EP0009885A1 - Procédé d'application d'une couche sur un substrat - Google Patents

Procédé d'application d'une couche sur un substrat Download PDF

Info

Publication number
EP0009885A1
EP0009885A1 EP19790301793 EP79301793A EP0009885A1 EP 0009885 A1 EP0009885 A1 EP 0009885A1 EP 19790301793 EP19790301793 EP 19790301793 EP 79301793 A EP79301793 A EP 79301793A EP 0009885 A1 EP0009885 A1 EP 0009885A1
Authority
EP
European Patent Office
Prior art keywords
coating composition
coating
substrate
carrying web
cured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19790301793
Other languages
German (de)
English (en)
Other versions
EP0009885B1 (fr
Inventor
William Henry Mccarty
Frank Andrew Nagy
John Phillip Guarino
Leon A. Psaty
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.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0009885A1 publication Critical patent/EP0009885A1/fr
Application granted granted Critical
Publication of EP0009885B1 publication Critical patent/EP0009885B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/64—Addition to the formed paper by contacting paper with a device carrying the material the material being non-fluent at the moment of transfer, e.g. in form of preformed, at least partially hardened 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B05D1/286—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers using a temporary backing to which the coating has been applied
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper

Definitions

  • This invention relates to a method for applying coatings to substrates and, in particular; to a method for producing high gloss coatings on substrates.
  • Coatings have traditionally been applied to substrates such as paper by dissolving the coating composition in an inert volatile carrier, directly applying it to the substrate, and heat-curing in an oven. On the application of heat the inert carrier is driven off and the coating composition cured. This procedure is often unsatisfactory with porous substrates because of the phenomenon known as "wicking" in which the uncured composition is absorbed into the substrate. This makes it difficult - if not impossible - to obtain high gloss coatings.
  • a difficult technique comprising applying a film of an unsaturated ester to a substrate and curing the ester by ionising radiation is disclosed in C.B. 1241851.
  • Another process employing ionising radiation (electron beam) curing is disclosed in G.B. 1519493; this process uses a release paper to effect a transfer of the coating.
  • an imporved transfer coating process which is capable of applying high gloss coatings to porous substrates and other substrates which are difficult to coat.
  • the process enables the absorbtion of the coating into the substrate to be reduced, thereby reducing the quantity of coating composition needed.
  • Substrates coated by this process demonstrate improved gloss and smoothness of surfact texture.
  • Particularly desirable surface textures may be created by applying the coating composition to the substrate in various patterns and/or film thicknesses prior to curing.
  • a particularly beneficial aspect of this process is that it may be carried out entirely in air and that no inert gaseous atmosphere is required during the curing stage.
  • the process according to the invention comprises applying a radiation curable coating composition to a smooth surfaced carrying web.
  • the substrate to be coated is then brought into contact with the coating composition by passing the substrate and the carrying web through a pair of nip rollers to form a laminar structure and initiating transfer of the coating composition from the carrying web to the substrate.
  • the structure is then subjected to a radiation curing process which the coating composition is polymerized and set. Upon removal from the radiation curing, the carrying web may be separated-from the coated substrate. The coated substrate is then removed and the carrying web is either discarded or recycled for reuse in the process.
  • the carrying web is selected so that the cured, polymerized coating composition will not adhere to its surface.
  • Radiation curable coatings differ in their ability to adhere to various substrates and it is therefore possible to select the carrying web and the substrate in such a manner that, for any given coating composition, the cured coating adheres to the substrate but not to the'carrying web.
  • the carrying web should be impervious to the coating composition and have a high degree of surface smoothness. Additionally, the web should be resistant to tearing and of a composition such that it will not stick to the coating.
  • the carrying webs may be in the form of continuous-films or an endless belt. They may be made, for example, from polyester film material, metal foil, or polished metal belt or drum.
  • the substrate may be fabricated from a wide variety of papers and film materials such as wood, fiber compositions or even metals, depending on the nature of the carrying web and the coating composition.
  • the present process is particularly suitable for use with porous substrates (e.g. coarse paper) because it enables very smooth glossy surfaces to be produced.
  • the coated substrate may subsequently be top coated with another material by the same or different process - for instance, coated paper may be metallized with aluminum by a conventional: metallizing process.
  • coated paper may be metallized with aluminum by a conventional: metallizing process.
  • the advantage of such operation is that the secondary coating will exhibit superior surface characteristics (smoothness, gloss, reflectance).
  • substrates coated by means of the present process will provide a superior casting and support surface for cast-forming plastic film material (e.g. vinyl, polyester, polyolefin, etc.): the good surface characteristics of the coated substrate are capable of producing cast plastic films having similar superior surface characteristics.
  • plastic film material e.g. vinyl, polyester, polyolefin, etc.
  • the coating composition is selected according to certain physicochemical characteristics. We have found that it is possible to effect a controlled decrease in the adhesive bond strength between the cured coating and most substrates of interest.
  • the cross link density may be conveniently defined by the calculated (i.e., theoretically possible) number of gram moles of - potential branch points per 100 grams of coating composition. Crosslink densities ranging from 0.02 to 1.0 have been found to be useful, but a range from 0.03 to 0.7 is preferred and, in particular, a range from 0.04 to 0.5 is found to be the most useful.
  • the adhesive force between the cured coating and the substrate of interest may be further modified by incorporating into or eliminating from the composition specific chemical groups that influence the adhesive bond to the substrate.
  • chemical groups are groups derived from Lewis or Bronsted acids or bases, hydroxyl or carboxyl groups combined with organic hydrocarbon molecules, ether linkages, urethane linkages, epoxide groups or mercaptan groups.
  • adhesion promoting groups on the surface of the substrate on which the cured coating is to remain after the removal of the carrying web. This may be accomplished by subjecting the substrate to treatment by corona discharge by open flame, or by other oxidizing or reducing atmospheres; or by any other suitable chemical or heat treatment. Physical treatment of the surface of the uncoated substrate with abrasives which serve to improve mechanical adhesion may also be used on nonporous substrates to improve the adhesive bond. Incorporation of release agents such as silicone oil, mineral oils, or waxes onto the surface of the carrying web may be used to decrease the adhesive bond, but these generally are not preferred as they tend to increase the cost of the process and are usually not necessary.
  • Figure 1 shows a typical processing line for applying high gloss coatings to paper substrates.
  • the uncoated substrate sheet 100 is fed to the line from substrate roll 1. It passes over tensioning roller 2 and on to roller 3 where a coating is applied.
  • Coating application is by mans of a conventional offset gravure process. Basically, the uncured coating composition is placed in pan 4 and is then picked up by steel gravure roll 5 which, as it rotates, transfers the coating composition to rubber offset roll 6. Then, as substrate sheet 100 passes between rollers 3 and 6, the coating composition is transferred to the surface of the substrate sheet.
  • the raw coated substrate sheet 101 is then fed to the curing'station 7.
  • the curing station will be referred to below as an "electron beam apparatus."
  • the coating composition is rapidly polymerized and cured.
  • the cured coated sheet 102 passes over and around tensioning rollers 8 and 9 and is would on take-up roller 10.
  • FIG. 2 shows one of the preferred embodiments of the process.
  • Carrying web roll 30 supplies a carrying web 200 to the line.
  • the carrying web 200 is passed over tensioning roller 31 and the coating composition is applied by the offset gravure process as described above, except this time it is applied to a carrying web 200.
  • both the web and the substrate sheet 100 are passed between nip' rollers 11 and 12 forming a laminar structured sheet 201.
  • Sheet 201 comprises substrate sheet on top, the carrying web on the bottom and. the uncured coating composition between the two.
  • the laminate 201 is passed quickly to the curing station to minimize or eliminate absorption of the coating composition by the substrate sheet.
  • the laminate or sandwich 201 is passed around tensioning rollers 8 and 9 as in Figure 1 and is wound on take-up roller 10.
  • the carrying web 200 may be peeled away from the coated substrate since the choice of materials is such that the cured coating composition will not adhere to the carrying web but will adhere to the paper substrate. Because the absorption of the raw coating composition by the substrate is substantially reduced, the amount of coating composition required to produce a suitably coated substrate sheet is also reduced.
  • the material which is to comprise the carrying web 200 it is possible to control the surface finish on the coated sheet.
  • An appropriate choice of material for the carrying web may result in a smooth and glossy finish on the coating or, if desired, a dull and flat finish.
  • a design may be imparted to the coated surface merely by appropriate choice or modification of the carrying web.
  • Figure 3 of the drawings shows another preferred embodiment of this invention.
  • the process line is set up as in the Figure 2 embodiment.
  • the laminate 201 is formed and passed through the electron beam apparatus; it is fed to separating rollers 13 and 14 where the carrying web 200 is released from the coated substrate 102 and separated from it.
  • the carrying web is passed around tensioning rollers 32 and 33 and wound on web take-up roller 34.
  • the carrying web may be reused merely by substituting the material on take-up roller 34 for the carrying web roll 30.
  • the substrate 102 is passed over tensioning roller 9 and wound on take-up roll 10 as before.
  • the apparatus illustrated in Figure 4 is a modification of the prvious apparatus.
  • the modification is particularly suitable in the coating of highly porous substrates.
  • the nip rollers 11 and 12 which help form laminate or sandwich 201 are positioned immediately before curing station 7 so as to minimize the distance which the laminate 201 must travel before being exposed to the electron beam radiation.of the curing station.
  • the purpose for this modification is to facilitate the coating.highly porous substrates which, prior to the present invention, have been difficult or even impossible to coat because of the high degree of substrate.porosity which resulted in most or all of the uncured coating composition being absorbed into the substrate instead of remaining on its surface.
  • both the coated substrate and the carrying web may be wound on the same roll, as shown in Figure 2.
  • Still another embodiment of the apparatus is illustrated schematically in Figure 5.
  • the carrying web roll 30 and carrying web take-up roll 34 are completely eliminated.and replaced by an endless belt of carrying web material 300.
  • BElt 300 is coated with the coating composition as described in the previous embodiments and the substrate sheet 100 brought into contact with the coating composition via nip rollers 11 and 12 as before to form laminate or sandwich 301.
  • Laminate 301 is then passed through the electron beam, where the coating composition is polymerized and cured.
  • the coated substrate 102 is subsequently stripped from belt 300, passed over tensioning roller 9 and wound on take-up roller 10.
  • Suitable sources of radiation for curing the coating composition comprise electron beam radiation, ultraviolet light, or even thermal radiation.
  • the preferred source of radiation for the initiation.of polymerization and curing is electron beam radiation.
  • Electron beam radiation may be obtained from high energy electrons produced by high voltage electron accelerator, resonant transformers, transformer rectifiers, microwave waveguide linear accelerator, and synchrotrons.
  • the primary reason for preferring electron beam radiation is that this type of radiation is not limited by the physical nature of either the web or the substrate; it will penetrate any combination of materials.
  • the primary limitation in an electron beam curing process is the density rather than the thickness of the total substrate which the beam must penetrate (i.e. the density of the laminate).
  • the beam will penetrate the entire laminate with some of the beam passing through, it needs only to penetrate as far as the coating composition.
  • the density limitation for any particular beam is determined by the intensity' of that beam. For example a 200 kv beam of electrons will penetrate up to 1C mils of unit density material, e.g. water.
  • Aluminum has a density of 3, and such a beam can penetrate only about 3 mils of aluminum.
  • Commercial polyester films also have a density of approximately 1. Denser materials, such as stainless steel, may be used in an electron beam curing steup but the laminate must be arranged so that the stainless steel layer comprises the back layer of the laminate relative to the direction of the electron beam radiation.
  • Ultraviolet radiation may be used for initiating the curing of the coating composition, provided at least one side of the sandwich is transparent to the U.V. light rays. In practice, this requirement usually means that the carrying web must be transparent, thereby eliminating metal or metallized carrying webs and materials such as polyester film which absorb the U.V. light. However, suitably transparent materials (e.g. polyethylene film) may be used with great success as carrying webs. Similarly, thermal radiation may be used in the process, as long as the curing or drying energy is sufficient to reach and cure the coating composition before significant absorption into the substrate sheet occurs.
  • Such means may include, for example, chemically induced polymerization or microwave or other types or sources of radiation.
  • the present process has the unexpected advantage of eliminating or substantially reducing the necessity of providing an inert gaseous atmosphere in the vicinity of the coated substrate while the coating composition is undergoing polymerization.
  • Previous processes such as that shown in Figure 1, have required an inert gas atmosphere in the area in which polymerization of the coating composition was taking place so as to avoid the undesirable effects brought about by the presence of unwanted substances introduced from the atmosphere.
  • Of particular concern has been the undesirable interference with the formation of cross-linking bonds in the polymer caused by the presence of atmospheric oxygen, the effect of which has been that the resultant cured coating composition had physical characteristics less desirable than those otherwise expected.
  • Another important advantage of this invention is the substantial savings realized in the amount of coating composition needed to be applied to the substrate in order to achieve a given surface effect, particularly with respect to the coating of porous substrates. It is now possible, by applying the coating compositions as disclosed herein, to get smooth, high gloss coatings on porous substrates (e.g.: tissue paper and textiles) while simultaneously using substantially less coating material. This improvement is the result of the very short contact times between the uncured compositions and the porous substrates.
  • porous substrates e.g.: tissue paper and textiles
  • the process of the present invention may be used to advantage in the manufacture of metallized papers and plastic films. It is desirable to obtain good surface characteristics with metallized substrates but this is especially difficult when the substrate is a porous material such as paper.
  • the basic difficulty encountered in the metallization of porous materials is that the metallized layer is extremely thin (typically of the order of a fraction of a micron) and any surface imperfections in the substrate are reproduced on the metallized surface. Surface imperfections may be removed, by applying a base coat to the substrate to fill in minor imperfections and provide a suitable high-gloss surface to receive the metal deposit.
  • Plastic materials which are substantially non-porous and usually already have reasonably smooth surfaces, are commonly base coated with lacquer, acrylic resins, alkyd resins (pure and modified), polyesters, conventional varnishes, urea-formaldehyde resins, vinyl polymers, acrylonitrile polymers, phenolic resins, cellulosic ' resins, polyurethanes, butyl rubber and chlorinated butyl rubber, silicone resins, melamine-formaldehyde resins, polystyrenes, natural rubber, and modified phenolic resins, either individually or in various combinations.
  • Porous substrate materials present considerably greater problems, both in degree and in kind, than do non-porous substrates because it is difficult to seal and fill the surface at reasonable cost and without substantially altering or destroying the desirable physical characteristics of L he substrate.
  • the selection of a material suitable for a base coat is not, however, difficult in itself. Generally, any of the types of materials enumerated above, as well as any other composition normally used to coat and give a high gloss finish to paper are suitable. The only criteria is that the coating block the pores of the substrate; have good holdout characteristics to give a smooth, high-gloss surface; and not be so hard or slippery as to inhibit the adhesion of the metal atoms to the surface. It is preferred that silicone lubricants on the surface of the cured coating be kept at a minimum because this material may tend to interfere with the deposition of the metal atoms.
  • the present process may be used to apply the base coat to porous substrates prior to deposition of the metal atoms; this results in a imporoved and desirable surface for metallizing.
  • the base coat is applied and cured as taught above and, after removal from the carrying web, the coated surface is metallized by any suitable means such as vacuum metallizing, electroplating and sputtering, as described in EXTRUSION AND OTHER PLASTICS OPERATIONS, N.M. Bikales editor (Ililey-Interscience, 1971) pages 249-277.
  • Another use for the present invention is in the cast-forming of plastic or other sheet material where the surface characteristics of the cast sheet are of major concern.
  • a coating to a support substrate by this process prior to casting the film, it is possible to impart a smoother surface to the substrate than previously obtainable.
  • the present process may be used to give otherwise unuseable substrates a superior surface finish suitable for use in cast-forming.
  • Most of the kinds of coating compositions mentioned previously will be employable in this type of application, but with certain added limitations concerning imperviousness to solvents and temperature stability. Basically, if the sheet or film to be cast-formed is to be cast from the melt - i.e.
  • the molten resin is to be applied directly to the support surface and allowed to cool - the cured coating composition which comprises the casting surface of the substrate must be substantially unaffected by the temperature of the molten resin.
  • the sheet or film is to be solvent-case - i.e. a solution of the resin is laid down on the support surface and the solvent subsequently removed - the cured coating composition must be immune to the solvent.
  • the substrates which may be used include, wide range of papers, both porous and nonporous, as well as coated and uncoated papers, film materials and even metals, depending primarily on the choice of carrying web material and coating composition.
  • the process may even be used to apply coatings to open weave fabrics, hardboard material and wood paneling.
  • the web It should be impervious to the raw coating composition and should be'selected so that it will not stick to the cured coating composition. Also, the carrying web should be resistant to tearing since it willbe under some degree of tension during the operation. Suitable materials include, for example, polyester film (e.g., the film material sold by the Dupont Company under the trade name MYLAR), metal foil, plastic resin film, and polished metal belts or drums. Another requirement for a suitable carrying web is that it must be resistant to the type of curing radiation utilized. If a high degree of surface smoothness is desired in the finished coated substrate, it is particularly important that the carrying web be chosen for its furface characteristics. In contrast, by imparting a design to the surface of the carrying web, it is possible to transfer the design to the coated substrate.
  • polyester film e.g., the film material sold by the Dupont Company under the trade name MYLAR
  • metal foil e.g., the film material sold by the Dupont Company under the trade name MYLAR
  • MYLAR metal foil
  • the raw coating composition may be applied to the carrying web by means of the offset gravure application method as described above or, alternatively, any other suitable method of applying a coating to the surface of the carrying web may be used.
  • application methods include, for instance; direct gravure coating, roll coating application, brushing and flow coating.
  • a choice of coating composition to be used in this process will be determined primarily by the nature of the substrate and the quality, texture and other characteristics which are desired in the final coated substrate. Other considerations include the nature of the means used to initiate polymerization in curing the coating. For example, if electron beam radiation is used, it is necessary to have an electron beam curable coating. Similarly, if the coating composition is to be cured by means of ultraviolet radiation a photoinitiator should generally be present in the coating composition. If the coating is to be thermally cured, then the composition must be'thermosettable. Finally, it is of primary importance that the combination of coating composition and carrying web material chosen be such that the cured coating will not adhere to the carrying web, thereby allowing transfer of the surface characteristics of the carrying web to the surface of the coating once polymerization has taken place:
  • the coating compositions generally comprise a mixture containing one or more materials contaiing one or more ethylenically unsaturated functional groups.
  • the coatings may be specifically designed to provide the desired degree of differential adhesive force or "selective adhesion" between two dissimilar substrate surfaces and still provide acceptable adhesion to the substrate of interest.
  • the basic variables controlling the adhesive force have been found to be the crosslink density of the coating, the presence (or relative absence) of specific adhesion promoting sites in the coating composition and/or on the surface of the respective substrates, and the glass transition temperature of the coating. By appropriate manipulation and control of these variables it is possible to formulate the coating composition so that its adhesion to the carrying web and the substrate can be controlled in the manner desired.
  • the bond strength between the cured coating composition and the substrate may be varied by changing the cross linkage density of the cured composition, with densities of 0.03 to 0.7, advantageously 0.04 to 0.15, being preferred.
  • lower shipping forces the force required to ship the cured composition off the carrying web
  • suitable control of the crosslink density This permits a correspondingly greater number of different materials to be used for the webs.
  • Increasing the crosslink density decreases the adhesion and conversely, decreasing the density increases the degree of adhesion.
  • Tg glass transition temperature
  • the Tg is important because, together with the crosslink density, it determines the mechanical strength of the coating. For instance, coatings which are too low in Tg may fail cohesively during the stripping operation. Similarly, if the Tg is too high brittle failure of the coating may occur during stripping. It has been found that a Tg falling within the approximate range of 80°C to +100°C may be useful in the invention, but we prefer that the Tg fall between -20 o C and +50°C, most preferably between 0°C and +30°C. We find that the latter range provides maximum toughness in the cured coating at room temperature for a given potential crosslink density. However, in many applications considerations of minimum applied coating cost will outweigh maximum toughness, in which case operation outside the preferred ranges may be desirable.
  • the coating composition for use in this invention because of the numerous factors entering into the specific design of the coating composition for use in this invention, we have devised the following procedure for selection of coating and carrying web for use with the substrate of interest.
  • Application of the coating to various plastic and metal film materials which might be useful as carrying webs is then performed and the coated film material brought into contact with the substrate of interest.
  • the sandwich formed thereby is-then subjected to appropriate curing means (electron beam, UV, thermal, etc.) and the coating composition polymerized.
  • the peel force required to strip the carrying web from the coated substrate is then determined.
  • the carrying webs may be ordered according to the peel force required to separate them from the substrate of interest.
  • polyolefin, polyester, and metal films used in commerce will perform exceptionally well as carrying webs exhibiting low peel strengths.
  • the order in the array may be altered by surface treatment. For example, if it is desired to transfer from polyester to polyethylene or metal films, the polyethylene may be subjected to corona discharge, or the metal film may be cleansed of the oils and soaps used in the manufacturing process by suitable washing, heat treatment, or by corona discharge treatment.
  • control of the crosslink density also controls the degree of adhesion. It is preferred that the crosslink density of the coating, as defined by the potential number of gram moles of branch points per 100 grams of coating (two branch points equals one crosslink) lie between 0.03 and 0.7; although the range from 0.02 to 1.0 may also be used with good results. A range from 0.04 to 0.5 is a particularly desirable range. This range provides coatings that demonstrate good adhesion to paper and vinyl film, while releasing acceptably from polyolefin, polyester, and "oily" metal films. The lower portion of the range also includes compositions that adhere well to treated polyethylene and clean metals, while stripping easily from polyolefin, polyester and "oily” metal films.
  • the composition of the carrying web is not critical (as far as the curing step is concerned) because penetration by the electrons can be assured by selection of sufficiently high voltage.
  • the selection of carrying web must be confined to films that transmit UV light in sufficient intensity to cure the coating.
  • polyolefins, particularly polyethylene are preferred for use with UV cure coatings due to the excellent transmission of UV light.
  • the range of materials that can be used as carrying webs can be extended by using UV initiators that absorb strongly in regions where UV transmission is highest.
  • polyester film can be used with UV cure coatngs by use of photoinitiators such as 2-chlorothioxanthone which absorbs light as the higher wavelengths.
  • Substrates coated by the present process may, in addition, be top-coated with other coating compositions by the same or a different application process.
  • Such top-coatings may be transparent and serve primarily a protective function, or they may be pigmented to provide additional decorating function - for example, wrapping paper or decorative wall coverings having multi-colored patterns and designs.
  • the coated substrate may be subsequently imprinted with written or printed messages or with designs using printing inks - for instance, labels or packaging materials carrying information of value to the user of the package.
  • Another application would be to decorate or print on the uncoated substrate and subsequently apply a clear protective coating by the present process.
  • a commercially obtainable 28 pound CIS paper stock obtained from the Consolidated Paper Company
  • a white pigmented coating having a viscosity of 2000 cp using a 150 quad gravure roll for application of the composition i the offset mode.
  • the ingredients in the coating composition are given in Table 1 below. *The combination of components 1 and 2 is disclosed in U.S. Patent No. 4,064,026.
  • EPON 828 is a trade mark for a diglycidyl ether of 4,4'-isopropylidenediphenol, epoxide equivalent weight of 185 to 200.
  • the coating composition was applied to a 0.5 mil thick carrying web comprising a sheet of polyester film material.
  • the coated carrying web was then brought into contact with the substrate arid the sandwich formed by passing the two sheets between a pair of nip rollers.
  • the sandwich, with the coating composition between the two layers, was then fed to an electron beam curing apparatus at a speed of 30.5 m. per minute.
  • the voltage of the beam was 175 kv.with a current of 10 ma and the dosage of 2 MR.
  • the carrying web was peeled from the coated substrate to reveal a coating surface having a high gloss and excellent smoothness.
  • Example 2 Using the same paper substrate and coating composition of Example 1, a superior matte finish was achieved by applying the coating composition to a carrying web comprising a 2.5 micron thick sheet of matte finish aluminum foil. The sandwich was then formed with the paper substrate as before and the coating composition cured by means of electron beam radiation using the conditions given in Example 1. Upon removal from the curing station the aluminum foil was peeled from the coated substrate to reveal the cured coating surface on the substrate having superior smoothness with a matte finish.
  • the porous side of the CIS 28 paper stock was coated with the coating composition and cured as in Example 1 using a polyester carrying web. After removal f the carrying web the cured coating composition could be seen to reside substantially on the surface of the paper and imparted a smooth, high gloss, reflective - finish to the paper.
  • Example 2 Using the same paper, coating composition, curing speed and electron beam dosage parameters as in Example 1, the coating was applied directly to the surface of the paper using conventional methods. Upon inspection after curing, it was seen that substantially all the composition had been drawn into the interstices of the paper and that the coated surface had a flat appearance with substantially no greater gloss or reflectivity than it had before coating.
  • Example 1 The coating composition of Example 1 was applied to a polyester film carrying web using a 150 quad offset gravure roll at 33.5 m./min. The coated surface of the carrying web was then brought into contact with a sheet of No. 60 lithographic grade paper stock and the coating composition cured by electron beam at 10 ma, 185 kv and a dosage of 2.0 MR. After removal of the polyester web the coated paper was visually examined for the quality of the cured coating. The surface was very smooth and exceptionally reflective.
  • Example 5 Using curing speed and parameters identical to those of Example 5, the coating was applied directly to the No. 60 litho stock in the conventional way. Upon inspection it was seen that, although the reflectivity of the coated surface had been improved, a substantial amount of the composition had been absorbed into the paper prior to polymerization end as a result the gloss and smoothness of the coating was substantially less at 10 ma and 185 kv with a dosage of 2.0 MR. The polymerized coating was smooth and glossy with a very high degree of reflectivity and very little of the brown paper color showing through the white coating.
  • the kraft paper was coated in the conventional manner (i.e. direct application of the coating composition to the paper) at 100 ft/min. Subsequent curing was by electron beam radiation at 185 kv and 30 ma with a dosage rate of 6.0 MR. The coated and cured surface was matte and was neigher substantially smoother nor more reflective than the uncoated paper. Additionally, although the coating lightened the color of the paper somewhat, the majority of the composition had been absorbed into the paper with the result that the coated paper was of substantially the same brown color as the uncoated kraft paper.
  • Coatings A, B and C are curable by electron beam radiation while Coatings D. E. F. G and H are curable by UV light.
  • the reported T-peel values for each coating composition on the various substrates and carrying webs were determined in accordance with ASTM procedure D-1876.
  • the substrates used for the illustration of this invention are identified in Table 2 below. The same materials were used in the experiments as both carrying webs and coatable substrates. Table 3 comprises a glossary of the nomenclature used in than that of Example 5.
  • the reverse (non-smooth) side of the No. 60 litho stock was coated by the transfer method at 30.5 m./min.
  • the surface having the cured coating composition was very smooth and well sealed, having a gloss and reflectivity comparable to that of Example 5, thereby demonstrating that coatngs may successfully be applied by the process of this invention to either the usual calendered side of a commercially useful grade of paper or to the reverse, relatively non-smooth side with equally good results.
  • Example 7 was repeated with the exception that the coating was applied at the rate of 50 ft/min. and the electron beam radiation cur had a current of 5ma. At the slower operating speed the polymerized coating was not as smooth as that of Example 7, although reflectivity and resistance to absorption were stll substantially better than that of the conventional appication method to the prepared side of the paper as in Example 6.
  • Example 1 Medium grade brown kraft paper was coated with the coating composition of Example 1 at the rate of 30.5 m./min.
  • the uncured coating was applied to a polyester carrying web using a 150 quad gravure roll in the offset mode and the kraft paper brought into contact with the coated surface. Curing was by electron beam radiation describing the compositions of the various coating vehicles.
  • EPON 828 (trade mark) Diglycidy ether of 4,4'-isopropylidenediphenol; epoxide equivalent weight of 185 to 200.
  • Trimethylol propane triacrylate mole weight of 299, three reactive acrylate groups per molecule.
  • Butyl carbamyl ethyl acrylate formed by reaction of equivalent amounts of butyl isocyanate and hydroxyethyl acrylate, mole weight of 215, one reactive acrylate group per molecule.
  • n-Vinyl pyrrolidone manufactured by GAF Corp., mole weight of 111, glass transition temperature of 80°C, one reactive unsaturated group per molecule.
  • An adduct prepared by reacting one mole of hydroxyethyl acrylate with five moles of propylene oxide as described in U.S. Patent No. 4,064,026.
  • the mole weight was 40 grams and there was one unsaturated group per molecule.
  • An adduct supplied by Dow Chemical Co. formed by reacting one mole of an epoxy resin with two moles of acrylic acid. Mole weight is approximately 400 and there are two unsaturated groups per molecule.
  • Methyldiethanolamine supplied by Union Carbide Company.
  • compositions suitable for cure by means of electron beam radiation are formulated using standard formulation techniques and a summary of each, together with the calculated potential crosslink density and the Tg (as determined by differential scanning calorimetry), is presented in Table 4 below.
  • Coating A is an example of a coating of relatively low potential crosslink density (0.11). T-peel results obtained for this coating are given in Table 5 below. These results indicate that the coating may be easily separated from polyethylene, polyester, and oily aluminum foil with peel strengths approaching zero. However, separation from cleaned aluminum, treated polyethylene, or vinyl film proved to be impossible, leading to ripping of the substrate or cohesive failure of the coating.
  • Coating B is similar in chemical structure structure to Coating A with the major change being an increase in TMPTA level to provide a crosslink density of 0.29.
  • This change roduces a coating which Separates easily from cleaned aluminum, providing yet another potential carrying web. Further increases in crosslink density could be made to include treated polyethylene as a carrying web.
  • Coating C provides an additional illustration of the invention for coatings with Tg below the preferred range but still within the scope of the invention.
  • the T-peel results obtained for release from the same substrates as used previously but in contact with paper only are given in Table 7 below. These results are listed using the same order of substrates as used in the previous Tables.
  • Coating C has a crosslink density only slightly higher than that of Coating B, the separation from the substrate is not as easily performed.
  • it will be found that low Tg coatings will tend to adhere to most substrates to some extent. This adherence is due to the extreme softness of these coatings, which can lead to blocking in the roll or difficulty of obtaining easy release. For this reason, it is most preferable to control the Tg from 0 to 30°C., which provides coatings of optimal release properties and toughness in the cured film.
  • each of the coatings was applied to carrying webs of polyethylene, polyester, and corona treated polyethylene and cured in contact with a paper substrate at 7.6m./min/lamp using a bank of four mercury filled lamps (two lamps operated at 118 watts/cm.-and two lamps operated at 78 watts/cm.).
  • Table 9 The results are summarized in Table 9 below. All of these coatings fall outside the preferred range of Tg, but still within the range acceptable in this invention. All coating cured well, as indicated by an absence of tackiness after cure, and released easily from the polyester and polyethylene films employed as carrying webs.
  • Coatings E and F having relatively high Tg, demonstrated a tendency toward brittle failure during stripping as illustrated by the attempts to transfer from Corona treated polyethylene. For this reason, it is preferred to keep the Tg of the coating between about 0° and about 30°C.
  • a coating composition was formulated to demonstrate the invention as applied to coatings cured by crosslinking through an epoxy function.
  • the coating composition was obtained by blending 19.9 parts by weight of FC504, 60.6 parts of ERL-4221, 14.0 parts of ARALDITE 6004, 5 parts of RD-2 and 0.5 parts of an internal silicone lubricant.
  • the composition was applied to carryng webs of polyethylene and polyester films and cured in contact with paper by means of UV light as described previously. The cure was found to be complete under the conditions utilized and release of the coated paper fromthe carrying webs was easy and complete.
  • the photoinitiator levels were selected .in accordance with amounts required for cure in direct contact with an oxygen-containing atmosphere. normally, the curing of coatings by means of free radical polymerization is inhibited by oxygen. Similarly, the cure through epoxy groups is inhibited by water vapor. Because the use of the present invention presents a barrier against the ambient atmosphere during the curing stage (the coating is sandwiched between the web and the substrate), the level of photoinitiator may be reduced substantially while maintaining full cure of the coating. This is a significant advantage inherent in the invention, especially since the photoinitiators available in commerce are usually more expensive than the other coating ingredients.
  • the initiator levels in Coatings D, E and F were reduced to the 1% level and the previously described transfer coating experiments repeated.
  • the results were substantially the same as those recited in Table VIII.
  • the cure speed may be increased while maintaining the higher initiator levels.
  • the choice between these two alternatives i.e. - lower cost vs. higher curing rate) should best be determined by the economics of the process in which the invention is utilized.
  • polyester film was roughened by rubbing steel wool against the surface.
  • the coating was then applied to the roughened surface and transferred to a paper substrate as before.
  • the gloss of the coated surface of the paper and that of the roughened polyester film were found to have substantially the same reading of 53%. This result was further substantiated by transfer from a dull aluminum foil carrying web.
  • the invention is also useful for the production of coatings having a superior gloss and smoothness suitable for subsequent metallization.
  • Coating C was applied directly to paper by direct roll-coating and cured by electron beam radiation.
  • a second sample was prepared by transferring the same coating composition from a polyester film carrying web to another identical paper substrate and curing. After vacuum metallization of the cured coating the appearance of the two metallized surfaces were compared. While gloss readings could not be obtained due to the spectral reflection of the metal, the difference in brightness of the two surfaces was readily perceivable by the eye.
  • the metal film deposited on the coating transferred from the polyester film presented a much brighter, cleaner appearance.
  • the utilization of the invention to transfer a coating that is applied in a pattern to the carrying web is another desirable aspect. This was demonstrated by pigmenting Coating C with titanium dioxide at the 40% level by weight.
  • the pigmented coating composition was applied as a stripe on polyester film, transferred to paper and cured. The stripe of pigmented coating transferred easily and cleanly to the paper.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
EP19790301793 1978-09-01 1979-08-31 Procédé d'application d'une couche sur un substrat Expired EP0009885B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US93909578A 1978-09-01 1978-09-01
US939095 1978-09-01
US96718978A 1978-12-07 1978-12-07
US96718878A 1978-12-07 1978-12-07
US967189 1978-12-07
US967188 1992-10-27

Publications (2)

Publication Number Publication Date
EP0009885A1 true EP0009885A1 (fr) 1980-04-16
EP0009885B1 EP0009885B1 (fr) 1983-11-02

Family

ID=27420692

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19790301793 Expired EP0009885B1 (fr) 1978-09-01 1979-08-31 Procédé d'application d'une couche sur un substrat

Country Status (2)

Country Link
EP (1) EP0009885B1 (fr)
DE (1) DE2966367D1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043063A1 (fr) * 1980-06-28 1982-01-06 Letron GmbH Procédé pour la fabrication d'une feuille-support revêtue d'une laque durcie par irradiation électronique
FR2544633A1 (fr) * 1982-09-07 1984-10-26 Energy Sciences Inc Procede et appareil pour effectuer un traitement par elec trons sur un tambour refroidi
EP0141796A1 (fr) * 1983-09-21 1985-05-15 U C B, S.A. Procédé pour appliquer un revêtement de résine durcie sur un substrat
EP0172143A1 (fr) * 1984-07-31 1986-02-19 SOCIETA ITALIANA VETRO - SIV SpA Procédé de fabrication d'une bande comportant un film d'une résine acrylate utilisée dans des verres stratifiés de sécurité et produit obtenu
US4623087A (en) * 1983-05-26 1986-11-18 Rolls-Royce Limited Application of coatings to articles
EP0283651A1 (fr) * 1987-03-19 1988-09-28 Alkor Gmbh Kunststoffe Méthode pour la fabrication d'une couche ou d'un film de laque
EP0801603A1 (fr) * 1995-01-05 1997-10-22 A*Ware Technologies, L.C. Feuille portant un revetement et son utilisation
WO1999061168A1 (fr) * 1998-05-28 1999-12-02 Adkin Services Limited Durcissage de peintures aux uv
WO2003084681A1 (fr) * 2002-04-10 2003-10-16 Metso Paper, Inc. Procede et dispositif pour le transfert d'une substance a une bande

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1936674A1 (de) * 1968-07-20 1970-07-09 Giorgio Grecchi Verfahren und Vorrichtung zum Beschichten von Platten mit harzartigen Massen
FR2339017A1 (fr) * 1976-01-26 1977-08-19 Royal Industries Tissu et/ou pellicule revetus et procede pour les produire
DE2619313A1 (de) * 1976-04-30 1977-11-10 Graphische Verfahrenstech Kg Verfahren und vorrichtung zum lackieren von flachmaterial mit photopolymerisierbaren lacken

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1936674A1 (de) * 1968-07-20 1970-07-09 Giorgio Grecchi Verfahren und Vorrichtung zum Beschichten von Platten mit harzartigen Massen
FR2339017A1 (fr) * 1976-01-26 1977-08-19 Royal Industries Tissu et/ou pellicule revetus et procede pour les produire
DE2619313A1 (de) * 1976-04-30 1977-11-10 Graphische Verfahrenstech Kg Verfahren und vorrichtung zum lackieren von flachmaterial mit photopolymerisierbaren lacken

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043063A1 (fr) * 1980-06-28 1982-01-06 Letron GmbH Procédé pour la fabrication d'une feuille-support revêtue d'une laque durcie par irradiation électronique
FR2544633A1 (fr) * 1982-09-07 1984-10-26 Energy Sciences Inc Procede et appareil pour effectuer un traitement par elec trons sur un tambour refroidi
EP0122998A2 (fr) * 1982-09-07 1984-10-31 Energy Sciences Inc. Méthode et appareil pour le durcissement par électrons sur un tambour refroidi
EP0147906A1 (fr) * 1982-09-07 1985-07-10 Energy Sciences Inc. Procédé et appareil pour la décoration de surfaces de substrats sensibles aux radiations avec des revêtements durcis par irradiation électronique
EP0122998A3 (en) * 1982-09-07 1985-08-28 Energy Sciences Inc. Method and apparatus for electron curing on a cooled drum
US4623087A (en) * 1983-05-26 1986-11-18 Rolls-Royce Limited Application of coatings to articles
EP0141796A1 (fr) * 1983-09-21 1985-05-15 U C B, S.A. Procédé pour appliquer un revêtement de résine durcie sur un substrat
EP0172143A1 (fr) * 1984-07-31 1986-02-19 SOCIETA ITALIANA VETRO - SIV SpA Procédé de fabrication d'une bande comportant un film d'une résine acrylate utilisée dans des verres stratifiés de sécurité et produit obtenu
US4734143A (en) * 1984-07-31 1988-03-29 Societa Italiana Vetro Siv S.P.A. Process for the production of a continuous composite ribbon including an acrylate resin film to be used in safety laminated glass panels
EP0283651A1 (fr) * 1987-03-19 1988-09-28 Alkor Gmbh Kunststoffe Méthode pour la fabrication d'une couche ou d'un film de laque
EP0801603A1 (fr) * 1995-01-05 1997-10-22 A*Ware Technologies, L.C. Feuille portant un revetement et son utilisation
EP0801603A4 (fr) * 1995-01-05 1998-09-16 Ware Technologies L C A Feuille portant un revetement et son utilisation
WO1999061168A1 (fr) * 1998-05-28 1999-12-02 Adkin Services Limited Durcissage de peintures aux uv
WO2003084681A1 (fr) * 2002-04-10 2003-10-16 Metso Paper, Inc. Procede et dispositif pour le transfert d'une substance a une bande

Also Published As

Publication number Publication date
EP0009885B1 (fr) 1983-11-02
DE2966367D1 (en) 1983-12-08

Similar Documents

Publication Publication Date Title
US4388137A (en) Process for transfer coating with radiation-curable compositions
US4289821A (en) Surface replication on a coated substrate
KR100354946B1 (ko) 내마모성을 갖는 장식재
EP0050398B1 (fr) Feuille antiadhésive ainsi que procédé et appareillage pour obtenir une réplique de surface dans un revêtement antiadhésif
EP0011274B1 (fr) Matériau composite pour l'emballage secondaire de récipients
US6103352A (en) Decorated sheet
US5436073A (en) Multi-layer composite
US4427732A (en) Surface replication on a coated substrate
CA1096288A (fr) Traduction non-disponible
US5037668A (en) Radiation cure release coatings without silicone
EP0009885A1 (fr) Procédé d'application d'une couche sur un substrat
EP1485211B1 (fr) Composition de revetement a chaud utilisee dans le transfert et le coulage de feuilles
US6057033A (en) Radiation-curable release compositions containing cellulose fibers
JP4184497B2 (ja) 化粧シート
EP1343939B2 (fr) Procede de revetement d'un substrat
JPH03130199A (ja) ハードコート転写箔
JP2000006325A (ja) 耐摩耗性を有する化粧材
JPH03130200A (ja) ハードコート転写箔
JPS632780B2 (fr)
JPH0479835B2 (fr)
CA1143697A (fr) Compositions radio-curables pour enduits de transfert
McCarty et al. Radiation curable compositions useful as transfer coatings
JPH1177944A (ja) 耐摩耗性を有する化粧材
JPH0759626A (ja) 化粧板
JPH02182997A (ja) 金属蒸着ラベル用支持体及び金属蒸着ラベル

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

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed
ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

REF Corresponds to:

Ref document number: 2966367

Country of ref document: DE

Date of ref document: 19831208

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19840601

Year of fee payment: 6

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

Ref country code: DE

Payment date: 19840604

Year of fee payment: 6

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

Ref country code: BE

Payment date: 19840630

Year of fee payment: 6

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

Ref country code: FR

Payment date: 19840703

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19860301

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
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: 19860430

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

Ref country code: DE

Effective date: 19860501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

BERE Be: lapsed

Owner name: MOBIL OIL CORP.

Effective date: 19860831

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

Ref country code: GB

Effective date: 19881118

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

Ref country code: BE

Effective date: 19890831