EP3774381A1 - Plaque décorative pouvant être décapée - Google Patents

Plaque décorative pouvant être décapée

Info

Publication number
EP3774381A1
EP3774381A1 EP19717769.4A EP19717769A EP3774381A1 EP 3774381 A1 EP3774381 A1 EP 3774381A1 EP 19717769 A EP19717769 A EP 19717769A EP 3774381 A1 EP3774381 A1 EP 3774381A1
Authority
EP
European Patent Office
Prior art keywords
layer
carrier layer
synthetic resin
coating agent
resin
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.)
Pending
Application number
EP19717769.4A
Other languages
German (de)
English (en)
Inventor
Roger Braun
Pius Steinmann
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.)
Swiss Krono Tec AG
Original Assignee
Swiss Krono Tec AG
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
Priority claimed from EP18165078.9A external-priority patent/EP3546240A1/fr
Priority claimed from EP18165082.1A external-priority patent/EP3546241A1/fr
Application filed by Swiss Krono Tec AG filed Critical Swiss Krono Tec AG
Publication of EP3774381A1 publication Critical patent/EP3774381A1/fr
Pending legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/80Paper comprising more than one coating
    • D21H19/84Paper comprising more than one coating on both sides of the substrate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B13/00Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
    • B32B13/04Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material comprising such water setting substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B13/08Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material comprising such water setting substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B13/00Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
    • B32B13/04Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material comprising such water setting substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B13/12Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material comprising such water setting substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B21/00Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/02Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board the layer being formed of fibres, chips, or particles, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B21/04Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/06Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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    • B32B29/002Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
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    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
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    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/10Applying flat materials, e.g. leaflets, pieces of fabrics
    • B44C1/105Applying flat materials, e.g. leaflets, pieces of fabrics comprising an adhesive layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00Processes for producing special ornamental bodies
    • B44C5/04Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/043Ornamental plaques, e.g. decorative panels, decorative veneers containing wooden elements
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/80Paper comprising more than one coating
    • D21H19/82Paper comprising more than one coating superposed
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/80Paper comprising more than one coating
    • D21H19/82Paper comprising more than one coating superposed
    • D21H19/822Paper comprising more than one coating superposed two superposed coatings, both being pigmented
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18Paper- or board-based structures for surface covering
    • D21H27/22Structures being applied on the surface by special manufacturing processes, e.g. in presses
    • D21H27/26Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207Heat-activated adhesive
    • B32B2037/1215Hot-melt adhesive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243Coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/10Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/12Coating on the layer surface on paper layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/26Polymeric coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/028Paper layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/02Cellular or porous
    • B32B2305/026Porous
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/718Weight, e.g. weight per square meter
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00Properties of the layers or laminate
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    • B44C5/0469Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
    • B44C5/0476Ornamental 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

Definitions

  • the invention relates to a method for producing a color changeable synthetic resin surface or paint surface according to claim 1, a material according to claim 13, a decorative paper according to claim 14 and a finish film according to claim 15.
  • Decorative surfaces of synthetic resin or paint are well known and are used for example in floor coverings, wall coverings, ceiling coverings or furniture surfaces. These have a decorative layer that includes a paper with a printed decor or a painted on a background decor. On the decorative layer usually a protective layer is arranged, which is formed either as buchharzge impregnated overlay or lacquer layer. In addition, it is known to provide the Oberflä surface with a structure decor, which may be, for example, embossed or painted. The layers arranged above the decor are at least semi-transparent so that the viewer can perceive the decor.
  • the disadvantage is that the color design of such surfaces can be influenced in retrospect hardly.
  • the end user individu elle colored surface design, as it is achieved for example in solid wood by pickling the surfaces, is no longer possible with such synthetic resin and paint surfaces.
  • the invention is therefore based on the object mattezu provide a decorative surface that changes particularly simple in their color of the end user who can and which is particularly inexpensive and durable.
  • the invention solves the problem by means of a method having the features of claim 1.
  • Advantageous further developments of the invention are in the dependent claims specified. In this case, all the features described in principle, in isolation or in any combination object of the invention, regardless of their summary in the entitlements or their relationship.
  • the method according to the invention for producing a color-changeable resin surface or lacquer surface comprises the steps of providing a carrier layer with a bottom side and a top side, core impregnations of the carrier layer with a liquid impregnating agent without pickling additive, at least drying of the impregnated carrier layer, applications of a layer of a coating agent the upper side of the carrier layer, drying the at least one coating agent layer, bonding the carrier layer to a material, wherein the one layer hardens during drying and / or bonding on the upper side to an open-pored, at least largely transparent layer.
  • the carrier layer has a decorative print which is printed on the upper side of the carrier layer.
  • the decor can show structures of a décor.
  • the decor is, for example, wood grains, stone grains, stone decors, tile decors or fantasy decors dar.
  • the decor can be used as a colored decor, Decor be designed in shades of gray or even black and white decor.
  • the decor is so well through the impregnant and through the one layer still visible to the viewer, so that both the impregnating agent and the one layer are at least semi-transparent, preferably completely transparent. Even after the Bei zen, ie, after changing the color the printed on the support layer decor is retained and visible, but it changes the overall hue of the resin surface or paint surface.
  • the inventive surface it is possible with the inventive surface to make a bright overall impression of the synthetic resin / lacquer surface, which is produced by a light-on-itself printed decor, for example, dark by means of a dark stain.
  • the applied dye color pigments
  • color changeable is understood to mean that the overall color impression of the synthetic resin surface which is predetermined by the decorative imprint on the carrier layer
  • che / paint surface is subsequently changed individually via an additional color input into the cured coating agent layer.
  • the subsequent change for example, be carried out industrially, according to an industrially carried out staining of wood veneer or solid wood.
  • the inventive color changeable decor surface also offers the possibility, only at a later date, d. H. in the post-industrial manufacturing sector, for example, by a mounting craftsman or the end user to perform a color change. Due to the fact that the layer of the coating composition is mostly worn over the entire surface, there is also the possibility of performing the color adjustment either also over the entire surface or even only on partial surfaces. Thus, just by the end user very individual color designs of Kunststoffharzoberflä
  • the decorative structures produced by the printed decor preferably remain visible, only the basic color tone of the synthetic resin surface / lacquer surface is changed again via the color change. This results in an extremely high level of individualization due to the respective end consumer possible.
  • Existing structure patterns (3-D surfaces), ie textured surfaces, are also retained because the layer of coating material replicates the 3-D structures and the color pigments penetrate into the surface.
  • their optical effect is also enhanced by the stain. Due to the three-dimensional structure, more stains accumulate in the region of recesses which, for example, represent pores or grain, than in the region of elevation. These areas thus also assume the color of the color pigments more than areas in which fewer color pigments are applied. In contrast, unstructured surfaces are evenly colored by the stain.
  • the color matching of the synthetic resin surfaces / lacquer surfaces can be carried out with the same pickling agents, for example a water-based stain, an oil-based stain or a solvent stain, as well as with the same devices as in a normal wood surface dressing.
  • the color changeable synthetic resin surface / lacquer surface is multi-layered and has at least one impregnated with an impregnating agent carrier layer and a layer of a coating agent on top of the carrier layer.
  • the art resin surface / paint surface is completely cured before performing a color change and, as already mentioned, a corresponding surface structure (3-D structure), for example.
  • a corresponding surface structure 3-D structure
  • the carrier layer is in particular a cellulose-based carrier layer which is provided in the form of a web or, for example, also in the form of a sheet.
  • the carrier layer is a paper web / a paper sheet, for example, a decorative paper / decorative sheet.
  • the carrier layer thus has a flat underside and one of the underside opposite the flat top side. The top corresponds to the visible in later use of a viewer page (visible side).
  • On the top of the decor can be printed.
  • the decor print can be produced by conventional printing methods.
  • the decor print is designed in particular as a wood decor, ie a wooden surface zei lowing.
  • the carrier layer is subjected to a core impregnation. This is understood to mean that the carrier layer is completely soaked once, ie, both the underside and the upper side, as well as in its material core (area between the outer surfaces), with a synthetic resin or lacquer.
  • the core impregnation in particular cavities in the carrier layer are to be filled up.
  • the core impregnation can be carried out with conventional impregnating devices, wherein in particular an impregnating bath is advantageous.
  • the support layer is irrespective of whether a synthetic resin surface or a lacquer surface is prepared, dried at least slightly after impregnation (possibly) also dried, but not completely cured (ie, it is further processed in a non-usable condition), whereby the subsequent top-side coating is greatly facilitated and a particularly good and insoluble bond between the resinated carrier layer and the coating agent layer is forth adjustable.
  • each pre-dry for example by means of heat, before also applied to the ge opposite side for the core impregnation an impregnating agent.
  • the drying can take place, for example, by means of hot air in a drying channel in Schwebever between 6o ° C and 200 ° C, in particular between 40 ° C and 6o ° C.
  • drying processes are carried out, for example, after the application of the topcoat coating layer. Also, for example, after the possibly carried out order of a bottom coating with an adhesive resin / adhesive drying done.
  • the core-impregnated carrier layer, the impregnating agent, the impregnating agent quantity and / or the degree of drying after the core impregnation can be formed as a largely rigid carrier layer or for a plate-shaped white or as a flexible carrier layer, for example a finish foil which can be rolled up ,
  • a flat, for example, by a corresponding drying largely rigid carrier layer can be easily placed on a plate-shaped material and transferred in a press.
  • the carrier layer as a flexible layer it can also be laminated onto the material, for example.
  • the material multilayer with the carrier layer to be layers.
  • a synthetic resin surface is understood to mean systems of impregnating agent and coating agent in which the complete curing of the impregnating agent and of the coating composition is carried out under the action of heat and pressure, for example in a short-cycle press or a continuous press.
  • the applied pressure is above the atmospheric pressure.
  • a paint surface is understood to be a system of impregnating agent and coating composition in which the complete curing of the impregnating agent and of the coating composition is unpressurised, ie. at maximum at atmospheric pressure and without pressing device and only under the action of heat, UV radiation, electron radiation and / or high frequency occurs.
  • the coating agent is designed such that it hardens as a porous surface (offenpo rig), whereby the subsequent color change is made possible.
  • the cured coating for acceptance of dyes is formed within the layer.
  • the Po ren are preferably not recognizable by an unaided eye.
  • the cured coating can be completely transparent, so that the printed on the carrier layer decor is not influenced noticeable. It is possible that the cured coating already sets a first basic color over the decor, which is later changed again by means of the application of paint and the inclusion of the dyes in the coating.
  • the bonding of the carrier layer to a material takes place depending on the design of the carrier layer and the impregnating agent and coating agent used either by means of an adhesive resin, such as a melamine resin, which also cures under pressure and heat, or by means of an adhesive, for example Cures hardened.
  • an open-pore hardening layer of lacquer based on acrylate resins such as, for example, the HYDRO-UV layer lacquer HUE 8656X from Hesse-Lignal.
  • a mixture comprising a synthetic resin with a pickling additive or a mixture comprising a lacquer and a pickling additive is applied as the coating agent.
  • a material, a finish foil or a De korpapier to be produced preferably impregnated with a resin carrier layer with a coating additive comprising a coating agent coating layer based on a synthetic resin and impregnated with a lacquer carrier layer with a coating agent layer comprising a pickling additive is coated on the basis of a lacquer, it being also possible to coat a base layer impregnated with synthetic resin with a lacquer-based coating agent layer and vice versa.
  • a pickling additive is understood as meaning an additive which is present in the coating composition and supports and / or effects the formation of a porous surface (open-pore) of the layer of coating applied and dried or hardened.
  • kaolin alumina, silica earth, chalk, mica, quartz sand, silicate, cellulose, natural fibers, glass beads or glass powder is used as a pickling additive.
  • kaolin can be used as a hydrated aluminum silicate.
  • the pickling additives may be silanized, in particular mica, glass beads and / or glass flour.
  • Particular preference is given to kaolin in hydrogenated and / or calcined form, with a mixture, for example. In the ratio of 5oGew. %: SoGew. %, which is beneficial to both forms.
  • the calcined form allows a particularly good fixation of the pickling colors, while the hydrated form is more transparent, and thus prevents a reduced coverage of the decor.
  • the preferred pickling additives can be used both in a lacquer coating agent and in a coating agent in the form of a synthetic resin.
  • silanized kaolin is preferably used, since this additionally improves the adhesion of the stain color.
  • This can be used as a mixture with non-silanized kaolin.
  • Particularly advantageous is the proportion of silanized Kao lins between 50 wt .-% to 80 wt .-% of the total kaolin need.
  • Kaolin and chalk also produce when applied as a liquid stain dyes egg NEN suction, by means of which the dyes are particularly easy to wear into the coating. In addition, with kaolin and chalk, a particularly good fixation of the dyes in the coating takes place.
  • the preferred weight ratios in the coating still to be applied ensure a particularly good and uniform open-pore formation of the surface, so that the recording of the color pigments in the surface of the resin surface / lacquer surface or the fixation thereof in the respective surface can be particularly uniform and good.
  • the coating composition used is a synthetic resin or a lacquer based on an aminoplastic, in particular a urea resin, such as UF or MUF, of acrylate, PU, phenolic resin, polyester, alkyd, nitrocellulose or latex or a mixture of at least two of the abovementioned substances used. It is also particularly preferred to use lacquers based on acrylate resins that can be used as primers, which if appropriate can be cured accordingly without a pickling additive.
  • an aminoplastic in particular a urea resin, such as UF or MUF, of acrylate, PU, phenolic resin, polyester, alkyd, nitrocellulose or latex or a mixture of at least two of the abovementioned substances used.
  • lacquers based on acrylate resins that can be used as primers, which if appropriate can be cured accordingly without a pickling additive.
  • a resin-kaolin mixture in particular a urea resin-kaolin mixture such as a mixture of a UF resin and kaolin or MUF resin and kaolin is particularly preferably used as a coating agent with Beizadditiv for producing a synthetic resin surface, as in these combinations
  • a resin-kaolin mixture in particular a urea resin-kaolin mixture such as a mixture of a UF resin and kaolin or MUF resin and kaolin is particularly preferably used as a coating agent with Beizadditiv for producing a synthetic resin surface, as in these combinations
  • the impregnating agent used is a synthetic resin or lacquer based on an aminoplastic, in particular a urea resin, such as UF resin or based on acrylate, PUR, phenolic resin, a melamine-formaldehyde resin or a mixture or a combination of the aforementioned resins. Irrespective of the base of the impregnating agent, this does not comprise pickling additives.
  • urea resin is used in the production of synthetic resin surfaces, while urea-formaldehyde resin, melamine-formaldehyde resin, a combination of urea-formaldehyde resin and melamine-formaldehyde resin and / or acrylates or PU are used in the production of lacquer surfaces.
  • the individual resin or coating systems for the core impregnation and for the coating applied on the top side are coordinated with one another in order, for example, to achieve a particularly good bond with one another and to prevent delamination effects.
  • the layer of a coating agent can be applied in liquid form.
  • a coating agent can be applied in liquid form.
  • the application of the Beschich processing medium on the upper side of the carrier layer by means of a rolling device, a Doctor blade or a spraying device takes place.
  • the application of the coating agent takes place exclusively on the upper side. For example, no impregnating bath is used for the coating medium application.
  • a coating agent layer can also be used, for example, as an impregnating agent for an overlay, so that the coating agent layer is formed by an overlay that has been impregnated with a coating agent with or without pickling additive.
  • the overlay was pressed with the carrier layer, for example, under an effect of heat and pressure and cured.
  • the overlay fulfills two functions in this version. On the one hand, it serves as a protective layer, on the other hand, it produces the treatability of the surface.
  • the coating agent layer can also comprise additives such as corundum or the like, which cause the coating agent layer to be reinforced against external influences.
  • a double effect protection and treatability
  • the color-adaptable carrier layers are arranged on a further material (a material carrier).
  • a material carrier This in turn is dependent on the design as a paint surface or as a synthetic resin surface.
  • the order can be made on the material either directly after or at Zeitli chem distance, so that the color-adaptable carrier layers are present as decorative paper or finish foils.
  • a layer of adhesive resin is applied to the underside of the carrier layer, which adheres under the action of pressure and heat, the carrier layer with the material ver.
  • adhesive resin in particular, a synthetic resin layer based on melamine or phenol is arranged. The application takes place, as in the case of the coating agent, preferably by means of a roller arrangement, a doctor blade or a spraying device.
  • melamine has the advantage that it can be cured to a transparent layer, so that no color change, such as a dark background, can arise from the underside.
  • the arrangement may be such that either at least one layer Kle resin is applied to the top of the material or at least one layer of adhesive resin on the underside of the carrier layer.
  • this is either applied (when solid state) or applied (in the liquid state).
  • the adhesive resin is present in solid form, for example as a film, and accordingly is placed on the material and / or on the upper side of the carrier layer when arranged between the material and the carrier layer.
  • a liquid adhesive resin is applied to the upper side of the material and / or the underside of the carrier layer. Both the liquid applied adhesive resin can be pre-dried after the orders. This can be done for example by means of heat.
  • the pressing of the (resin-impregnated and provided with a synthetic resin coating agent on the top) carrier layer with the material takes place for example in a conventional wood-based press. Depending on the Ausry tion of materials, this may be formed, for example, as a short-cycle press or as a continu ous press. The pressing takes place, for example, simultaneously with the action of heat and pressure on the synthetic resin surfaces. In particular, at materials that are not plate-shaped, but for example arcuate, round or similar shaped, and alternative pressing devices can be used.
  • the dried carrier layer is laminated onto a material for bonding with an adhesive, wherein a hotmelt, PUR or a PVAC glue is used as adhesive in particular.
  • the lamination is done in particular Chen in support layers with Lackoberflä, but can also be done on synthetic resin surfaces that have already been fully cured.
  • a material is basically a material carrier material understood, which is connected to the carrier layer.
  • the material may, for example, as the carrier material as one or more glued together layers of paper, example, be executed as kraft paper.
  • a kind of HPL or CPL can be generated by means of the method.
  • the material used is a wood-plastic composite (WPC) or a wood material, in particular a fiber material, CDF material, MDF material, HDF material, chip material or OSB material , Under WPC ent speaking modifications with paper or bamboo are understood as a filler.
  • WPC wood-plastic composite
  • the material can basically have any coated form.
  • the work can be sheet-shaped surfaces, for example, designed as a round rod.
  • the material may have the shape of a rectangular bar.
  • in an all-round coating also heated frame components for furniture doors made with a corresponding synthetic resin surface who the.
  • a plate-shaped material in particular a Faserze mentplatte.
  • Gypsum fiber board, WPC board or a wood-based panel used can be used in an advantageous manner, for example, for wall coverings, ceiling coverings, floor coverings or fillings for furniture doors.
  • wood-based panels such as CDF plates, MDF boards, HDF boards, chipboard or OSB boards.
  • a rod-shaped material from appropriate fiber cement material, Gipsturama material, WPC material or wood material, such as MDF, HDF, CDF chip or OSB material can be made.
  • the object is achieved by a material having a color-changeable synthetic resin surface or lacquer surface at least comprising a carrier layer bonded to the material, wherein the carrier layer is impregnated with an impregnating agent without pickling additive, an adhesive resin arranged between the underside of the carrier layer and the upper side of the material Adhesive and arranged on the top of the carrier layer, at least largely transparent, open-pored and cured layer of a coating agent with or without a pickling additive.
  • the carrier layer preferably comprises a decor printed on the upper side, which is visible through the layer of coating agent.
  • Resistant synthetic resin surface or paint surface is provided, which can be subsequently color-adjusted (stained) after complete curing.
  • a Derar term color adjustment has been known in particular only by pickling solid wood surfaces. The color adjustment can be carried out in particular by the end consumer.
  • the subsequent color processing can pickle in particular by means of conventional wood, in particular conventional water pickling, oil pickling or solvent pickling for wood surfaces done.
  • the predetermined by the decor base color of the resin surface is subsequently, d. H. after the actual industrial Fertigstel len of the resin surface individually changed.
  • the inventive material is compared to the heatable solid wood surfaces significantly cheaper and more resistant to external influences.
  • a decor paper with a color changeable synthetic resin surface or lacquer surface comprising a carrier layer formed as a decorative paper, for example, with a bottom side and a top side, which is impregnated with an impregnating agent and does not comprise pickle additives, one on top of the carrier layer coated and at least dried layer of a coating by means of with or without a pickling additive, which with the complete curing an additional At least largely transparent and open-pored surface forms.
  • a carrier layer formed as a decorative paper for example, with a bottom side and a top side, which is impregnated with an impregnating agent and does not comprise pickle additives, one on top of the carrier layer coated and at least dried layer of a coating by means of with or without a pickling additive, which with the complete curing an additional At least largely transparent and open-pored surface forms.
  • a particular embodiment of the intermediate decorative paper also provides ei NEN complementary order of an adhesive resin on the underside of the resin-impregnated carrier layer, wherein as adhesive resin in particular melamine is arranged.
  • the decor paper can be produced as an intermediate from the described Heinrichsverfah ren. In each case, at least one drying process takes place after the core impregnation and the application of the coating to the upper side, wherein in each case after the core impregnation and after the jobs a corresponding drying can be carried out.
  • the decorative paper has, in particular, a synthetic resin surface which is predried and on which a coating agent and pickling additive is applied, which likewise contains a synthetic resin.
  • a finish film with a color changeable ren pre-dried paint surface comprising a carrier layer having a top and a bottom, wherein the carrier layer is impregnated with an impregnating agent, which does not comprise a pickling additive and applied to the top and cured layer of a coating composition, which comprises a varnish with or without a pickling additive and forms an open-pored surface.
  • the impregnation of the Trä ger Anlagen the finish foil in particular with an impregnating agent based on UF, MUF, phenolic resin, acylate, polyester, alkyd, nitrocellulose, latex, a Tränkstoffgemisch or a combination of impregnating impregnation of at least two impregnants carried out on the aforementioned basis.
  • an impregnating agent based on UF, MUF or phenolic resin and may be formed as a synthetic resin.
  • a UV varnish be particularly suitable.
  • the decor paper as well as the finish film can be produced as an intermediate from the described manufacturing process.
  • At least one drying process takes place after the core impregnation and the application of the coating to the upper side, wherein in each case after the core impregnation and after the jobs a corresponding drying can be carried out.
  • the backing layer of the finish film may be, for example, as a plastic film, but is preferably removablebil det as a cellulosic web.
  • the color modification (pickling) of the cured synthetic resin surface / lacquer surface subsequent to the production of the synthetic resin surface or lacquer surface may comprise the steps of applying a dye, in particular a color stain to the cured coating, the dye penetrating the coating medium layer and the overall color tone of the synthetic resin surface / Lacquer surface changed, optionally ablation of the excess dye and / or drying of the applied and penetrated dye, and optionally orders a protective layer, for example, another resin layer or a lacquer layer on the color matched to the coating.
  • One possibility is to design correspondingly porous layers of lacquer, in particular lacquer layers based on acrylate, at least the outer lacquer layer by means of the drying process.
  • the drying takes place, for example, over several drying stages, whereby a porous, open, i.e., not fully permanently closed surface can be formed in the outer layer, which has a porosity not visible to the unaffected th eye. In the pores, the mordant can penetrate and fixed.
  • matting agents such as For example, sand, glass dust, mineral powder, silica, silicate, polyethylene and / or a copolymer in at least the outer layer of Lackober surface or synthetic resin surface. Due to the increased addition of the matting agents, it is likewise possible to achieve a porosity of the corresponding layer, so that in this case also etching agents (color pigments in solvent) can penetrate into the outer layer and be fixed.
  • matting agents such as For example, sand, glass dust, mineral powder, silica, silicate, polyethylene and / or a copolymer in at least the outer layer of Lackober surface or synthetic resin surface. Due to the increased addition of the matting agents, it is likewise possible to achieve a porosity of the corresponding layer, so that in this case also etching agents (color pigments in solvent) can penetrate into the outer layer and be fixed.
  • the decorative paper or the overlay is impregnated with respect to a conventional impregnation with a significantly lower amount of synthetic resin, for example, only with egg nem underside resin coat inset, so this has a fene outer surface after curing and thus also is porous. In the resulting pores, also not visible to the unaided eye, a suitable mordant can be added and dried.
  • a lean impregnated overlay can also be produced, for example, by piercing a decorating paper placed under the overlay, ie. H. For example, provided with a resin surplus and the overlay is pressed together with this high-density decorative paper. Since at the resin penetrates from the decorative paper on the underside of the overlay and the overlay forms a corresponding open-pored surface that is anzbar.
  • a color-changeable synthetic resin surface can be prepared, for example, without dressing additive and only with lean-set decorative paper and / or overlay as follows: provision of a decorative paper (for example 6 sg / m 2 ), impregnation of the decorative paper with a MUF synthetic resin (for example with 50 g / m 2 ), so that the impregnated decor paper has a weight of about 115 g / m 2 , placing an unimpregnated overlay (eg on a cellulose basis) with a weight of, for example, 14 g / m 2 on the decor paper and co-curing under the action of pressure and heat, for example in a press.
  • a decorative paper for example 6 sg / m 2
  • MUF synthetic resin for example with 50 g / m 2
  • an unimpregnated overlay eg on a cellulose basis
  • An alternative variant provides for the use of a decorative paper with a weight of about 80 g / m 2 , which is impregnated with 80 g / m 2 resin, for example.
  • MUF final weight soaked decorative paper: i6og / m 2
  • Decorative paper for example, with a weight between 14 g / m 2 to 25 g / m 2 together under the action of Pressure and heat is pressed in a press.
  • an overlay soaked with a coating agent with pickling additive can also be pressed onto one of the decorative papers described above.
  • the overlay can have, for example, a weight between 14 g / m 2 to 25 g / m 2 .
  • a coating agent with pickling additive for example, a MUF-kaolin mixture can be used for the impregnation, of which about 75 g / m 2 are introduced, so that the overlay soaked with a coating agent with pickling additive has a weight of about 100 g / m 2 has.
  • aspects have been described in the context of a material, a decorative paper, and / or a finish film, it will be understood that these aspects also constitute a description of the corresponding method, so that a block or component of the material / decor paper or finish film also as a corre sponding process step or as a feature of a process step is to be understood. Similarly, aspects described in connection with or as a method step also include a description of a corresponding block or detail or feature of the material, decor paper, and / or finish.
  • Figure 1 is an inventive material produced by the inventive process material plate with a synthetic resin surface in an exploded view.
  • FIG. 2 shows a material plate produced by the inventive method with a painted finish foil in an exploded view
  • Ex.i describes another method for producing a color changeable decor surface.
  • Figure 1 shows a side view of a material 1 with a heatable resin surface 8 in an exploded view. Contrary to the illustration, the individual layers (2, 3, 4, 7) in the sequence shown are fixed to each other and insoluble connected.
  • the material l has a material top 2.
  • a layer of synthetic resin 3 is arranged on the upper side of the material 2.
  • a carrier layer 4 with a bottom 5 and top 6 is shown above the synthetic resin 3, which adheres the carrier layer 4 and the material 1 mitei nander.
  • a coating 7 is arranged, which comprises the synthetic resin 7a. All layers are completely cured.
  • the coating 7 with synthetic resin 7a is open-pored (not shown here).
  • the open-pored formation takes place, in particular, by the arrangement of a filler 7b in the region of the coating 7, which has been applied as a coating 7 together with the synthetic resin 7a as a mixture.
  • the material 1 consists of a material plate.
  • the material plate is formed from a fiber material, here an MDF material. D. h.,
  • the material plate is a wood-based panel, but could alternatively be formed out of WPC material, chipboard, HDF material or CDF material, for example.
  • the carrier layer 4 was impregnated with a urea resin (not shown here) alternatively a melamine resin.
  • the carrier layer 4 with the material 1 bonding synthetic resin 3 here includes melamine resin.
  • the synthetic resin 3 bonds the upper side 2 of the material 1 to the underside 5 of the carrier layer 4.
  • the decor print shows in this case a colored wood decor, but could also be designed as a color decor or in grayscale.
  • the decor print reproduces both the structure of the wood and the color of the wood.
  • the coatings 7 applied on the upper side 6 comprise a urea resin formed as synthetic resin 7a with kaolin as filler 7b.
  • the mixture of kaolin and urea resin was applied in liquid to the top 6.
  • the weight ratio between urea resin and kaolin is before the mixture is applied 50% by weight: 50% by weight, preferably 20% by weight of kaolin to 80% by weight of liquid resin. After making the sandwich from the individual layers, this was introduced into a cycle press and pressed together under the action of pressure and heat.
  • Figure 2 shows schematically in a side exploded view produced by the inventions derischen method color-changeable paint surface 11 on a material 1.
  • the material 1 is here also plate-shaped, but may also have any other arbitrary shape.
  • the material 1 is a wood material, here an MDF board.
  • On the material plate 1 is a carrier layer 4, which is designed as a finish film 10 is laminated.
  • an adhesive 9, here a hotmelt arranged between the bottom 5 of the carrier layer 4 and the material upper side 2 of the material plate 1, an adhesive 9, here a hotmelt arranged.
  • the material 1 and the coated cured carrier layer 4 (finish foil) were on a laminating (not shown here) with each other a related party.
  • the finish foil 10 comprises a paper layer (carrier layer 4) which is impregnated with a liquid acrylate (not shown here) and on whose upper side 6 a decoration (not shown here) is printed. The impregnation takes place in an impregnating bath (not shown here).
  • the core-impregnated carrier layer 4 has no pickling additives 7b. After impregnation, the carrier layer 4 was dried by means of heat.
  • a layer 7 of a coating agent was applied with a spray device (not shown here).
  • the coating agent is in the form of a lacquer and comprises an acrylate 12 and pickling additives 7b may, if appropriate, also be carried out without a pickling additive if the acrylate of phenol is cured.
  • the coating agent was also dried by heat and cured.
  • Beizadditive 7b the surface of the layer 7 is open-pored and can pick up the color pigments of a stain men.
  • the layer 7 of coating agent contains kaolin. Before application of the coating composition, the ratio was 20% by weight of kaolin to 80% by weight of acrylate.
  • Another Brasssbespiel for producing a subsequently variable Synthetic resin or lacquer surface provides for soaking a carrier layer with a liquid impregnating agent without pickling additive.
  • the impregnating agent consists of melamine resin and / or urea resin.
  • additives such as wetting agents, release agents and / or anti-dust agents, but no pickling additives are added.
  • the impregnation is carried out with an amount between 8o wt.% And 250 wt.% Based on the carrier layer.
  • the carrier layer is here a paper.
  • the paper has a color decor and is thus a decorative paper.
  • the final weight of the impregnated carrier layer is after the impregnation process about i20g / m 2 to 220g / m 2 .
  • the soaked carrier layer is dried.
  • the drying takes place thermally. It can be carried out at temperatures between 6o ° and 200 °, but in particular takes place at temperatures between 40 ° C and 6o °.
  • the drying is carried out until a residual moisture content and / or a residual volatile content of 4% to 10% based on the final weight of the carrier layer is reached.
  • the drying is carried out in particular in a drying channel in the suspended process Runaway.
  • a layer of the coating composition is applied to the carrier layer.
  • the coating agent layer 10-90 microns
  • the order is carried out in particular by means of a roller application by a rubber roller.
  • the rubber roller preferably has a SHORE hardness A 40 (Shore A 40).
  • the coating agent layer is also thermally dried. This can be done again in the drying channel.
  • the drying temperatures are preferably between 60 ° and 180 °, the drying time between about 10 to 20 sec.
  • the carrier layer can be bonded to a material, in particular a material plate, for example a wood-based material plate such as a fiberboard or chipboard.
  • a material plate for example a wood-based material plate such as a fiberboard or chipboard.
  • the impregnated and coated carrier layer is pressed with a material plate in a short-cycle press. This takes place in particular special with a pressing pressure between 200 N / cm to 750 N / cm, a temperature between see 140 ° C and 200 ° C at the surface of the carrier layer and about 8 sec to 40 sec.
  • the coating agent here is a coating lacquer based on acrylate resins which can be used as a primer, for example the coating agent Hydro-UV lacquer HUE 8656X from Hesse-Lignal. Both coating lacquers form a ready-to-use, heatable surface due to the drying passages, the thin application method with the rubber roller and the pressing in the short cycle press, which has sufficient poosity so that subsequently applied color particles can accumulate in the outer surface layer.
  • the fully cured decorative surface is ready for use.
  • nachträgli chen color changing this decorative surface for example, commercial pickling based on water or other solvents can be used.
  • the stain "Parquet-Color" from Hesse-Lignal can be used.
  • the stained and dried surface can also be subsequently repainted with a corresponding protective layer (or fixing layer).
  • a coat of lacquer based on a two-component PUR acrylic resin lacquer is recommended.
  • the coating agent PUR SUN-CAPE DE 4800X from Hesse-Lignal can be used.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Inorganic Chemistry (AREA)

Abstract

L'invention concerne un procédé pour la fabrication d'une surface de résine synthétique ou d'une surface laquée de couleur variable, comprenant les étapes de fourniture d'une couche de support pourvue d'une face inférieure et d'une face supérieure, imprégnation de la partie centrale de la couche de support d'un agent d'imprégnation liquide sans additif de décapage, et au moins de séchage de la couche de support imprégnée. L'objet de l'invention est de permettre d'obtenir une surface décorative, dont le coloris peut être modifié particulièrement facilement par le consommateur final et qui est particulièrement peu onéreuse et résistante. À cet effet, une couche d'un agent de revêtement est appliquée sur la face supérieure de la couche de support et séchée, et la couche de support est ensuite reliée à un matériau, l'une des couches, lors du séchage et/ou de la liaison sur la face supérieure, durcissant de manière à obtenir une couche à pores ouverts au moins dans une très large mesure transparente.
EP19717769.4A 2018-03-29 2019-03-29 Plaque décorative pouvant être décapée Pending EP3774381A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP18165078.9A EP3546240A1 (fr) 2018-03-29 2018-03-29 Surface en résine synthétique pouvant être décapée
EP18165082.1A EP3546241A1 (fr) 2018-03-29 2018-03-29 Plaque décorative pouvant être décapée
DE102018129628 2018-11-23
PCT/EP2019/058049 WO2019185887A1 (fr) 2018-03-29 2019-03-29 Plaque décorative pouvant être décapée

Publications (1)

Publication Number Publication Date
EP3774381A1 true EP3774381A1 (fr) 2021-02-17

Family

ID=66182487

Family Applications (2)

Application Number Title Priority Date Filing Date
EP19717768.6A Pending EP3774380A1 (fr) 2018-03-29 2019-03-29 Surface pouvant être décapée
EP19717769.4A Pending EP3774381A1 (fr) 2018-03-29 2019-03-29 Plaque décorative pouvant être décapée

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CN115231879B (zh) * 2022-08-15 2023-07-25 东莞环球经典新型材料有限公司 一种可变色的无机人造石及其制备方法
CN115434187B (zh) * 2022-09-01 2023-06-09 浙江京华新材料科技有限公司 一种非造纸过程染色生产透芯专色涂布卡纸的方法

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RU2020135054A3 (fr) 2022-05-04
CA3094470A1 (fr) 2019-10-03
CN111918776A (zh) 2020-11-10
WO2019185886A1 (fr) 2019-10-03
EP3774380A1 (fr) 2021-02-17
RU2020135397A3 (fr) 2022-04-29
RU2020135054A (ru) 2022-05-04
UA127688C2 (uk) 2023-11-29
UA127260C2 (uk) 2023-06-28
CA3093625A1 (fr) 2019-10-03
CN111936318A (zh) 2020-11-13
RU2020135397A (ru) 2022-04-29
US20210009841A1 (en) 2021-01-14
WO2019185887A1 (fr) 2019-10-03
US20210010203A1 (en) 2021-01-14

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