EP0216269B1 - Dekorative Platte mit verbesserten Oberflächeneigenschaften - Google Patents

Dekorative Platte mit verbesserten Oberflächeneigenschaften Download PDF

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Publication number
EP0216269B1
EP0216269B1 EP19860112598 EP86112598A EP0216269B1 EP 0216269 B1 EP0216269 B1 EP 0216269B1 EP 19860112598 EP19860112598 EP 19860112598 EP 86112598 A EP86112598 A EP 86112598A EP 0216269 B1 EP0216269 B1 EP 0216269B1
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EP
European Patent Office
Prior art keywords
layer
radiation
polymerized
decorative
paper
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Expired - Lifetime
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EP19860112598
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German (de)
English (en)
French (fr)
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EP0216269A2 (de
EP0216269A3 (en
Inventor
Johannes Christinus Van Der Hoeven
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Trespa International BV
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Hoechst AG
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Priority to AT86112598T priority Critical patent/ATE75448T1/de
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Publication of EP0216269A3 publication Critical patent/EP0216269A3/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
    • B44C5/0476—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper with abrasion resistant properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31859—Next to an aldehyde or ketone condensation product
    • Y10T428/31862—Melamine-aldehyde
    • Y10T428/31866—Impregnated or coated cellulosic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to a decorative panel, composed of a core layer and a decorative layer on one or both sides, and to a method for the production thereof.
  • Panels of this type are used for indoor or outdoor applications in the construction sector, depending on their thickness they are used as cladding panels or as self-supporting elements.
  • the previously used decorative panels are, for example, decorative laminated panels (DIN 16 926), so-called "high pressure laminates” (HPL panels). They consist of a heat-pressed stack of resin-soaked paper webs as the core layer and a top layer of resin-soaked decorative paper. These plates have the disadvantage that they are attacked by mineral acids, in particular at concentrations above 10% and an exposure time of longer than 10 minutes. In addition, these standard panels are not sufficiently weather-resistant because the type of resin used in the top layer is sensitive to hydrolysis. Plates of this type can therefore only be used to a limited extent as worktops in chemical laboratories or for the production of wet cells which have to be cleaned with acids. When used outdoors, additional complex measures are required to improve their resistance to weather influences.
  • Laminates and sheets based on plastics such as polyester or acrylate sheets are particularly scratch-sensitive and not sufficiently resistant to organic solvents. For this reason, they are also less suitable for these applications.
  • DE-A-30 10 060 describes a multilayer plate which has a lacquer surface, the lacquer surface consisting of a lacquer which can be hardened by electron beams. Slabs with matt surfaces are not described.
  • a decorative plate which is particularly suitable for exterior applications, for interior fitting and for the production of special furniture, the surface of which is not sensitive to hydrolysis and has sufficient resistance to weathering influences, mineral acids and organic solvents and high surface hardness, is the subject of the unpublished EP application 85105851.1 (EP-A -0 166 153). It is made up of a core layer and a decorative layer on one or both sides. At least the outermost layer of the plate on at least one of the two plate surfaces consists predominantly of a synthetic resin composed of one or more components polymerized by radiation, selected from the group of unsaturated acrylates and methacrylates. This layer shows a particularly high surface hardness.
  • a liquid surface layer which comprises the radiation-polymerizable components, is applied to a base and then polymerized by radiation. Only after a further step in which the surface layer polymerized by radiation is pressed together with the base at elevated temperature. the plate surface shows the required properties.
  • this decorative plate shows the often undesirable property of being more or less shiny.
  • the plate surface can have a structure structured according to the surface of the separation medium, for example an orange peel-like surface structure, but its surface gloss is still very high.
  • matting agents such as silicon dioxide pigments in the outermost surface layer of the plate practically does not reduce the gloss, because the pigment-matt surface, which was initially silk-matt after the radiation polymerization, strangely shines again as soon as the plate is subsequently subjected to heat compression.
  • the plate is a flat body, its surface shape and Surface structure is adapted to the application and can, for example, also have a curved shape.
  • a plate in the sense of the invention is also to be understood as films.
  • the force with which a diamond needle creates a visible scratch on the plate surface is determined. This assessment is carried out immediately after the action of the diamond needle, since the surface layer can be gradually reset due to the elasticity of the surface layer after the scratching.
  • the scratch resistance is a measure of the surface hardness.
  • this decorative plate with the special synthetic resin layer polymerized by radiation on at least one of the outer surfaces not only has excellent weather resistance compared to the previously known plates, but surprisingly has an increased surface hardness. It is also much less sensitive to acids and organic solvents.
  • the reflectometer value is used as a measure of the gloss of the plate surface with a reflectometer type RB / Dr. Determined for a long time according to DIN 67 530.
  • a reflectometer value determined according to this standard represents an optical parameter for the surface of a test specimen which is related to the gloss of the surface. It is to take into account that the gloss is not a purely physical, but also a physiologically and psychologically related variable. A direct measurement of the gloss is therefore not possible, but the "glossiness", namely the proportion which the surface contributes to the appearance of the gloss due to its reflective properties, can in principle be measured in a suitable manner.
  • the reflectometer value can be used as a measure of the gloss, because it is essentially determined by the reflective properties of the surface.
  • the reflectometer system defined by this standard is based on the arrangements described in the ASTM D 523-67 standard.
  • the radiation angles 20 °, 60 ° and 85 ° are chosen arbitrarily.
  • the 20 ° measuring geometry is used for test specimens with a 60 ° reflectometer value above 70, the 85 ° measuring geometry for test specimens with a 60 ° reflectometer value below 30.
  • a light source is imaged centrally in the opening of an aperture.
  • the light rays hit the surface of the plate at the specified angle of incidence (20 °, 60 ° or 85 °) and are reflected in a scattered manner.
  • the luminous flux passing through the aperture is measured with a photoelectronic receiver located behind the aperture.
  • the core layer has the supporting function of the plate. They is made of wood, for example. Sheets or foils made of plastic, for example based on polyvinyl chloride, polyethylene and polystyrene, or made of metal, for example made of steel, aluminum, copper, brass or other alloys, are also suitable as the core layer.
  • the radiation-polymerized synthetic resin layer is located directly on the surface of these core layers or is connected to the core layer by means of glue films or glue joints, but preferably with adhesion-promoting synthetic resins such as phenol-formaldehyde or resorcinol-formaldehyde precondensate. Glue joints are pure adhesive layers, glue films are carrier layers that are coated or soaked with adhesive. Adhesion promoters are substances that, without being adhesive themselves, promote the connection of two different types of material.
  • the core layer can also consist of the sheets of paper, in particular sodium kraft paper, impregnated with heat-curable synthetic resin, in particular phenol-formaldehyde resin, which are customary in H.P.L. plates and are pressed in the heat. Depending on the desired plate thickness, 1 to about 100 sheets are superimposed in the heat.
  • the core layer can also consist of pressure-hardened nonwoven or mats made of mineral fibers, glass fibers, plastic fibers or a fiber mixture, but preferably made of cellulose.
  • Cellulose-containing fiber layers are, for example, tangled wood fibers or wood chips.
  • the nonwoven, or mat, made of wood and / or cellulose fibers is produced by applying a synthetic resin to the fibers, drying the resin-coated fibers, shaping a fiber mat and pre-compressing this mat under the action of pressure (EP-A-0 081 147) .
  • this fiber-containing core layer On the outer surface (s) of this fiber-containing core layer there is possibly an underlay which contains a thermosetting aminoplast or phenoplast resin.
  • This layer consists e.g. from a pigmented or unpigmented nonwoven or paper.
  • the fiber-containing core layer or this underlay layer is followed directly by a radiation-polymerized synthetic resin layer which is decorative, i.e. shows special optical effect or decorative effect by added dyes.
  • a radiation-polymerized synthetic resin layer which forms the outermost surface (s) of the plate; however, it is entirely possible to omit this clear synthetic resin layer, so that the decorative synthetic resin layer (s) then form (s) the outermost layer (s).
  • a decorative layer based on a colored and / or printed plastic film or based on paper can also be used are, which usually consists of a pigmented, colored and / or printed decorative paper.
  • the synthetic resin layer polymerized by radiation, in this case transparent and dye-free, is located on the plastic film or the decorative paper.
  • the decorative paper contains the usual thermosetting synthetic resin, in particular aminoplast resin, and is located on core layers, which are made up of the sodium kraft paper typical of HPL boards or of phenol-resinous, tangled wood or cellulose fibers.
  • the compounds provided for the production of the uppermost layer of resin polymerized by radiation comprise acrylic acid esters or methacrylic acid esters which are radically polymerizable by actinic radiation and which are present individually or together in a polymerizable mixture.
  • the preferred component is a polyfunctional, ie polyunsaturated, prepolymer.
  • a further component with a diluting effect is optionally present in the copolymerizable mixture, which component is referred to as the dilution monomer or dilution oligomer.
  • the polyfunctional prepolymer has a proportion of 50 to 100, in particular 60 to 90,% by weight of the total weight of the copolymerizable components.
  • Low viscosity prepolymers (less than 100 poise at 20 ° C) are used without the thinning monomers or oligomers.
  • the components used have a strong tendency to polymerize radically when exposed to actinic radiation. Close UV light or high-energy radiation comes as actinic radiation, e.g. Electron-corpuscular or X-ray radiation into consideration.
  • the free-radically polymerizable prepolymer is a polyfunctional unsaturated aliphatic or aromatic acrylate or methacrylate, preferably an unsaturated polyester acrylate oligomer, but in particular an aliphatic urethane acrylate oligomer.
  • Aromatic urethane acrylate oligomers also lead to scratch-resistant surface layers, but yellow after a while in outdoor applications.
  • a mono-, di-, tri-, tetra-, penta- or hexaacrylate or -methacrylate is used in the free-radically copolymerizable mixture as an additional suitable monomer or oligomer.
  • These mono- to hexaacrylates or methacrylates are esters of polyols with 1 to 6 OH groups with acrylic acid or methacrylic acid and are therefore also referred to as polyol acrylates or polyol methacrylates.
  • Suitable diacrylates are esters of acrylic acid with aliphatic, dihydric alcohols, in particular ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butanediols, 1,6-hexanediol or neopentyl glycol, with aliphatic ether alcohols, in particular diethylene glycol, dipropylene glycol, dibutylene glycol, polyethylene or polyethylene Polypropylene glycols, with oxyalkylated compounds of the aforementioned aliphatic Alcohols and ether alcohols or also with aromatic dihydroxyl compounds, in particular bisphenol A, pyrocatechol, resorcinol, hydroquinone, p-xylylene glycol or p-hydroxybenzyl alcohol.
  • aliphatic, dihydric alcohols in particular ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butanediols, 1,6-hexanediol
  • Preferred diacrylates are 1,6-hexanediol diacrylate, tripropylene glycol diacrylate and 1,4-butanediol diacrylate.
  • Preferred triacrylates are trimethylolpropane triacrylate and pentaerythritol triacrylate.
  • suitable polyfunctional prepolymers are also epoxy acrylate and silicone acrylate oligomers, which are preferably used in the free-radically copolymerizable mixture with the diacrylates or triacrylates mentioned.
  • the prepolymers are known compounds and are produced, for example, from hydroxylated copolymers in which the hydroxyl groups are randomly distributed along the copolymer chain.
  • Statistically unsaturated acrylic copolymers are obtained from this copolymer by esterification of the hydroxyl groups with acrylic acid.
  • the hydroxyl group is attached to the end of the chain in the preparation of the hydroxylated copolymer.
  • Urethane acrylate oligomers are produced by reacting (meth) acrylic acid esters containing hydroxy groups, for example hydroxyethyl methacrylate, with polyvalent isocyanates, preferably diisocyanates.
  • the di- or polyisocyanates can preferably be reaction products of diols, polyether diols or polyester diols with a stoichiometric excess of monomeric di- or polyisocyanate.
  • the chemical nature of the base polymer determines the properties of the hardened surface layer.
  • the added mono- to hexaacrylate or methacrylate, as the diluting monomer or oligomer, allows the viscosity of the mixture to be cured to be adjusted, which is normally in a viscosity range from 20 to 100 poise (20 ° C.), and fully takes on the radical polymerization part.
  • the coating is cured by radical polymerization between the double bonds of the prepolymer and the dilution monomers or oligomers which may be present.
  • photoinitiators When curing under the action of actinic radiation, photoinitiators must be added which absorb UV light and facilitate the initiation of radical polymerization with the formation of radicals. On the other hand, no photoinitiators are required when curing with electron beams. Most photoinitiators contain at least one carbonyl group that is conjugated to an aromatic ring. A photoinitiator system consisting of several components is usually used.
  • the radiation-polymerized synthetic resin contains, if necessary, to achieve the desired decorative, mechanical and physical surface properties suitable additives such as plasticizers, fillers, dye pigments, agents to improve the abrasion resistance and stabilizers.
  • suitable additives such as plasticizers, fillers, dye pigments, agents to improve the
  • the liquid compounds polymerizable by radiation are applied to the substrate to be coated, e.g. by spraying, pouring, a doctor blade system, a roller or screen printing.
  • the applied layer when applied to a decorative layer, is transparent. But it can also be decorative itself and is then colored and is on a non-decorative paper layer or directly on the core layer.
  • an additional layer which can be polymerized by radiation, is applied to this decorative synthetic resin layer after radiation curing, but is not decorative but transparent.
  • the base used for the application of the compounds polymerizable by radiation is thus a paper layer, a decorative paper layer or the above-mentioned core layers based on wood, plastic, metal or a stack of further fiber-containing layers, which forms the core of the plate obtained later.
  • the fibrous layers of the stack which are preferably made of sodium kraft paper or a Nonwovens made of wood and / or cellulose fibers contain the heat-curable pre-hardened resins that are customary in HPL boards, in particular phenol-formaldehyde resins, while the papers which may additionally be present on the stack contain an aminoplast resin, but in particular a phenoplast resin .
  • the content of thermosetting resins is 20 to 250 wt .-%, based on the respective layer.
  • the fiber-containing layers or the paper layers are impregnated or impregnated, for example, by immersion in a bath with a solution or dispersion containing the thermosetting resin or by application or spraying on using a metering system.
  • the solvent or dispersant is aqueous-alcoholic, aqueous-acetone or aqueous. It can also contain up to 20% by weight of flame retardant.
  • the distribution of the desired amount of resin is then carried out by stripping or squeezing, e.g. with rollers.
  • thermosetting resins of the base are precured and dried as usual.
  • the outermost, still liquid layer is made of radiation-polymerizable compounds with a film or plate made of plastic or paper or a composite film various plastic layers or plastic and paper layers with a rough surface structure, which must be sufficiently permeable to actinic radiation.
  • the film or plate provided for covering must not have a highly porous surface, since otherwise there is a risk that the liquid compounds which can still be polymerized by radiation penetrate into the surface. In this case, the film or plate can no longer be removed after the polymerization.
  • This outermost liquid layer can itself be decorative and contain a dye or non-decorative, that is to say transparent, and can then be located on a decorative layer or on a decorative synthetic resin layer polymerized by radiation.
  • Films with a thickness of up to 0.1 mm are preferably used, since thicker covers for electron beams or UV rays do not have sufficient permeability or require relatively long exposure times.
  • foils with a thickness of 20 to 60 ⁇ m are used, since on the one hand they are sufficiently transparent to the radiation and on the other hand they also have sufficient mechanical strength. For the sake of simplicity, the following is referred to as foils or cover foils.
  • the plastic film consists in particular of a polyester or polypropylene film oriented by biaxial stretching.
  • the rough structure of the film provided for covering is produced, for example, by adding pigments, at least in the vicinity of its outer surface. This surface roughness is due to Elevations in the film surface, the height of which, however, is only small in comparison to the film thickness and is in the range of a maximum of a few micrometers.
  • the pigments consist, for example, of inorganic particles, in particular of aluminum oxide, aluminum sulfate, barium sulfate, calcium carbonate, magnesium carbonate, kaolin, talc, silicon dioxide, titanium dioxide or microglass beads, or organic plastic particles which are incompatible with the plastic of the film and are dispersed in the film in particulate form.
  • the pigments usually have a particle size of 0.1 to 20 ⁇ m, the average particle size being in the range of 0.1 to 4 ⁇ m.
  • Their concentration is 0.01 to 10% by weight, based on the film weight.
  • the concentration of the pigments in the film and their size is set depending on the desired surface roughness of the plastic film.
  • the cover film is applied to the liquid layer which can still be polymerized by radiation by first applying this liquid layer to the base in the manner described above and then providing it with the cover film, the rough surface side of the cover film having the liquid, polymerisable layer Layer comes into contact.
  • the roughness of the surface is reflected on the surface of the transferred by radiation to the layer to be polymerized, which then adopts the surface structure of the cover film and receives a matt surface. This result is all the more surprising since the surface gloss of the end product can practically no longer be reduced by using structured separating media during the final pressing.
  • a common source of free radical formation such as e.g. a photoinitiator, or just heat is applied. If the photopolymerizable layer contains photoinitiators, the polymerization is initiated as it passes under mercury vapor lamps. The absence of oxygen is not required for curing with UV radiation.
  • the electron beams used to harden the polymerizable compounds expediently have an energy corresponding to 150 to 350 KeV.
  • the energy of the electron accelerator is determined by the thickness of the synthetic resin layer to be formed, the necessary radiation dose and the duration of exposure or the speed at which it is carried out.
  • the devices used to accelerate the electron beams are commercially available. These are the accelerators known as “scanner type” and “linear cathode type”. By interacting with the components of the polymerizable layer, free radicals are formed. This curing process is usually carried out at room temperature. Also for curing by means of electron beams, it is not necessary for this process to take place in an inert, ie largely oxygen-free, atmosphere, since the polymerizable surface layer is protected by the plastic film lying thereon.
  • the cover film can be removed. However, the cover film can also only be removed after the process has ended, i.e. after heat pressing, remove or use as a covering of the finished plate. If they are sufficiently flexible, the documents are wound up for storage or cut to the desired format. If the base comprising the radiation-polymerized resin consists only of a paper layer, it is placed on a stack of fiber-containing layers forming the core layer. It is also possible to additionally provide the lower side of the stack with such a base.
  • the resulting layer package of fiber-containing core layer and radiation-polymerized surface layer (s) and, if necessary, intermediate layers of paper or decorative paper is, as is customary in the production of HPL plates, pressed into a decorative plate in the heat, the thermosetting resins being cured .
  • the temperature is preferably 120 to 210 ° C, the pressure in the range of 10 to 100 bar and the exposure time is 1 to 30 minutes.
  • the temperature and pressure can usually be reduced to values of 80 ° C and 5 bar.
  • the pressing takes place in a known stationary, continuous or continuous pressing device.
  • the number and the thickness of the fiber-containing layers of the core layer or the thickness of the core layer is selected depending on the use of the plate, with plate thicknesses of 3 to 25 mm being required for external applications depending on the intended use.
  • the individual plates are separated from one another by a separating medium.
  • the separation medium is e.g. a layer of paper, plastic film or metal plate. If the separation medium has a rough surface structure, i.e. Elevations or depressions, the rough outer structure of the respective plate is given this rough structure, while the existing matt fine structure is retained. The degree of gloss of the plate surface already determined by the radiation process can practically no longer be changed by the separating medium.
  • the decorative panels produced are surprisingly particularly weather-resistant and extremely scratch-resistant, which may be unpredictable Interaction between the different resins or maybe also based on a post-crosslinking of the free-radically polymerizable compounds during the heat pressing.
  • the scratch resistance and chemical resistance is surprisingly much higher than in the case of a plate which is coated with the same compounds which can be polymerized by radiation and whose coating - without the heat compression - has only been radically polymerized by radiation.
  • the plate surface shows a greatly reduced gloss, which cannot be achieved even when matting agents are used in the surface layer.
  • FIGS. 1 to 4 The invention is illustrated by FIGS. 1 to 4 and the following examples.
  • the percentages are percentages by weight.
  • the partially cured synthetic resin-containing kraft paper 1 is provided with a dye-containing radiation-polymerizable liquid layer 2.
  • the layer 2 is covered with the plastic film 3 and cured in the device 4 with electron beams.
  • the dye-containing layer 5 has already been partially cured by radiation when it is provided with the transparent liquid layer 6 polymerizable by radiation.
  • the plastic film 3 is applied to the layer 6. 3 differs from FIG. 1 only in that there is still a transparent liquid layer 6 polymerizable by radiation on the plastic film 3.
  • the deflection rollers are 7,8,9,10 and the coating devices 11 and 12. 1a and 3a, according to the layer arrangements of FIGS. 1, 2 and 3, pressed plates 14 can be seen.
  • the stack forming the core is designated 13.
  • a paste-like liquid 2 (viscosity 50 poise at 25 ° C) from a radiation.
  • a paste-like liquid 2 viscosity 50 poise at 25 ° C
  • a first hardened with phenol-formaldehyde resin (resin application 70%) impregnated polymerizable mixture of 85 parts by weight aliphatic urethane acrylate oligomers as prepolymer, 15 parts by weight Hexanediol diacrylate as a dilution monomer and 10 parts by weight organic dye pigments applied, forming a closed film (layer thickness about 80 microns).
  • the absorbed radiation dose is 60 kGy.
  • the 10 mm thick decorative plate 14 obtained on both sides has a scratch resistance of greater than 3.0 N (DIN 53799, part 10). It is insensitive to hydrolysis and shows no changes after boiling in water for 100 hours. Concentrated mineral acid does not attack its surface for a period of 6 hours (DIN 53230). The light fastness of this plate is rated 8 (DIN 54004). The resistance of the plate to weather influences is measured according to ASTM G 53-84, whereby a time cycle of 4 h UV / 4 h CON (condensation period) at a test temperature of 50 ° C. is observed over 1500 h.
  • the decorative surfaces show a low surface gloss corresponding to a reflectometer value of 20-22, radiation angle 60 ° or a reflectometer value of 44-45, radiation angle 85 ° (DIN 67 530). After weathering, the panel shows no discoloration or change in gloss.
  • the decorative plate 14 obtained has a scratch resistance of greater than 2.0 N (DIN 53 799, part 10). Concentrated mineral acid does not attack its surface for 6 hours. The light fastness of this plate is rated 8 (DIN 54 004). It shows a surface gloss corresponding to a reflectometer value of 22-24, radiation angle 60 °, or a reflectometer value of 44-45, radiation angle 85 ° (DIN 67 530).
  • the pasty dye-containing liquid 2 made of radiation-polymerizable compounds of Example 1 is applied to a sodium kraft paper 1 initially impregnated with heat-curable phenol-formaldehyde resin (resin application 70%), a closed film (layer thickness approximately 80 ⁇ m) trains (see FIG. 3).
  • a transparent layer 6 of a pasty, dye-free liquid made of the same compounds polymerizable by radiation (layer thickness about 20 to 40 ⁇ m) is applied to a matted plastic film 3 made of polypropylene.
  • the paper 1 and the plastic film 3 are then placed one on top of the other in sheet or web form, so that the two liquid layers 2, 6 come into contact with one another. Make sure that there are no air pockets.
  • the polymerizable compounds are crosslinked by means of electron beams which strike the liquid layers 2, 6 through the plastic film 3.
  • the absorbed dose is 60 kGy.
  • the paper 1 with the polymerized surface layer 2, 6 is further processed into a decorative plate 14 by heat pressing with a paper stack 13 as described in Example 2.
  • the synthetic resin layers polymerized by radiation in the examples still show relatively low scratch resistance values in the range from about 0.7 to 0.9 Newton before the hot pressing. Only after the synthetic resin layer polymerized by radiation has been subjected to heat compression according to the invention is a surprisingly obtained a significantly higher surface hardness of the plate.
  • a long reflectometer value measured according to DIN 67 530 is 45 to 47, radiation angle 20 ° or approximately 83, radiation angle 60 ° if the matt plastic film is missing when crosslinked with electron beams. It can be reduced to values from 37 to 41, angle of incidence 20 ° or approximately 79, angle of incidence 60 °, if structured pressing elements are used in the heat pressing, which, for example, include an outermost layer of the plate Give surface texture similar to orange structure.
  • By adding matting agents to the surface layer even lower reflectometer values can be achieved, which are approximately 30 to 36, angle of incidence 20 °, or approximately 75, angle of incidence 60 °.
  • the particularly low gloss values according to the invention can only be achieved by the special measures in the polymerization of the synthetic resin layer.

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  • Laminated Bodies (AREA)
  • Panels For Use In Building Construction (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Paper (AREA)
EP19860112598 1985-09-21 1986-09-11 Dekorative Platte mit verbesserten Oberflächeneigenschaften Expired - Lifetime EP0216269B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86112598T ATE75448T1 (de) 1985-09-21 1986-09-11 Dekorative platte mit verbesserten oberflaecheneigenschaften.

Applications Claiming Priority (2)

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DE19853533737 DE3533737A1 (de) 1985-09-21 1985-09-21 Dekorative platte mit verbesserten oberflaecheneigenschaften
DE3533737 1985-09-21

Publications (3)

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EP0216269A2 EP0216269A2 (de) 1987-04-01
EP0216269A3 EP0216269A3 (en) 1988-12-21
EP0216269B1 true EP0216269B1 (de) 1992-04-29

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EP19860112598 Expired - Lifetime EP0216269B1 (de) 1985-09-21 1986-09-11 Dekorative Platte mit verbesserten Oberflächeneigenschaften

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US (1) US4789604A (ja)
EP (1) EP0216269B1 (ja)
JP (1) JP2536853B2 (ja)
AT (1) ATE75448T1 (ja)
AU (1) AU597272B2 (ja)
CA (1) CA1290718C (ja)
DE (2) DE3533737A1 (ja)
ES (1) ES2002759A6 (ja)
NO (1) NO863746L (ja)

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Publication number Priority date Publication date Assignee Title
EP2927017B1 (en) 2014-04-04 2018-02-21 Unilin, BVBA Method of covering a substrate
EP2927017B2 (en) † 2014-04-04 2022-01-19 Flooring Industries Limited, SARL Method of covering a substrate

Also Published As

Publication number Publication date
ATE75448T1 (de) 1992-05-15
CA1290718C (en) 1991-10-15
ES2002759A6 (es) 1988-10-01
EP0216269A2 (de) 1987-04-01
US4789604A (en) 1988-12-06
NO863746L (no) 1987-03-23
JPS6299147A (ja) 1987-05-08
AU6303686A (en) 1987-03-26
AU597272B2 (en) 1990-05-31
EP0216269A3 (en) 1988-12-21
DE3685074D1 (de) 1992-06-04
NO863746D0 (no) 1986-09-19
DE3533737A1 (de) 1987-03-26
JP2536853B2 (ja) 1996-09-25

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