing films of low gloss by exposure to ultraviolet light
US4309452A (en) Dual gloss coating and process therefor
US4017652A (en) Photocatalyst system and ultraviolet light curable coating compositions containing the same
CA1120631A (fr) Finis a faible brillance par cure a intensite progressive
US4170663A (en) Method for producing coatings of low gloss
US4326001A (en) Radiation cured coating and process therefor
US4439480A (en) Radiation cured coating and process therefor
EP0693002B2 (fr) Procedes d'obtention de revetements durcis par rayonnement d'une haute brillance
EP1485211B1 (fr) Composition de revetement a chaud utilisee dans le transfert et le coulage de feuilles
JPH1085660A (ja) 補修コーティングの形成方法
US3850675A (en) Use of ultraviolet light to cure uncured surface layer resulting from air inhibition in preceding high energy ionizing radiation curing process
US4091050A (en) Method for the preparation of mixtures of (meth)acrylic terminated polyether resin and 3-halo-2-hydroxypropyl (meth)acrylate
RU2211848C2 (ru) Способ отверждения порошкообразных лаков
US3993798A (en) Cured opaque coating with high hiding power produced from normally transparent polyester paste filler compositions
US4065624A (en) Radiation curable coating composition
US5605740A (en) Actinic radiation-curable colored coating composition for use in vacuum-forming film, vacuum-forming film and vacuum-formed product
US3907656A (en) Process for ultraviolet pigmented hardening of pigmented paint films
US5732477A (en) Process for ultraviolet curing
WO1995008596A1 (fr) Compositions de revetement durcissables aux rayonnements, a pigment noir et au fini mat
US4212899A (en) Process for producing a colorant containing highlighted coated substrate
EP1633496B1 (fr) Reparation localisee de substrats revetus
JPH0671217A (ja) 塗装方法
JP4597831B2 (ja) 化粧シート
CA1113882A (fr) Methode de production d'un colorant sur un substrat a enduit repousse

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950927

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19960610

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

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

Ref country code: NL

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

Effective date: 19971015

REF Corresponds to:

Ref document number: 159276

Country of ref document: AT

Date of ref document: 19971115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: ISLER & PEDRAZZINI AG

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69406278

Country of ref document: DE

Date of ref document: 19971120

ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R.L.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2109687

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 19971017

ET Fr: translation filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: CIBA SPECIALTY CHEMICALS HOLDING INC.

Effective date: 19980707

26 Opposition filed

Opponent name: HERBERTS GMBH

Effective date: 19980709

Opponent name: CIBA SPECIALTY CHEMICALS HOLDING INC.

Effective date: 19980707

NLR1 Nl: opposition has been filed with the epo

Opponent name: HERBERTS GMBH

Opponent name: CIBA SPECIALTY CHEMICALS HOLDING INC.

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: PPG INDUSTRIES OHIO, INC.

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: PPG INDUSTRIES, INC. TRANSFER- PPG INDUSTRIES OHIO

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: ISLER & PEDRAZZINI AG

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: PPG INDUSTRIES OHIO, INC.

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

NLS Nl: assignments of ep-patents

Owner name: PPG INDUSTRIES OHIO, INC.

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: CIBA SPECIALTY CHEMICALS HOLDING INC. * 19980709 D

Effective date: 19980707

NLR1 Nl: opposition has been filed with the epo

Opponent name: DUPONT PERFORMANCE COATINGS GMBH & CO. KG

Opponent name: CIBA SPECIALTY CHEMICALS HOLDING INC.

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: CIBA SPECIALTY CHEMICALS HOLDING INC. * 19980709 D

Effective date: 19980707

NLR1 Nl: opposition has been filed with the epo

Opponent name: DUPONT PERFORMANCE COATINGS GMBH & CO.KG

Opponent name: CIBA SPECIALTY CHEMICALS HOLDING INC.

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

RTI2 Title (correction)

Free format text: METHODS FOR PRODUCING HIGH GLOSS RADIATON CURABLE COATINGS

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

Ref country code: FR

Payment date: 20010302

Year of fee payment: 8

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

Ref country code: DK

Payment date: 20010305

Year of fee payment: 8

Ref country code: CH

Payment date: 20010305

Year of fee payment: 8

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

Ref country code: SE

Payment date: 20010306

Year of fee payment: 8

Ref country code: GB

Payment date: 20010306

Year of fee payment: 8

Ref country code: AT

Payment date: 20010306

Year of fee payment: 8

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

Ref country code: NL

Payment date: 20010307

Year of fee payment: 8

Ref country code: DE

Payment date: 20010307

Year of fee payment: 8

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

Ref country code: PT

Payment date: 20010316

Year of fee payment: 8

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

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

Ref country code: GR

Payment date: 20010329

Year of fee payment: 8

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

Ref country code: IE

Payment date: 20010330

Year of fee payment: 8

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

Ref country code: ES

Payment date: 20010406

Year of fee payment: 8

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

Ref country code: BE

Payment date: 20010410

Year of fee payment: 8

27A Patent maintained in amended form

Effective date: 20010502

AK Designated contracting states

Kind code of ref document: B2

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM * AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

NLR2 Nl: decision of opposition
ITF It: translation for a ep patent filed

Owner name: MODIANO & ASSOCIATI S.R.L.

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

Ref country code: DK

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

Effective date: 20010802

Ref country code: AT

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

Effective date: 20010802

ET3 Fr: translation filed ** decision concerning opposition
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Kind code of ref document: T5

Effective date: 20010802

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

Ref country code: PT

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

Effective date: 20011130

REG Reference to a national code

Ref country code: PT

Ref legal event code: MP4A

Effective date: 20010802

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: IE

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

Effective date: 20020318

Ref country code: GB

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

Effective date: 20020318

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

Ref country code: SE

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

Effective date: 20020319

Ref country code: ES

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

Effective date: 20020319

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

Ref country code: LI

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

Effective date: 20020331

Ref country code: CH

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

Effective date: 20020331

Ref country code: BE

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

Effective date: 20020331

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

Ref country code: DE

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

Effective date: 20021001

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

Ref country code: GR

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

Effective date: 20021007

EUG Se: european patent has lapsed

Ref document number: 94912806.0

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

Effective date: 20020318

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: FR

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

Effective date: 20021129

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030410

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

Ref country code: IT

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

Effective date: 20050318

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO