EP2219883B1 - Plaque composite multicouche - Google Patents

Plaque composite multicouche Download PDF

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Publication number
EP2219883B1
EP2219883B1 EP08863535A EP08863535A EP2219883B1 EP 2219883 B1 EP2219883 B1 EP 2219883B1 EP 08863535 A EP08863535 A EP 08863535A EP 08863535 A EP08863535 A EP 08863535A EP 2219883 B1 EP2219883 B1 EP 2219883B1
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EP
European Patent Office
Prior art keywords
gloss
particles
range
layer
composite board
Prior art date
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Application number
EP08863535A
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German (de)
English (en)
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EP2219883A1 (fr
Inventor
Donald Schaefer
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.)
Resopal GmbH
Original Assignee
Resopal GmbH
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Filing date
Publication date
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Priority to PL08863535T priority Critical patent/PL2219883T3/pl
Publication of EP2219883A1 publication Critical patent/EP2219883A1/fr
Application granted granted Critical
Publication of EP2219883B1 publication Critical patent/EP2219883B1/fr
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Classifications

    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements

Definitions

  • the present invention relates to a composite panel and a panel comprising this composite panel.
  • Multilayer composite panels also called laminate panels or laminates
  • laminate panels are used today in many areas of life for utility and decoration purposes. For example, they are used in interior design for cladding windows, stairs and floors, and in the coating of furniture in both private and commercial areas.
  • Multilayer composite panels usually consist of a certain number of different sheets of paper, which are impregnated with curable synthetic resins, stacked on top of each other and pressed together under heat and high pressure by means of press plates (often referred to as press plates).
  • the core of these composite panels is usually an array of sheets of kraft paper on which a sheet of decor paper decorated with patterns or colors is usually placed.
  • a usually transparent overlay can be attached to the decorative paper sheet.
  • High-pressure laminates (HPLs) produced in this way are sold, for example, under the trade name Resopal.
  • Multilayer composite panels are often processed into panels, such as floor panels, which are used as interior or exterior floor coverings of buildings.
  • the floor panels serve as a permanent footboard and footprint and are therefore exposed to high mechanical stresses.
  • a high abrasion resistance of surfaces of composite panels or laminate flooring having these composite panels is achieved, in particular, by incorporating into the composite panels corundum particles which are naturally characterized by a high degree of hardness.
  • the abrasion resistance can be controlled in particular by the size and the amount of corundum particles used.
  • the paper sheet should be provided on at least one side with 2 to 20 g / m 2 , preferably 3 to 12 g / m 2 hard particles. According to this document, unacceptable fog formation is observed at levels of more than 20 g / m 2 of hard particles.
  • Another decisive criterion for the quality of composite panels is not only the abrasion resistance but also the gloss level of the surface.
  • the high gloss of the surface which is usually desired by the user, is decisively determined by the type of cured binder lying on the surface of the composite panel.
  • the gloss level of the surface of composite panels also depends on the surface finish of the press plate used for the compression of the composite panels.
  • smooth, high-gloss press plates can be used to produce composite panels with a high-gloss surface.
  • EP 0219 769 B1 describes a decorative laminate and a method of making such a laminate.
  • the decorative sheet of the laminate is coated with particulate abrasive material having a hardness greater than that of silica.
  • abrasive material 0.2 to 10 g / m 2 , preferably 4 to 6 g / m 2 applied. For orders of more than 10 g per square meter, the appearance of the surface may be dim.
  • the resistance of the laminate surface to scratching was tested by measuring the loss of gloss after shearing. The 10 post double rub gloss loss using 3M Scotch Brite type 8A Abrasive Pads is 4%.
  • AT 40 807 E claims a decorative laminate bonded by heat and pressure, the outermost surface of the laminate containing mineral particles having a Mohs hardness of at least 5 and present in an amount in the range of 0.5-25 g / m 2 .
  • the laminates often become cloudy and lose their shine. Luster loss after scrubbing with 10 double strokes using 3M Scotch Brite type 8A abrasive pads is approximately 5%.
  • the decorative laminate consists of a decorative layer and a protective layer firmly connected to the decorative layer, which consists of a mixture of at least one heat-hardened synthetic resin, hard particles (Mohs hardness at least 5) and at least one wax.
  • the addition of the wax has a favorable effect on the tool stress, in particular in the manufacturing process.
  • a preferred embodiment which contains no hard particles in the decorative sheet or the coating sheet. This will give you a better visual impression of the pattern. No wear and abrasion tests were performed.
  • EP 0 875 399 A2 relates to a decorative laminate with abrasion-resistant surface coating.
  • the particles of the hard material, such as corundum are distributed.
  • the wear layer contains a corundum loading of 69g / m 2 . This is achieved by special additives in the resin matrix. There is no information on the gloss and gloss retention of the laminates.
  • DE 197 10 619 A1 relates to solid particles coated with melamine resin, wherein the hardness of the solid particles according to Mohs is at least 7. Furthermore, the invention relates to aqueous impregnating solutions which contain these coated solid particles and other substances, such as are customary in solutions which are suitable for the production of overlay and decorative films, and the overlay and decorative films produced therewith. There is no information on the gloss and the gloss resistance of the laminates.
  • WO 2005/042 644 A1 describes a decorative paper with scattered abrasion-resistant particles. Overlay and decorative paper are preferably combined and pressed so that the abrasion-resistant particles form an intermediate layer. There is no information on the gloss and gloss retention of the laminates.
  • DE 1 629 426 A describes abrasion resistant decorative laminates, characterized in that the resin composition of the surface layer contains finely divided material having a hardness of at least 9 on the Mohs hardness scale. There is no information on the gloss and gloss retention of the laminates.
  • WO 2008/128702 A1 is a document under Art. 54 (3) EPC and discloses a wear shield containing hotshot particles on an HDF board.
  • Composite panels are therefore known from the prior art whose surfaces show increased abrasion resistance or increased gloss retention.
  • the present invention is therefore based on the object to provide a composite panel whose surface is characterized by excellent gloss retention and high abrasion resistance.
  • one or more sheets of kraft paper are included.
  • the kraft paper used in the present invention is a paper which consists predominantly of Kraft pulp, to which Kraft paper can be added, and which has a high strength, in particular a high tensile strength, and a high resistance.
  • Kraft paper is usually made from at least 90 percent fresh, preferably unbleached sulphate pulp (kraft pulp).
  • kraft paper may contain starch, alum and / or glue in addition to the pulp in order to achieve, for example, certain surface effects and increases in strength.
  • kraft paper has kraft paper with a grammage of 150 - proved to 300 g / m 2, in particular 220-270 g / m 2 to be particularly advantageous.
  • a preferred kraft paper is soda kraft paper familiar to those skilled in the art of HPL.
  • the number of kraft paper sheets used depends essentially on the desired thickness of the core layer or composite panel.
  • the composite panel of the present invention contains one to eight sheets, more preferably 3 to 7 sheets, and more preferably 4 to 6 sheets of kraft paper.
  • the weight of the kraft paper used in the invention is not further limited. It depends in particular on the number of kraft paper sheets used and thus on the desired thickness of the composite panel. According to a preferred embodiment, the weight of the kraft paper sheets used is in the range of 125 to 250 g / m 2 , preferably 140-230 g / m 2 .
  • the final thickness of the composite panel according to the invention is in the range of 0.75 to 0.85 mm, preferably 0.8 mm.
  • the final thickness of the composite panel according to the invention is in the range of 0.95 to 1.05 mm, preferably 1.0 mm.
  • the final thickness of the composite panel according to the invention is in the range of 1.15 to 1.25 mm, preferably 1.2 mm.
  • a decorative layer is applied which comprises a sheet of decorative paper.
  • the decorative layer designates that layer applied to the core layer whose pattern can be visually perceived by the viewer.
  • decorative paper refers to any material that is suitable for bonding to the underlying core layer and, optionally, the overlying overlay layer, and that can render a décor.
  • the preferred material for decor paper is paper.
  • films, for example plastic films, or veneers can be covered by the term decorative paper.
  • Veneers are Wood leaves, which usually have a thickness of 0.1 to 3 mm and the decorative layer can give a wooden look, for example, a certain grain.
  • the decor is applied to the decorative paper by means of a printing process.
  • any desired motif can be created and imprinted on the decor paper in gravure printing.
  • the motif may consist of wood, stone, ceramic, color and / or fantasy patterns.
  • the motif can also be done by painting the decor paper with one or more colors.
  • the basis weight of the decorative paper used is not further limited.
  • the basis weight is preferably in the range from 40 to 120 g / m 2 , more preferably in the range from 60 to 100 g / m 2 , in particular from 70 to 90 g / m 2 .
  • an underlay layer may be arranged between the core layer and the decorative layer.
  • this underlay layer may serve to prevent distortion of the composite panel or to reduce electrostatic charges.
  • the underlay layer comprises one or more sheets of kraft paper.
  • the composite panel has an overlay layer, then this preferably forms the cover layer for the multilayer composite panel according to the invention and is applied to the decorative layer.
  • the overlay layer comprises one or more sheets of a preferably fibrous material.
  • the basis weight of the sheets used for the overlay layer is not further limited. It is preferably in the range of 12 to 40 g / m 2 , more preferably in the range of 20 to 35 g / m 2 and even more preferably in the range of 25 to 32 g / m 2 .
  • the overlay material preferably has a high resistance to chemical, thermal and mechanical stress. If fibrous material is used to make the overlay, then it contains fibrous material preferably bleached pulp fiber, in particular cellulose, for example ⁇ -cellulose.
  • the overlay material is preferably of a nature which ensures that the motif of the decorative paper layer underlying the overlay is visible after being pressed into the decorative, multilayer composite material according to the invention. Therefore, the overlay preferably has a high degree of transparency.
  • the particles contained in the composite panel according to the invention have a Mohs hardness of at least 8, preferably at least 8.5, and more preferably at least 9.
  • the particles are preferably particles of corundum (aluminum oxide), silicon carbide, aluminum boride, boron carbide or mixtures thereof. Particularly preferred are corundum particles, in particular particles of corundum.
  • the corundum particles can for example be predominantly sharp-edged or cubic and are preferably predominantly cubic.
  • the particles may be surface-treated in a manner known to those skilled in the art.
  • the particles may have a coating with silane compounds.
  • the particles are uncoated.
  • the particles having a Mohs hardness of at least 8 preferably have a certain particle size distribution, which is determined according to the FEPA standard 42-2: 2006.
  • d3 values, d94 values and D50 values are defined, whereby the D50 value indicates the mean particle size of the particles.
  • the mean grain size is grain size, in which 50 percent of the particles have a particle size smaller and 50 percent of the particles have a particle size greater than the mean grain size.
  • the mean particle size D50 of the particles used having a Mohs hardness of at least 8 is in the range of 5 to 100 ⁇ m, more preferably in the range of 5 to 75 ⁇ m, even more preferably in the range of 12 to 75 ⁇ m, in particular in the range of 45 to 75 ⁇ m, for example at 68 ⁇ m.
  • the maximum d3 value is preferably above the average particle size of the particles, for example 1.4 to 2.2 times, more preferably 1.5 to 2.2 times, even more preferably 1.5 to 2, 0 times, and more preferably 1.5 to 1.8 times above the average particle size of the particles.
  • the maximum d3 value may be in the range of 10 ⁇ m to 156 ⁇ m, more preferably in the range of 10 ⁇ m to 118 ⁇ m, even more preferably in the range of 23 ⁇ m to 118 ⁇ m, in particular in the range of 72 ⁇ m to 118 ⁇ m.
  • the minimum d94 value is preferably below the mean grain size of the particles, and is, for example, 0.20 to 0.68 times, more preferably 0.23 to 0.65 times, still more preferably 0 , 34- to 0.65-fold, and more preferably from 0.60 to 0.65 times the mean particle size of the particles.
  • the minimum d94 value may be in the range of 1 ⁇ m to 65 ⁇ m, more preferably in the range of 1 ⁇ m to 50 ⁇ m, even more preferably in the range of 5 ⁇ m to 50 ⁇ m and in particular in the range of 25 ⁇ m to 50 ⁇ m ,
  • Particles which have an average particle size D50 in the range from 45 ⁇ m to 75 ⁇ m, preferably in the range from 63 ⁇ m to 73 ⁇ m, in particular from 68 ⁇ m, may be preferred according to the invention.
  • the maximum d3 value may then preferably be in the range from 70 ⁇ m to 120 ⁇ m, more preferably in the range from 96 to 115 ⁇ m, and in particular at 105 ⁇ m.
  • the minimum d94 value in this case may preferably be in the range from 28 ⁇ m to 49 ⁇ m, more preferably in the range from 40 ⁇ m to 48 ⁇ m, in particular at 44 ⁇ m.
  • particles may also be preferred which have an average particle size in the range from 42 ⁇ m to 50 ⁇ m, more preferably in the range from 45 ⁇ m to 50 ⁇ m, and in particular 47.5 ⁇ m.
  • the maximum d3 value may then preferably be in the range from 65 ⁇ m to 78 ⁇ m, more preferably in the range from 70 ⁇ m to 78 ⁇ m, and in particular at 74 ⁇ m.
  • the minimum d94 value in this case can be in the range from 25 ⁇ m to 31 ⁇ m, more preferably in the range from 28 ⁇ m to 31 ⁇ m, and in particular at 30 ⁇ m.
  • Particles which have an average particle size in the range from 35 ⁇ m to 40 ⁇ m, more preferably in the range from 37 to 40 ⁇ m, and in particular from 39.9 ⁇ m, may also be preferred.
  • the maximum d3 value may then preferably be in the range from 56 ⁇ m to 65 ⁇ m, more preferably in the range from 60 ⁇ m to 64 ⁇ m, and in particular at 64 ⁇ m.
  • the minimum d94 value in this case may be in the range from 20 ⁇ m to 26 ⁇ m, more preferably in the range from 22 ⁇ m to 26 ⁇ m, and in particular at 26 ⁇ m.
  • particles of the type ZWSK 280 can therefore be used.
  • the maximum d3 value may then preferably be in the range from 46 ⁇ m to 55 ⁇ m, more preferably in the range from 49 ⁇ m to 55 ⁇ m, and in particular at 54 ⁇ m.
  • the minimum d94 value in this case can be in the range from 14.5 ⁇ m to 20 ⁇ m, more preferably in the range from 17 ⁇ m to 19.5 ⁇ m, and in particular at 19.5 ⁇ m.
  • particles of the ZWSK 320 type can therefore be used.
  • the maximum d3 value may then preferably be in the range from 37 ⁇ m to 47 ⁇ m, more preferably in the range from 42 ⁇ m to 47 ⁇ m, and in particular at 46 ⁇ m.
  • the minimum d94 value in this case may be in the range of 9 to 15.5 ⁇ m, more preferably in the range of 12.5 ⁇ m to 15.0 ⁇ m, and in particular 14.5 ⁇ m.
  • particles of the ZWSK 360 type can therefore be used.
  • the average particle size of the particles is preferably in the range of 12.5 microns to 28 microns and more preferably in the range of 17 to 27 ⁇ m.
  • the maximum d3 value is preferably in the range from 24 ⁇ m to 48 ⁇ m and particularly preferably in the range from 31 ⁇ m to 47 ⁇ m.
  • the minimum d94 value is preferably in the range of 5 ⁇ m to 15.5 ⁇ m and particularly preferably in the range of 7.5 ⁇ m to 15.5 ⁇ m.
  • the maximum d3 value may then preferably be in the range from 37 ⁇ m to 47 ⁇ m, more preferably in the range from 42 ⁇ m to 47 ⁇ m, and in particular at 46 ⁇ m.
  • the minimum d94 value in this case may be in the range of 9 to 15.5 ⁇ m, more preferably in the range of 12.5 ⁇ m to 15.0 ⁇ m, and in particular 14.5 ⁇ m.
  • particles of the ZWSK 360 type can therefore be used.
  • Particles which have a mean particle size in the range from 16.3 ⁇ m to 22 ⁇ m, more preferably in the range from 17 ⁇ m to 22 ⁇ m, and in particular at 21.4 ⁇ m, may also be preferred.
  • the maximum d3 value may then preferably be in the range from 30 ⁇ m to 40 ⁇ m, particularly preferably in the range from 32 ⁇ m to 40 ⁇ m, and in particular at 37 ⁇ m.
  • the minimum d94 value in this case may be in the range of 7 ⁇ m to 12 ⁇ m, more preferably in the range of 8 ⁇ m to 12.0 ⁇ m, and in particular 21 ⁇ m.
  • Particles which have an average particle size in the range from 11.8 ⁇ m to 17.5 ⁇ m, more preferably in the range from 12.5 ⁇ m to 17.5 ⁇ m, and in particular at 17.14 ⁇ m, may also be preferred.
  • the maximum d3 value may then preferably be in the range from 23 ⁇ m to 33 ⁇ m, particularly preferably in the range from 24 ⁇ m to 33 ⁇ m, and in particular at 31 ⁇ m.
  • the minimum d94 value in this case can range from 4 ⁇ m to 8.5 ⁇ m, more preferably in the range from 4.5 ⁇ m to 8.0 ⁇ m, and in particular at 7.5 ⁇ m.
  • the composite panel according to the invention has a binder arrangement in which the core layer and the decorative layer are provided and which forms a binder layer arranged on the decorative layer which contains the particles having a Mohs hardness of at least 8
  • the binder assembly according to the invention contains at least one, but preferably at least two different binders in the cured state.
  • the individual sheets of kraft paper are interconnected and the core layer formed from the kraft paper sheets and the decorative layer are joined together.
  • the decorative layer is applied to the core layer formed from kraft paper sheets.
  • On the decorative layer in turn is a cured binder layer containing the particles having a Mohs hardness of at least 8.
  • the binder which in the cured state bonds the kraft paper sheets together and the core layer composed of the kraft paper sheets to the decorative layer, is a thermosetting resin.
  • Preferred binders are liquid or liquefiable resins which cure on their own or with reactants, for example hardeners or accelerators, without elimination of volatile components by polymerization or polyaddition via crosslinking reactions to thermosets. Phenol resins have proved to be particularly preferred for this purpose. Phenolic resins are defined according to DIN 16916, Part 1 and ISO 10082 as condensation products of phenols and aldehydes. Unsubstituted phenol and formaldehyde are the main raw materials for the production of phenolic resins.
  • the binder which, when cured, bonds the decorative layer to the core layer and forms the binder layer containing the particles having a Mohs hardness of at least 8 is also preferably a thermosetting resin.
  • aminoplasts are polycondensation products of carbonyl compounds, preferably aldehydes, such as formaldehyde, or ketones, and compounds containing NH groups, such as urea, melamine, urethanes, cyanide or cyanamide, aromatic amines and sulfonamides, which are linked together in a Mannich reaction and harden to thermosets during use.
  • Preferred aminoplasts are urea resins, melamine resins, urethane resins, cyanide or cyandiamide resins, aniline resins and sulfonamide resins.
  • the use of melamine-formaldehyde resins has proven to be particularly preferred. These are hardenable condensation products of melamine and formaldehyde. Furthermore, melamine-urea-formaldehyde resins may also be preferred.
  • the composite panel of the present invention also includes an overlay layer disposed on the decorative layer.
  • the binder layer containing the particles having a Mohs hardness of at least 8 is not formed on the decorative layer but on the overlay layer.
  • the same binder preferably one of thermosetting resins described above, more preferably one of the above-described aminoplasts, such as a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin.
  • the binder which optionally connects the underlay sheets to one another, the core layer to the underlay layer and the underlay layer to the decorative layer, preferably one of the above-described thermosetting resins, particularly preferably one of those described above Aminoplasts, such as a melamine-formaldehyde resin or a melamine-urea formaldehyde resin.
  • the composite panel according to the invention is obtained by producing a structure which contains the kraft paper sheets, the decorative paper sheet and optionally the overlay sheet, as well as the particles and a suitable binder system, this structure between special press plates brings, presses and the binder system hardens.
  • Binder system is understood to mean a single suitable binder or a combination of suitable binders.
  • Suitable binders are preferably to be understood as meaning those binders which have been described above as being preferred for bonding the individual layers contained in the composite board or for joining the sheets forming the layers.
  • the decorative paper sheet or “the” overlay sheet it is understood by the person skilled in the art that, depending on the desired composition of the composite panel, it is also possible to use a plurality of decorative paper sheets or overlay sheets.
  • the construction of the composite panel or of the construction comprising a plurality of decorative paper sheets or overlay sheets is obvious to the person skilled in the art from the following statements.
  • the particles described above having a Mohs hardness of at least 8 are applied to the (uppermost) decorative paper sheet or, if an overlay layer is desired, to the (uppermost) overlay sheet.
  • the application of the particles always takes place at least on the outside of the uppermost decorative paper sheet or, if present, at least on the outside of the uppermost overlay sheet.
  • the outside of a sheet means that surface of said sheet which is not in contact with any other sheet of the construction.
  • the attribute "uppermost" in connection with said signature means that arc of the respective layer farthest from the core paper sheets.
  • Particulate application may be by any of the conventional techniques such as the wet-on-wet process (see, for example, U.S. Pat EP 122396 . EP 693030 ), the dry-on-wet process (see for example EP 1011969 . EP 837771 . US 4940503 ) or the wet-on-dry process.
  • the wet-on-wet process a suspension containing, in addition to the particles, a suitable binder or water is applied to the outside of the topmost decor paper sheet or overlay sheet impregnated with a suitable binder.
  • the particles are in the dry state without the addition of binders on the outside of the top, impregnated with a binder decor paper sheet or Overlay sheets applied.
  • a suspension which contains a suitable binder in addition to the particles is applied to the outside of the uppermost, dry, unimpregnated decor paper sheet or overlay sheet.
  • the mass of the particles to be applied having a Mohs hardness of at least 8 is determined by the desired loading of the composite panel with these particles and is accordingly 21 to 35 g / m 2 , preferably 22 to 32 g / m 2 and even more preferably 23 to 29 g / m 2 , based on the surface of the composite panel.
  • the decorative sheets coated with the particles having a Mohs hardness of at least 8 and impregnated with a suitable binder can be used directly for the preparation of the structure described above.
  • the decorative sheets coated with the particles may also first be subjected to drying to produce so-called pre-pregs.
  • individual sheets, preferably all sheets, of the various layers are preferably impregnated with a suitable binder.
  • the structure comprises a plurality of kraft paper sheets, preferably three to six kraft paper sheets.
  • a decorative paper sheet is arranged on the top kraft paper sheet.
  • the particles having a Mohs hardness of at least 8 may be applied. If an overlay layer is provided, then the particles are not applied to the decorative paper sheet but to the overlay sheet. In this case, the particle-coated overlay sheet is arranged on the decorative paper sheet.
  • the decorative paper sheet applied to the uppermost kraft paper sheet is a pre-preg of decorative paper, a suitable binder and particles with a Mohs hardness of at least 8 arranged on the surface of the decorative paper.
  • the overlay sheet applied to the decorative paper sheet covering the kraft paper sheets is a pre-preg of overlay sheets, a suitable binder and particles having a Mohs hardness of at least 8 arranged on the surface of the overlay sheet ,
  • an overlay sheet is first pre-impregnated with melamine-formaldehyde resin.
  • melamine-formaldehyde resin for this preimpregnation 40 to 60 weight percent, more preferably 50 to 55 weight percent, of the intended amount for the impregnation of the overlay sheet amount of binder, preferably a melamine-formaldehyde resin is preferably used.
  • a suspension containing the particles to be applied with a Mohs hardness of at least 8 and the remainder of the intended for the impregnation of the overlay sheet melamine-formaldehyde resin (preferably so 60 to 40 weight percent, more preferably 50 to 45 weight percent of for the impregnation of the overlay sheet provided amount of binder, preferably a melamine-formaldehyde resin), applied to the overlay sheet.
  • This particle-coated overlay sheet is applied to the melamine-formaldehyde resin-impregnated decal sheet such that the particles having a Mohs hardness of at least 8 are on the outside of the overlay sheet, and therefore are not in contact with the decal sheet.
  • decal sheet, overlay sheets and particles is finally applied to the top of the kraft paper sheets impregnated with a suitable binder, preferably a phenol-formaldehyde resin, in such a way that the decal sheet is in contact with a kraft paper sheet.
  • a suitable binder preferably a phenol-formaldehyde resin
  • the particles are arranged on the outside of the uppermost decoration sheet or of the uppermost overlay sheet.
  • the kraft paper sheets present in the structure are preferably impregnated with a phenol-formaldehyde resin.
  • Binder content of the impregnated kraft paper sheet is preferably in the range of 25 to 40 weight percent, more preferably in the range of 28 to 36 weight percent and even more preferably in the range of 30 to 34 weight percent.
  • the decorative paper sheet present in the structure is preferably impregnated with a melamine-formaldehyde resin or a melamine-urea-formaldehyde resin.
  • the binder content of the impregnated decal sheet depends inter alia on the motif of the decal sheet. For plain colors, the binder content of the impregnated decal sheet is preferably in the range of 35 to 65 weight percent, more preferably in the range of 42 to 60 weight percent, and even more preferably in the range of 48 to 55 weight percent.
  • the binder content of the impregnated decal sheet is preferably in the range of 35 to 65 weight percent, more preferably in the range of 37 to 50 weight percent and even more preferably in the range of 40 to 45 weight percent.
  • the binder content of the optional overlay sheet is preferably in the range of 60 to 90 weight percent, more preferably in the range of 65 to 86 weight percent, and even more preferably in the range of 70 to 83 weight percent.
  • press plates having a smooth, high gloss and abrasion resistant surface coated with titanium diboride, zirconium diboride, hafnium diboride, molybdenum diboride, tantalum boride, tungsten diboride or vanadium diboride.
  • the coating with this diboride is preferably carried out in a magnetron sputter coating system and preferably has a Vickers hardness of at least 2000. Press plates have proven to be particularly suitable, as in the EP 0 826 790 are disclosed.
  • the compression of the structure is preferably carried out at a temperature in the range of 110 to 140 ° C, more preferably in the range of 120 ° C to 150 ° C and at elevated pressure of preferably at least 4 N / mm 2 , more preferably at least 5 N / mm 2 .
  • the pressing time is preferably in the range of 40 to 90 minutes, more preferably in the range of 50 to 80 minutes.
  • the product obtained after the compression of the construction and the curing of the resins is finally referred to as a composite panel.
  • the finished composite panel has, depending on the chosen structure, different thicknesses. Typical thicknesses are in the range of 0.5 mm to 2 mm, preferably in the range of 0.6 to 1.5 mm and particularly preferably in the range of 0.8 to 1.2 mm. However, it is also possible to produce composite panels with much larger thicknesses, such as in the range of 2 mm to 20 mm.
  • the composite panel contains an overlay layer
  • its thickness is preferably in the range from 80 to 120 ⁇ m, particularly preferably in the range from 80 to 110 ⁇ m.
  • the thickness of the overlay layer is understood as meaning the distance between the outer side facing away from the decorative layer and the binder layer containing the particles having a Mohs hardness of at least 8 and the outer side of the decorative paper sheet in contact with the overlay layer.
  • the thickness of the decorative layer is preferably in the range of 65 to 140 microns, more preferably in the range of 65 to 80 microns.
  • the thickness of the decorative layer is understood to be the distance between the outside of the decorative paper sheet which is in contact with the overlay layer and the outside of the kraft paper sheet of the core layer which is in contact with the decorative layer.
  • the thickness of the core layer can vary greatly depending on the desired thickness of the composite panel and is preferably in the range of 250 to 1900 microns, more preferably in the range of 500 to 1500 microns.
  • the thickness of the decorative layer is likewise preferably in the range from 65 to 140 ⁇ m, particularly preferably in the range from 80 to 140 ⁇ m.
  • the thickness of the decorative layer is defined in this case as the distance between the outer layer facing away from the core layer of the binder layer containing the particles having a Mohs hardness of at least 8 and the outside of the with the Decorative layer in contact kraft paper sheet of the core layer.
  • the thickness of the core layer can be, for example, in the range from 250 to 1900 .mu.m, particularly preferably in the range from 500 to 1500 .mu.m, independently of the presence of an overlay layer.
  • the final weight of the composite panel according to the invention depends on several factors, such as the thickness of the composite panel, the weight of the components used and the number of sheets used.
  • the weight of the composite panel is in the range of 1.2 to 1.6 kg per m 2 surface area of the composite panel (kg / m 2 ), more preferably in the range of 1.3 to 1.5 kg / m 2 , for example 1.4 kg / m 2 .
  • the surface of the composite panel formed by the binder layer containing the particles having a Mohs hardness of at least 8 has a gloss reduction GR X and GRS X after abrasion in the gloss level reduction test, which does not exceed a maximum value.
  • the degree of gloss is measured before and after a defined abrasion stress in order to determine the degree of gloss reduction.
  • the test for determining the degree of gloss reduction is designated according to the invention as gloss level reduction test.
  • the determination of the gloss level is always within the scope of the invention according to DIN 67530 at a light incidence angle of 60 °.
  • the obtained reflectometer values at 60 ° light incidence are related to a black, polished glass standard with a defined refractive index. For this standard, the reading is calibrated to 100 gloss units (100 GE).
  • the original degree of gloss is understood to mean that degree of gloss of the surface of the composite panel which is obtained before the abrasion stress in the degree of gloss reduction test.
  • This initial gloss level is at least 80 GE, preferably at least 85 GE and more preferably 90 GE.
  • the abrasion under the gloss level reduction test is carried out as follows:
  • the linear movement is subsequently repeated in the direction of movement opposite to the first direction of movement.
  • a double stroke is understood to mean a completely closed movement in one direction and in the opposite direction to that direction, so that the carriage covers the same distance twice in a double stroke (reciprocation).
  • the abrasion is performed by performing a defined number of double strokes, whereby the contact area coming into contact with the abrasive medium on the surface of the composite is determined by the first double stroke and remains the same throughout the abrasion stress.
  • the degree of gloss reduction GR X (or GRS X ) after abrasion in the gloss level reduction test
  • the difference between the original gloss level and the gloss level after abrasion in the X double rub gloss reduction test is determined and the ratio between this difference and the original gloss level calculated.
  • the value obtained is multiplied by 100 percent and referred to as the degree of gloss reduction after abrasion in the gloss level reduction test, GR X (or GRS X ).
  • the abrasion in the gloss level reduction test to determine the gloss loss GR X by using a sandpaper from Type P 1200 as abrasive refers to the designation of the body in accordance with the international standard ISO 6344-1: 1999. Accordingly, the corundum particles have a d s0 value of max. 58 ⁇ m, a d s3 value of max. 29.7 ⁇ m, a mean particle size (d s50 value) of 15.3 ⁇ 1.0 ⁇ m and a d s95 value of min. 10.2 ⁇ m, measured with the US sedimentometer according to ISO 8486-2.
  • the corundum content of the abrasive paper used is 24.3 g / m 2 .
  • the weight of the abrasive paper used is 250 g / m 2 .
  • GR 500 double rubs are performed for determining the degree of gloss loss after GR X shearing load in the degree of gloss reduction test.
  • the value obtained for the degree of gloss reduction is accordingly referred to as "GR 500 ".
  • the surface of the composite panel formed by the binder layer containing the particles having a Mohs hardness of at least 8 has a gloss reduction GR 500 after abrasion in the gloss reduction test of at most 7%, preferably at most 6%, more preferably at most 5%, and still more preferably at most 4%.
  • a gloss reduction GR X after abrasion in the gloss level reduction test can also be measured with a different number of double strokes.
  • 250 double strokes can be carried out for abrasion.
  • the thus determined value for the gloss reduction is also referred to as GR 250 .
  • the surface of the composite panel formed by the binder layer containing the particles having a Mohs hardness of at least 8 preferably has a rubbing degree reduction after abrasion in 250 double rubs gloss level reduction test, GR 250 , of at most 5%, more preferably not more than 4%, more preferably not exceeding 3%, and in particular not exceeding 2%.
  • the abrasive medium used for the abrasive stress in the gloss level reduction test may also be steel wool.
  • steel wool is grade 1 steel wool, which consists of rectangular chips made from a material that complies with DIN 17145 of type 11Mn4Si with the material number 1.0492.
  • the abrasive stress is preferably carried out by performing 500 double strokes.
  • the value obtained for gloss level reduction is accordingly designated GRS 500 .
  • the surface formed by the binder layer containing the particles having a Mohs hardness of at least 8 has a GRS 500 gloss level reduction after abrasion in the steel wool gloss reduction reduction test of at most 10%, preferably at most 7%, more preferably at most 5%, even more preferably at most 3% and in particular at most 1%.
  • An abrasion stress in the gloss level reduction test using steel wool can also be performed by applying 250 double strokes.
  • the corresponding value obtained for gloss level reduction is consequently referred to as GRS 250 .
  • the surface formed by the binder layer containing the particles having a Mohs hardness of at least 8 has a gloss reduction GRS 250 after abrasion in the steel wool gloss reduction reduction test of at most 5%, preferably at most 4%, more preferably at most 3%, even more preferably at most 2% and in particular at most 1%.
  • the surface of the composite panel formed by the binder layer containing the particles having a Mohs hardness of at least 8 has an abrasion resistance according to DIN EN 13329, Annex E, which permits the classification of the composite panel into the abrasion class AC3. preferably AC4 and in particular AC5 allowed.
  • the abrasion resistance according to the test carried out according to DIN EN 13329, Annex E preferably at an IP value (initial point) of at least 5000 revolutions, more preferably at least 5700 revolutions, most preferably at least 6500 revolutions.
  • IP value initial point
  • a preferred range is an IP value of 5,000 to 10,000 revolutions, more preferably 6,000 to 9,500 revolutions, and most preferably 6,500 to 9,000 revolutions.
  • the unit of measurement is the IP value, ie the number of revolutions after which the signs of wear occur.
  • an emery paper defined in DIN EN 13329 is used which is characterized in particular by a basis weight of 70 g / m 2 to 100 g / m 2 and is open-coated with 180 grit of alumina having a grain size which is determined by a Sieve with openings of 100 microns fits, but not through openings of 63 microns.
  • the surface of the composite panel formed by the binder layer containing the particles having a Mohs hardness of at least 8 has impact resistance in accordance with the standard EN 13329, Annex F, which allows the composite panel to be classified into the Class IC2, preferably IC3, allowed.
  • the drop height is preferably at least 1300 mm, more preferably at least 1500 mm and especially at least 1700 mm.
  • the impact resistance is preferably in the range of 15 to 25 N, more preferably in the range of 17 to 23 N, and in particular in the range of 18 to 22 N.
  • the invention relates to a panel comprising a support and a composite panel adhered to the support of the invention.
  • the panel is a floor panel (floor panel).
  • the panel may also be another plate, such as a table top.
  • Preferred supports are chipboard, plywood, support plates (optionally coated with laminate), high density fiberboard, medium density fiberboard, hardboard, blockboard, veneer, solid wood, honeycomb, foam, metal plates, sheets, mineral substrates, natural and artificial stone, tiles and plasterboard.
  • the supports may be coated with a suitable binder, such as a melamine resin, or uncoated.
  • the composite panel can be applied to both liquid-absorbent (absorbent) substrates, such as uncoated particle board and uncoated wood, and non-liquid-absorbent (non-absorbent) substrates, such as metals, ceramics, glass, coated woods, coated chipboard, etc.
  • the fixed connection of composite panel and carrier can be done by gluing or by means of known from the prior art fasteners.
  • the bonding of the composite plate to the substrate material is performed such that the surface of the composite plate opposite to the surface containing the particles having a Mohs hardness of at least 8 is in contact with a surface of the substrate.
  • a surface of the carrier and a surface formed by the core layer of the composite plate are in contact in the panel.
  • the panel may also include other functional materials known in the art.
  • materials for flame protection, for shielding radiation, for sound damping, for stabilization and for moisture barrier may be mentioned.
  • Preferred functional materials include a back-pull and / or impact sound damping, as they are preferably used in floor panels.
  • the thickness of the panel is not limited. It is preferably in the range of 9 to 15 mm, more preferably in the range of 10 to 14 mm and most preferably in the range of 11 to 13 mm.
  • the thickness of the composite panel present in the panel may, as described above, preferably in the range of 0.5 to 2 mm, more preferably in the range of 0.6 to 1.5 mm, and most preferably in the range of 0.8 to 1 , 2 mm lie.
  • the thickness of the support for example a high-density fiberboard, is preferably in the range of 5 to 13 mm, more preferably in the range of 8 to 10 mm, most preferably in the range of 9.0 to 9.6 mm.
  • the optionally provided counter-pull and / or the impact sound damping preferably have a thickness in the range of 0.5 to 3 mm, particularly preferably in the range of 1 to 2 mm.
  • the final weight of the panel is not particularly limited. It is preferably in the range of 8 to 13 kg per m 2 surface of the panel (kg / m 2 ), more preferably in the range of 9 to 12 kg / m 2 and most preferably in the range of 10 to 11 kg / m 2 .
  • the panel according to the invention can be processed in a manner which is obvious to a person skilled in the art. If the panel is a bottom plate, then this can be provided with a tongue and groove structure to allow the surface-connecting a plurality of such floor panels for the production of board-like or tile-like structures.
  • An overlay paper made of ⁇ -cellulose having a basis weight of 30 g / m 2 was soaked to saturation with melamine resin. The excess resin was removed on the surface between two polished steel rolls. The melamine resin applied to the overlay paper was allowed to dry for 2 hours at room temperature to obtain a preimpregnated overlay paper.
  • Example 1.3 Production of a composite panel according to the invention
  • the thus prepared structure was placed between two press plates with smooth, coated with titanium diboride in the magnetron sputter coating system, high gloss surfaces, pressed at a pressure of 10 N / mm 2 and a maximum temperature of 135 ° C for 35 min and then cooled to room temperature ,
  • the obtained composite plate showed high gloss and high transparency and showed no traces of corundum coating and no fogging.
  • a structure suitable for pressing with two press plates was first produced.
  • four sheets of Kraft paper impregnated with a phenolic resin were placed on both sides of a 30 ⁇ m-thick sheet of a polypropylene release sheet.
  • a sheet of decorative paper was placed on the uppermost sheet of kraft paper and one sheet of Mead-822 overlay paper (in accordance with the US 3798111 ) applied.
  • overlay paper corundum particles are not distributed on the surface or surfaces of the paper consisting of ⁇ -cellulose, but are distributed in the fiber layer.
  • the thus prepared structure was placed between two press plates with smooth, coated with titanium diboride in the magnetron sputter coating system, high gloss surfaces, pressed at a pressure of 10 N / mm 2 at a maximum temperature of 135 ° C for 35 min and then cooled to room temperature ,
  • the thus prepared structure was placed between two press plates with smooth, coated with titanium diboride in the magnetron sputter coating system, high gloss surfaces, pressed at a pressure of 10 N / mm 2 at a maximum temperature of 135 ° C for 35 min and then cooled to room temperature ,
  • the surface of the composite sheets obtained by the binder layer disposed on the overlay layer of the composite sheets obtained in the embodiment and Comparative Examples 1 and 2 was subjected to abrasion abrasion with abrasive paper in the gloss reduction test. After the specified number of double strokes, the gloss level was measured at a light incidence angle of 60 ° according to DIN 67530. The values obtained are shown in Table 1: ⁇ b> Table 1: Degree of gloss at 60 ° after the specified number of double strokes.
  • Gloss level in GE exemplary embodiment Gloss level in GE: Comparative Example Gloss level in GE: Comparative Example double strokes 1 2 0 109.2 103.6 115.5 50 110.4 90.5 63.2 100 109.3 92.8 63.2 250 107.5 93.3 69.3 500 105.2 93.8 64.6
  • Gloss level in GE exemplary embodiment Gloss level in GE: Comparative Example Gloss level in GE: Comparative Example double strokes 1 2 0 114.2 102.8 118.2 50 114.6 99.2 115.7 100 114.2 92.5 111.9 250 114.2 89.9 101.3 500 114.3 80.5 88.6
  • the EP 0 219 769 B1 and AT 40 807 E have studied the resistance of the laminate surface to scratching. In each case, the gloss loss of the laminate surface was measured by abrasion in two places. The scrubbing was done by rubbing with 10 double strokes, using a Crockmeter apparatus, using 3M Scotch Brite type 8A abrasive pads. The investigations showed a gloss loss of 4% and 5%, respectively.
  • the composite panel according to the invention has a very low gloss loss of only 1.5% and thus a much lower degree of gloss reduction than the composite panels, which in EP 0 219 769 B1 respectively. AT 40 807 E are disclosed.
  • the outstanding properties are inventively by the choice of the size of the particles having a Mohs hardness of at least 8, the amount of particles having a Mohs hardness of at least 8, and the particular arrangement of the particles having a Mohs hardness of at least 8 at the Surface of the composite panel reached. This is particularly noteworthy because in the prior art to achieve these properties partly contrary measures have been proposed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Floor Finish (AREA)

Claims (9)

  1. Plaque composite, comprenant:
    a) une couche d'âme, contenant une ou plusieurs feuilles de papier kraft,
    b) une couche de décoration, contenant une feuille de papier décoratif,
    c) des particules présentant une dureté Mohs d'au moins 8,
    d) un agencement d'agent liant, contenant au moins un agent liant à l'état durci, dans laquelle la couche d'âme et la couche de décoration sont prévues dans l'agencement d'agent liant et dans laquelle il se trouve sur la couche de décoration une couche d'agent liant durci, qui contient les particules présentant une dureté Mohs d'au moins 8,
    dans laquelle le degré de brillance de la plaque composite vaut au moins 80 unités de brillance (UB), et dans laquelle
    (i) la surface de la plaque composite formée par la couche d'agent liant présente une réduction du degré de brillance après une opération d'abrasion au test de réduction du degré de brillance GR500 au maximum de 7 %, dans laquelle le degré de brillance initial vaut au moins 80 UB,
    (ii) les particules présentent une taille moyenne de grain dans la plage de 5 à 100 µm, et
    (iii) la charge de la plaque composite avec les particules, rapportée à la surface de la plaque composite, se situe dans la plage de 21 à 35 g/m2,
    dans laquelle la détermination du degré de brillance est toujours effectuée selon la norme DIN 67530 sous un angle d'incidence de la lumière de 60°.
  2. Plaque composite, comprenant
    a) une couche d'âme, contenant une ou plusieurs feuilles de papier kraft,
    b) une couche de décoration, contenant une feuille de papier décoratif,
    b1) une couche overlay, comprenant une ou plusieurs feuilles d'un matériau de préférence contenant des fibres,
    c) des particules présentant une dureté Mohs d'au moins 8,
    d) un agencement d'agent liant, contenant au moins un agent liant à l'état durci, dans laquelle la couche d'âme, la couche de décoration et la couche overlay sont prévues dans l'agencement d'agent liant et dans laquelle il se trouve sur la couche overlay une couche d'agent liant durci, qui contient les particules présentant une dureté Mohs d'au moins 8,
    dans laquelle le degré de brillance de la plaque composite vaut au moins 80 unités de brillance (UB), et dans laquelle
    (i) la surface de la plaque composite formée par la couche d'agent liant présente une réduction du degré de brillance après une opération d'abrasion au test de réduction du degré de brillance GR500 au maximum de 7 %, dans laquelle le degré de brillance initial vaut au moins 80 UB,
    (ii) les particules présentent une taille moyenne de grain dans la plage de 5 à 100 µm, et
    (iii) la charge de la plaque composite avec les particules, rapportée à la surface de la plaque composite, se situe dans la plage de 21 à 35 g/m2, dans laquelle la détermination du degré de brillance est toujours effectuée selon la norme DIN 67530 sous un angle d'incidence de la lumière de 60°.
  3. Plaque composite selon la revendication 1 ou 2, dans laquelle la surface de la plaque composite formée par la couche d'agent liant présente une réduction du degré de brillance après une opération d'abrasion au test de réduction du degré de brillance GRS500 au maximum de 10 %.
  4. Plaque composite selon l'une quelconque des revendications précédentes, dans laquelle la surface de la plaque composite formée par la couche d'agent liant présente une résistance à l'abrasion selon la norme DIN EN 13329, annexe E, exprimée en valeur IP, d'au moins 5000 révolutions.
  5. Plaque composite selon l'une quelconque des revendications précédentes, dans laquelle les particules sont des particules de corindon présentant une dureté Mohs d'au moins 8.
  6. Plaque composite selon la revendication 5, dans laquelle la taille moyenne de grain des particules de corindon se situe dans la plage de 45 à 75 µm.
  7. Plaque composite selon l'une quelconque des revendications précédentes, dans laquelle la charge de la plaque composite avec les particules, rapportée à la surface de la plaque composite, se situe dans la plage de 23 à 29 g/m2.
  8. Panneau comprenant une plaque composite selon l'une quelconque des revendications précédentes.
  9. Panneau selon la revendication 8, sous la forme d'une plaque de sol.
EP08863535A 2007-12-20 2008-11-25 Plaque composite multicouche Active EP2219883B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08863535T PL2219883T3 (pl) 2007-12-20 2008-11-25 Wielowarstwowa płyta kompozytowa

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007062407A DE102007062407B4 (de) 2007-12-20 2007-12-20 Mehrschichtige Verbundplatte
PCT/EP2008/009961 WO2009080171A1 (fr) 2007-12-20 2008-11-25 Plaque composite multicouche

Publications (2)

Publication Number Publication Date
EP2219883A1 EP2219883A1 (fr) 2010-08-25
EP2219883B1 true EP2219883B1 (fr) 2012-10-17

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Application Number Title Priority Date Filing Date
EP08863535A Active EP2219883B1 (fr) 2007-12-20 2008-11-25 Plaque composite multicouche

Country Status (6)

Country Link
EP (1) EP2219883B1 (fr)
DE (1) DE102007062407B4 (fr)
PL (1) PL2219883T3 (fr)
PT (1) PT2219883E (fr)
RU (1) RU2449894C2 (fr)
WO (1) WO2009080171A1 (fr)

Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
DE102009036538A1 (de) 2009-08-07 2011-02-10 Resopal Gmbh Paneel mit mindestens einer Nut
DE102009036541A1 (de) 2009-08-07 2011-02-10 Resopal Gmbh Schaumstoff-Paneel
EP2763850B1 (fr) 2011-10-03 2018-07-18 Unilin, BVBA Panneau de sol
DE102012109660A1 (de) * 2012-10-10 2014-04-10 Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh Transparente Oberflächenschutzschicht
DE102021127405A1 (de) 2021-10-21 2023-04-27 Ludwig Leitermann Verfahren zum Herstellen einer Verbundplatte sowie Verbundplatte

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US3798111A (en) 1972-03-24 1974-03-19 Mead Corp Multiple layer decorated paper,laminates prepared therefrom and process
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US4505974A (en) * 1983-10-03 1985-03-19 Formica Corporation Decorative laminate having mar-resistant surface
US4880689A (en) * 1985-10-18 1989-11-14 Formica Corporation Damage resistant decorative laminate
SE460274B (sv) 1988-02-18 1989-09-25 Perstorp Ab Foerfarande foer framstaellning av ett noetningsbestaendigt, dekorativt haerdplastlaminat
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DE3916099A1 (de) * 1989-05-17 1990-11-29 Roemmler H Resopal Werk Gmbh Verfahren zur herstellung von dekorativen schichtpressstoffplatten
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DE19710619A1 (de) * 1997-03-14 1998-09-17 Basf Ag Mit Melaminharz beschichtete Festkörperpartikel
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AT405265B (de) * 1997-04-30 1999-06-25 Kaindl M Dekorlaminat und verfahren zu seiner herstellung
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KR20060063973A (ko) * 2003-09-30 2006-06-12 크로노스판 테크니컬 컴파니 리미티드 접착제로 피복된 강옥이 살포되어 있는 장식지
DE10355180B4 (de) * 2003-11-26 2010-04-08 Thomas C. Linnemann Verfahren zum Herstellen eines Dekorlaminats
EP1937476B1 (fr) * 2005-10-10 2016-01-13 Kronoplus Technical AG Plaques resistant a l'usure comprenant une surface decorative
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DE102007019179A1 (de) * 2007-04-20 2008-10-30 Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh Verschleißschutzschicht

Also Published As

Publication number Publication date
WO2009080171A1 (fr) 2009-07-02
PL2219883T3 (pl) 2013-05-31
PT2219883E (pt) 2013-01-28
DE102007062407B4 (de) 2010-05-12
EP2219883A1 (fr) 2010-08-25
RU2010130085A (ru) 2012-01-27
RU2449894C2 (ru) 2012-05-10
DE102007062407A1 (de) 2009-06-25

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