EP2528752B1 - Method for applying nanoparticles - Google Patents
Method for applying nanoparticles Download PDFInfo
- Publication number
- EP2528752B1 EP2528752B1 EP11737371.2A EP11737371A EP2528752B1 EP 2528752 B1 EP2528752 B1 EP 2528752B1 EP 11737371 A EP11737371 A EP 11737371A EP 2528752 B1 EP2528752 B1 EP 2528752B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nanoparticles
- sheet
- photocatalytic
- paper
- panel
- 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.)
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- 239000002105 nanoparticle Substances 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 47
- 230000001699 photocatalysis Effects 0.000 claims description 54
- 238000005470 impregnation Methods 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 31
- 239000012530 fluid Substances 0.000 claims description 28
- 239000002952 polymeric resin Substances 0.000 claims description 23
- 229920003002 synthetic resin Polymers 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 12
- 229920000877 Melamine resin Polymers 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241000202567 Fatsia japonica Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures 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
- D21H27/28—Structures 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 treated to obtain specific resistance properties, e.g. against wear or weather
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
Definitions
- the disclosure generally relates to methods of applying nanoparticles on a surface to create a layer with embedded photo catalyst nanoparticles. Furthermore, the disclosure relates to a method to achieve a homogenous distribution of nanoparticles in the upper layer of boards and panels.
- WFF Wood Fibre Floor
- US2009/0208646A1 describes a wet-in-wet application of a coating to an impregnated overlay by means of a coating inlet.
- the control of the thickness of the layer is obtained by wipers that wipe of the excess coating.
- the document shows a method of producing an overlay, in particular for laminates, involving impregnation of a paper with the following method steps:
- US3798111 describes the incorporation of particles in the paper machine where the particles can be found throughout the paper, entangled by the fibres.
- WO2007144718 discloses a hard nanoparticle suspension applied to the resin pre-treated carrier sheet.
- the method states that the suspension comprises resin.
- the method comprises adding the suspension by means of a wire doctor roll and/or a raster roll or other methods comprising rolls and/or knifes. Also air-knives.
- Embodiments of the invention relates to a method of applying nanoparticles on a surface to create a sheet or a surface layer with photocatalytic nanoparticles.
- the aim is to improve the effect of the photocatalytic nanoparticles when the particles are embedded in the sheet or the surface layer, i.e. keeping the activity level at a high level and maintaining the desired properties of the sheet or the layer with the embedded particles.
- a first aspect of the invention is a method of manufacturing a sheet comprising photocatalytic nanoparticles, the method comprising the steps of:
- the sheet may comprise cellulose fibres.
- the impregnation fluid composition comprises a solvent comprising water.
- the method may comprise a step between impregnating and spraying step in which step the polymer resin is partly dried.
- the impregnation fluid composition may comprise photocatalytic nanoparticles and a solvent, said solvent being selected from water, ethylene glycol, butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol or methoxypropanol or combinations thereof.
- a solvent selected from water, ethylene glycol, butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol or methoxypropanol or combinations thereof.
- a second aspect of the invention is a method to produce a laminate board or panel by arranging the sheet produced according to the first aspect on a core, preferably an HDF panel and applying heat and pressure.
- a third aspect not presently claimed is a method of manufacturing a sheet comprising photocatalytic nanoparticles, the method comprising the steps of:
- a fourth aspect not presently claimed is a method to produce a paper sheet comprising photocatalytic nanoparticles in the paper plant, preferably prior to rolling of the paper.
- a fifth aspect not presently claimed is a method to produce a WFF panel comprising photocatalytic nanoparticles, the method comprises the step of:
- Step 2 and 3 of the method may be applied in any of the methods disclosed in WO2009/065769 and WO2009/124704 for production of WFF panels.
- the method is preferably performed in the numbered order 1-4.
- the organic solvent preferably comprises ketone, such as acetone and methyl ethyl ketone, and/or alcohol, such as ethanol, propanol and methanol, and/or acetate, such as butyl acetate, ethyl acetate.
- ketone such as acetone and methyl ethyl ketone
- alcohol such as ethanol, propanol and methanol
- acetate such as butyl acetate, ethyl acetate.
- the organic solvent is in a preferred embodiment ethanol.
- the method comprised the step of applying, preferably before step 2, a fluid with a wetting agent on the mix, preferably in the form of water containing 1% weight content of BYK-348 from BYK Chemie.
- a fluid with a wetting agent on the mix preferably in the form of water containing 1% weight content of BYK-348 from BYK Chemie.
- the fluid with the wetting agent and the organic solvent may also be applied together.
- the embedded nanoparticles have a primary particle size or crystal size of ⁇ 50 nm, such as ⁇ 30 nm, preferably a primary particle or crystal size of ⁇ 20 nm.
- ⁇ 50 nm such as ⁇ 30 nm
- ⁇ 20 nm preferably a primary particle or crystal size of ⁇ 20 nm.
- the embedded nanoparticles have a cluster or aggregate size of ⁇ 100 nm, such as ⁇ 80 nm, preferably a cluster or aggregate size of ⁇ 60 nm, such as ⁇ 40 nm, and even more preferably a cluster or aggregate size of ⁇ 30 nm, such as ⁇ 20 nm.
- said nanoparticles may be easier to disperse homogeneously in said overlaying layer, and said layer become more optically transparent.
- the concentration of said nanoparticles in said impregnation fluid may be > 1 wt%, such as > 5 wt%, preferably a concentration of said nanoparticles > 10 wt%, such as > 15 wt%, and even more preferably a concentration of said nanoparticles > 20 wt%, such as > 25 wt%.
- the nanoparticles in said impregnation fluid composition may have a cluster or aggregate size of ⁇ 100 nm, such as ⁇ 80 nm, preferably a cluster or aggregate size of ⁇ 60 nm, such as ⁇ 40 nm, and even more preferably a cluster or aggregate size of ⁇ 30 nm, such as ⁇ 20 nm.
- the amount of impregnation fluid composition per square meter of overlaying sheet(s) may be in the range 1-200 ml/m2, such as in the range 5-100 ml/m2, and preferably in the range 10-50 ml/m2, such as 20-40 ml/m2, of said impregnation fluid composition per square meter of overlaying sheet(s) to be impregnated.
- the polymer resin used for said polymer resin composition not presently claimed comprising nanoparticles may be selected from the group comprising melamine formaldehyde resin, phenol formaldehyde resin, urea formaldehyde resin, melamine urea formaldehyde resin, acrylamide resins, urethane resins, epoxy resins, silicon resins, acrylic resins, vinylic resins or mixtures thereof.
- the photocatalytic nanoparticles in said nanoparticle polymer resin composition may be introduced as a dry powder, as a paste or as a suspension and then dispersed in the polymer resin.
- a solvent of said suspension of photocatalytic nanoparticles to be dispersed in the polymer resin composition is selected from water, ethylene glycol, butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol or methoxypropanol or combinations thereof.
- Embodiments may in a sixth aspect not presently claimed be obtained by a method of manufacturing a board or a panel, the method comprising
- the coating fluid may in any of the above aspects be applied to said material surface by spraying, dipping, rolling, brushing or by other conventional application methods.
- the amount of coating fluid composition per square meter of said material surface may be in the range 1-200 ml/m2, such as in the range 5-100 ml/m2, and preferably in the range 10-50 ml/m2, such as 15-25 ml, of said coating fluid composition per square meter of said material surface.
- the present invention is concerned with manufacturing of an overlay or boards or panels, such as laminate boards or panels, comprising different types of photocatalytic nanoparticles, which makes the manufactured products photocatalytic active.
- Each layer and process step can be preferred from the others e.g. depending upon the price of the laminate boards and panels (low cost/high cost product) and the facilities available by the laminate manufacturers.
- Laminate boards and panels are typically made of a base of fibre board (mainly high density fibre board HDF) and 3 or more sheets: a decor sheet, an overlay sheet of cellulose on top and one or more backing sheets sitting on the opposite side of the fibre board base to balance the board and prevent it from curving. Other sheets are often placed between the fibre board and the decor sheet.
- the decor sheet could be monochromatic or patterned to look like e.g. wood, cork, stone, tiles or a more abstract pattern.
- the overlay sheet typically contains wear resistant particles, normally a certain amount of alumina oxide (Al2O3), to give the laminate better abrasive resistance.
- the overlay sheet is impregnated with a polymer resin, typically melamine formaldehyde resin.
- the other sheets are also impregnated with resin.
- the decor sheet is typically impregnated with melamine formaldehyde resin whereas phenol formaldehyde resin often is used in the core of the laminate.
- the laminate board or panel is assembled applying heat and pressure, making the resin polymerise in a thermosetting reaction. After lamination the polymerised overlay sheet and decor paper constitute the top layer of the laminate board or panel and thus needs to be optically transparent right from the upper surface of the laminate through to the decorative print of the decor paper.
- the photocatalytic nanoparticles are applied as a wet-in-wet spray coating (43, 40) to the upper and/or lower surface of the paper (10), after a first (42) and/or a second (41) impregnation of the paper (10) with a resin and wear resistant particles, preferably aluminium oxide.
- the paper may be dried (44,45) after each impregnation.
- the photocatalytic nanoparticles are applied after the impregnation step but before the drying step.
- the paper (10) is in a first step (46) moistened with a resin and/or impregnated in a resin through.
- This method of spraying the photocatalytic nanoparticles may be incorporated in any production line for producing overlay or decor paper, also in the line shown in fig 1 and described above under US2009/0208646 .
- the spraying of the photocatalytic nanoparticles may in the fig 1 line be performed at any stage after the moistening (14) of the paper web (10).
- a suitable type of spray nozzle for the spray coating of photocatalytic nanoparticles is an electronically controlled Autojet Pulsajet B10000jjau.
- Preferred spray velocity of overlay or decor paper may be > 1 m/s, such as > 2 m/s, preferably a velocity of > 5 m/s, such as > 8 m/s, and even more preferably a velocity of > 10 m/s.
- the photocatalytic nanoparticles are applied as a wet-on-dry spray coating to the upper and/or lower surface of the overlay and/or decor paper, after a first or a second impregnation of the paper with resin and wear resistant particles, preferably aluminium oxide.
- the paper is normally dried after each impregnation.
- the photocatalytic nanoparticles may be mixed with a wetting agent and/or an alcohol prior to the spray coating step to improve the wettability of the impregnation fluid on the overlay and/or decor sheet.
- the photocatalytic nanoparticles may be applied as a combination between wet-in-wet and wet-in-dry spray coating.
- photocatalytic nanoparticles are applied as a polymer mixture in the resin impregnation step.
- photocatalytic nanoparticles are incorporated into an overlay sheet, e.g., in the decor paper itself prior to polymer resin impregnation.
- a photocatalytic layer can be readily introduced applying the existing methods used for manufacturing laminate boards or panels i.e. polymer resin impregnation of the photocatalytic overlay sheet or decor paper followed by laminate board fabrication in a heat pressing laminating step.
- Said photocatalytic nanoparticle impregnation and drying/curing steps may be incorporated into an existing production line immediately prior to the polymer resin impregnation of said overlay sheet or decor paper or said photocatalytic impregnated and cured overlay sheet or decor paper can be stored until needed.
- a suitable type of nanoparticle for use in the coating fluid composition is Titania.
- the nanoparticles of Titania may according to some aspects of the present invention further comprise other elements.
- such elements may be introduced into said nanoparticles with the aim to improve the photocatalytic activity of said nanoparticles by altering the absorption range of said titania photocatalytic nanoparticles.
- the solvent of said coating fluid composition may comprise water, methanol, ethanol or isopropanol or combinations thereof, or may just be water.
- the particle concentration of said photocatalytic nanoparticles in the manufactured board or panel may be increased by repeating said coating step several times.
- a preferred embodiment of the produced impregnated paper comprises discrete photocatalytic nanoparticles on and in said overlay sheet or decor paper. Said nanoparticles or clusters of nanoparticles may in many applications according to the present invention be of substantially the same size as the effective particle size in said impregnation fluid composition.
- the produced impregnated paper comprising the photocatalytic nanoparticles, may be used in all known process, to produce laminated building panel, preferably floorboards, wall panels and kitchen tabletops
- the photocatalytic composition to be dispersed in the polymer resin may preferably comprise photocatalytically active nanoparticles of Titania (TiO2).
- said nanoparticles comprise the anatase and/or the rutile and/or the brookite crystal form of Titania or a combination thereof.
- said photocatalytically active nanoparticles are according to the present invention predominantly present in their final crystal form in said composition i.e. no heat treatment is required for transformation of said nanoparticles into their active form.
- the average primary particle size or crystallite size of the nanoparticles e.g.
- Titania expressed as an equivalent spherical diameter may preferably be below 30 nm, such as below 20 nm, and preferably below 15 nm, such as below 10 nm.
- the average primary particle size or crystallite size may be measured by X-ray Diffraction (XRD) using Scherer's formula. It is further preferred that the particle size distribution of said nanoparticles is relatively narrow.
- the photocatalytic composition to be dispersed in the polymer resin may be added to the polymer resin at any given time.
- the photocatalytic composition is dispersed into the polymer resin immediately prior to the impregnation of overlay sheets or decor papers with polymer resin. Said dispersion process may be aided by a specially designed machine or apparatus.
- Example 1 is presented as an embodiment of the present invention
- This example illustrates the production of a polymeric surface containing embedded nanoparticles.
- the particles were applied as dispersion via a spray system onto the freshly impregnated polymeric surface while still wet.
- the following dispersion was used as a feedstock. 30% TiO2 dispersion in water containing particle agglomerates of no bigger size than 80 nm as determined using the Particle Matriz Nanotrack NPA 252. The stock solution was then sprayed onto freshly impregnated melamine paper right after the paper had left the impregnation roller. The dispersion was applied onto the paper using an autojet spray system, pumping the fluid to the nozzles via a low pressure tank whit a pressure of 1.8 bar. The nozzles were pulsejet nozzles with air atomizing tips (air pressure 1.5 bar) placed 35 cm above the freshly impregnated paper right in front of the entrance to the first drying oven.
- the autojet system was set to deliver 30ml fluid/m2 of paper; the paper was then dried in two consecutive heating ovens. This yielded a melamine paper with embedded TiO2 agglomerates of a very small size, penetrating approximately the first couple of hundred micrometers of the melamine paper.
- Example 2 is presented as an example of an embodiment not presently claimed.
- This example illustrates the production of a polymeric surface containing embedded nanoparticles.
- the particles were applied as dispersion via a spray system onto the polymeric surface after this was dried in the heating oven.
- Example 3 is presented as an example of an embodiment not presently claimed.
- This example illustrates the production of a polymeric surface containing embedded nanoparticles.
- the particles were applied as dispersion via a spray system onto the raw paper before the paper was impregnated with melamine.
- Treatment Appearance (a) Stability (b) Distribution (c) Blank - Reference 1 1 - Test I: Wet-in-wet 1 1 1 1 Test II: Wet-on-dry 2 1 3 Test III: Wet- in-dry 4 4 2
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Laminated Bodies (AREA)
Description
- The disclosure generally relates to methods of applying nanoparticles on a surface to create a layer with embedded photo catalyst nanoparticles. Furthermore, the disclosure relates to a method to achieve a homogenous distribution of nanoparticles in the upper layer of boards and panels.
- It is well known to produce laminated building panels with a surface comprising laminated paper sheets. Also known is a new type of panel called Wood Fibre Floor (WFF) that is disclosed in
WO2009/065769 , which shows both products and methods to produce such a product also using nanoparticles. Furthermore it is shown inWO2009/062516 to apply nanoparticles on a laminate surface or on an overlay paper - The documents below describe several ways to treat papers or impregnated papers prior to the final oven and before the paper can be used in laminate panels.
-
US2009/0208646A1 describes a wet-in-wet application of a coating to an impregnated overlay by means of a coating inlet. The control of the thickness of the layer is obtained by wipers that wipe of the excess coating. The document shows a method of producing an overlay, in particular for laminates, involving impregnation of a paper with the following method steps: - 1) Unrolling of an overlay base paper from a roll for the purpose of obtaining a paper web (10);
- 2) Moistening of the paper web (10) on one side with an impregnating medium (14);
- 3) Impregnating the paper web (10) with an impregnating medium (18)
- 4) Wet-in wet application of a coarse corundum and resin dispersion (27) on one side onto the paper web (10)
- 5) Opposite wet-in-wet application of a coating substance (29), in the form of resin and fine corundum, onto the paper web (10);
- 6) A dosage of the applied coating substance (29) by a wiper (32), to the desired application weight;
- 7) Drying the paper web (10) using a drying duct.
-
US3798111 describes the incorporation of particles in the paper machine where the particles can be found throughout the paper, entangled by the fibres. -
WO2007144718 discloses a hard nanoparticle suspension applied to the resin pre-treated carrier sheet. The method states that the suspension comprises resin. The method comprises adding the suspension by means of a wire doctor roll and/or a raster roll or other methods comprising rolls and/or knifes. Also air-knives. - Embodiments of the invention relates to a method of applying nanoparticles on a surface to create a sheet or a surface layer with photocatalytic nanoparticles. The aim is to improve the effect of the photocatalytic nanoparticles when the particles are embedded in the sheet or the surface layer, i.e. keeping the activity level at a high level and maintaining the desired properties of the sheet or the layer with the embedded particles.
- It is shown in
WO2009/062516A2 to use photocatalytic nanoparticles in a surface layer for improvement of e.g. the cleanability. Furthermore a method to apply the nanoparticles is disclosed. The method according to embodiments of the invention provides an improved transparency, increased lifetime and improved distribution of the nanoparticles. - A first aspect of the invention is a method of manufacturing a sheet comprising photocatalytic nanoparticles, the method comprising the steps of:
- impregnating a sheet with a polymer resin, preferably comprising wear resistant particles;
- spraying the sheet, freshly impregnated with the polymer resin in an uncured and wet state, with an impregnation fluid composition comprising dispersed photocatalytic nanoparticles; wherein the photocatalytic nanoparticles have a cluster or aggregate size of <100 nm;
- drying and/or at least partly curing said impregnated sheet comprising the polymer resin and the impregnation fluid.
- The sheet may comprise cellulose fibres.
- Preferably, the impregnation fluid composition comprises a solvent comprising water.
- The method may comprise a step between impregnating and spraying step in which step the polymer resin is partly dried.
- By applying the photocatalytic nanoparticles in a wet surface particularly the distribution of the particles is improved.
- The impregnation fluid composition may comprise photocatalytic nanoparticles and a solvent, said solvent being selected from water, ethylene glycol, butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol or methoxypropanol or combinations thereof.
- A second aspect of the invention is a method to produce a laminate board or panel by arranging the sheet produced according to the first aspect on a core, preferably an HDF panel and applying heat and pressure.
- A third aspect not presently claimed is a method of manufacturing a sheet comprising photocatalytic nanoparticles, the method comprising the steps of:
- mixing the photocatalytic nanoparticles in a polymer resin, to obtain an impregnation mix;
- applying the impregnation mix to a sheet, preferably by spraying.
- A fourth aspect not presently claimed is a method to produce a paper sheet comprising photocatalytic nanoparticles in the paper plant, preferably prior to rolling of the paper.
- A fifth aspect not presently claimed is a method to produce a WFF panel comprising photocatalytic nanoparticles, the method comprises the step of:
- 1) Scattering of a dry mix comprising wood fibres, a thermosetting resin, preferably melamine resin, and wear resistant particles on a core;
- 2) Applying an organic solvent on the mix on the core;
- 3) Spraying an impregnation fluid composition comprising dispersed photocatalytic nanoparticles, preferably dispersed in water;
- 4) Applying heat and pressure.
- Step 2 and 3 of the method may be applied in any of the methods disclosed in
WO2009/065769 andWO2009/124704 for production of WFF panels. - The method is preferably performed in the numbered order 1-4.
- The organic solvent preferably comprises ketone, such as acetone and methyl ethyl ketone, and/or alcohol, such as ethanol, propanol and methanol, and/or acetate, such as butyl acetate, ethyl acetate. The organic solvent is in a preferred embodiment ethanol.
- In another embodiment the method comprised the step of applying, preferably before step 2, a fluid with a wetting agent on the mix, preferably in the form of water containing 1% weight content of BYK-348 from BYK Chemie. The fluid with the wetting agent and the organic solvent may also be applied together.
- It is well known that a nanomaterial is not just a nanomaterial, and the characteristics of the embedded nanoparticles are important for their performance and e.g. the properties of said board or panel. In a particularly preferred embodiment in any of the aspects the embedded nanoparticles have a primary particle size or crystal size of < 50 nm, such as < 30 nm, preferably a primary particle or crystal size of < 20 nm. Hereby, the efficacy of the nanoparticles is improved and/or less nanoparticles are needed to obtain a specific effect.
- Primary particles are rarely present as individual primary particles, but in a more or less aggregated form. An efficient control of the agglomerate and/or cluster size is greatly preferred. Hence, in preferred embodiments the embedded nanoparticles have a cluster or aggregate size of < 100 nm, such as < 80 nm, preferably a cluster or aggregate size of < 60 nm, such as < 40 nm, and even more preferably a cluster or aggregate size of < 30 nm, such as < 20 nm. Thereby, said nanoparticles may be easier to disperse homogeneously in said overlaying layer, and said layer become more optically transparent.
- In any embodiment of the present invention, the concentration of said nanoparticles in said impregnation fluid may be > 1 wt%, such as > 5 wt%, preferably a concentration of said nanoparticles > 10 wt%, such as > 15 wt%, and even more preferably a concentration of said nanoparticles > 20 wt%, such as > 25 wt%.
- Further, in any embodiments the nanoparticles in said impregnation fluid composition may have a cluster or aggregate size of < 100 nm, such as < 80 nm, preferably a cluster or aggregate size of < 60 nm, such as < 40 nm, and even more preferably a cluster or aggregate size of < 30 nm, such as < 20 nm.
- In all of the aspects of the invention the amount of impregnation fluid composition per square meter of overlaying sheet(s) may be in the range 1-200 ml/m2, such as in the range 5-100 ml/m2, and preferably in the range 10-50 ml/m2, such as 20-40 ml/m2, of said impregnation fluid composition per square meter of overlaying sheet(s) to be impregnated.
- The polymer resin used for said polymer resin composition not presently claimed comprising nanoparticles, may be selected from the group comprising melamine formaldehyde resin, phenol formaldehyde resin, urea formaldehyde resin, melamine urea formaldehyde resin, acrylamide resins, urethane resins, epoxy resins, silicon resins, acrylic resins, vinylic resins or mixtures thereof.
- In embodiments not presently claimed the photocatalytic nanoparticles in said nanoparticle polymer resin composition may be introduced as a dry powder, as a paste or as a suspension and then dispersed in the polymer resin.
- In embodiments not presently claimed a solvent of said suspension of photocatalytic nanoparticles to be dispersed in the polymer resin composition is selected from water, ethylene glycol, butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol or methoxypropanol or combinations thereof.
- Embodiments may in a sixth aspect not presently claimed be obtained by a method of manufacturing a board or a panel, the method comprising
- providing the upper surface of a base or an assembled laminate board or panel with a coating applying a coating fluid composition comprising photocatalytic nanoparticles; and
- drying and/or curing said base or laminate board or panel, subsequent to said coating step.
- The coating fluid may in any of the above aspects be applied to said material surface by spraying, dipping, rolling, brushing or by other conventional application methods. The amount of coating fluid composition per square meter of said material surface may be in the range 1-200 ml/m2, such as in the range 5-100 ml/m2, and preferably in the range 10-50 ml/m2, such as 15-25 ml, of said coating fluid composition per square meter of said material surface.
- Several combinations of the ingredients can be made into fully functional products. Three examples are given below as to show three functional embodiments of the innovation.
- The disclosure will in the following be described in connection to preferred embodiments and in greater detail with reference to the appended exemplary drawing, wherein
- Fig 1
- Illustrates a production line for producing an overlay paper.
- Fig 2
- Illustrates a production line for producing an overlay paper comprising spraying unit.
- The present invention is concerned with manufacturing of an overlay or boards or panels, such as laminate boards or panels, comprising different types of photocatalytic nanoparticles, which makes the manufactured products photocatalytic active. Each layer and process step can be preferred from the others e.g. depending upon the price of the laminate boards and panels (low cost/high cost product) and the facilities available by the laminate manufacturers.
- Laminate boards and panels are typically made of a base of fibre board (mainly high density fibre board HDF) and 3 or more sheets: a decor sheet, an overlay sheet of cellulose on top and one or more backing sheets sitting on the opposite side of the fibre board base to balance the board and prevent it from curving. Other sheets are often placed between the fibre board and the decor sheet. The decor sheet could be monochromatic or patterned to look like e.g. wood, cork, stone, tiles or a more abstract pattern. The overlay sheet typically contains wear resistant particles, normally a certain amount of alumina oxide (Al2O3), to give the laminate better abrasive resistance. Furthermore, the overlay sheet is impregnated with a polymer resin, typically melamine formaldehyde resin. The other sheets, most often paper sheets, are also impregnated with resin. The decor sheet is typically impregnated with melamine formaldehyde resin whereas phenol formaldehyde resin often is used in the core of the laminate. The laminate board or panel is assembled applying heat and pressure, making the resin polymerise in a thermosetting reaction. After lamination the polymerised overlay sheet and decor paper constitute the top layer of the laminate board or panel and thus needs to be optically transparent right from the upper surface of the laminate through to the decorative print of the decor paper.
- In one embodiment of the invention (
fig 2 ) the photocatalytic nanoparticles are applied as a wet-in-wet spray coating (43, 40) to the upper and/or lower surface of the paper (10), after a first (42) and/or a second (41) impregnation of the paper (10) with a resin and wear resistant particles, preferably aluminium oxide. The paper may be dried (44,45) after each impregnation. Preferably the photocatalytic nanoparticles are applied after the impregnation step but before the drying step. In one embodiment the paper (10) is in a first step (46) moistened with a resin and/or impregnated in a resin through. This method of spraying the photocatalytic nanoparticles may be incorporated in any production line for producing overlay or decor paper, also in the line shown infig 1 and described above underUS2009/0208646 . The spraying of the photocatalytic nanoparticles may in thefig 1 line be performed at any stage after the moistening (14) of the paper web (10). - A suitable type of spray nozzle for the spray coating of photocatalytic nanoparticles is an electronically controlled Autojet Pulsajet B10000jjau.
- Preferred spray velocity of overlay or decor paper may be > 1 m/s, such as > 2 m/s, preferably a velocity of > 5 m/s, such as > 8 m/s, and even more preferably a velocity of > 10 m/s.
- In another embodiment not presently claimed the photocatalytic nanoparticles are applied as a wet-on-dry spray coating to the upper and/or lower surface of the overlay and/or decor paper, after a first or a second impregnation of the paper with resin and wear resistant particles, preferably aluminium oxide. The paper is normally dried after each impregnation.
- In a preferred embodiment of the invention the photocatalytic nanoparticles may be mixed with a wetting agent and/or an alcohol prior to the spray coating step to improve the wettability of the impregnation fluid on the overlay and/or decor sheet.
- In another embodiment not presently claimed the photocatalytic nanoparticles may be applied as a combination between wet-in-wet and wet-in-dry spray coating.
- In another embodiment not presently claimed photocatalytic nanoparticles are applied as a polymer mixture in the resin impregnation step.
- In another embodiment not presently claimed photocatalytic nanoparticles are incorporated into an overlay sheet, e.g., in the decor paper itself prior to polymer resin impregnation. Thus using said photocatalytic overlay sheet or decor paper a photocatalytic layer can be readily introduced applying the existing methods used for manufacturing laminate boards or panels i.e. polymer resin impregnation of the photocatalytic overlay sheet or decor paper followed by laminate board fabrication in a heat pressing laminating step.
- Said photocatalytic nanoparticle impregnation and drying/curing steps may be incorporated into an existing production line immediately prior to the polymer resin impregnation of said overlay sheet or decor paper or said photocatalytic impregnated and cured overlay sheet or decor paper can be stored until needed.
- A suitable type of nanoparticle for use in the coating fluid composition is Titania. The nanoparticles of Titania may according to some aspects of the present invention further comprise other elements. In some embodiments such elements may be introduced into said nanoparticles with the aim to improve the photocatalytic activity of said nanoparticles by altering the absorption range of said titania photocatalytic nanoparticles.
- The solvent of said coating fluid composition may comprise water, methanol, ethanol or isopropanol or combinations thereof, or may just be water.
- The particle concentration of said photocatalytic nanoparticles in the manufactured board or panel may be increased by repeating said coating step several times.
- A preferred embodiment of the produced impregnated paper comprises discrete photocatalytic nanoparticles on and in said overlay sheet or decor paper. Said nanoparticles or clusters of nanoparticles may in many applications according to the present invention be of substantially the same size as the effective particle size in said impregnation fluid composition.
- The produced impregnated paper, comprising the photocatalytic nanoparticles, may be used in all known process, to produce laminated building panel, preferably floorboards, wall panels and kitchen tabletops
- The photocatalytic composition to be dispersed in the polymer resin may preferably comprise photocatalytically active nanoparticles of Titania (TiO2). In a preferred embodiment said nanoparticles comprise the anatase and/or the rutile and/or the brookite crystal form of Titania or a combination thereof. Further, said photocatalytically active nanoparticles are according to the present invention predominantly present in their final crystal form in said composition i.e. no heat treatment is required for transformation of said nanoparticles into their active form. The average primary particle size or crystallite size of the nanoparticles, e.g. Titania expressed as an equivalent spherical diameter may preferably be below 30 nm, such as below 20 nm, and preferably below 15 nm, such as below 10 nm. The average primary particle size or crystallite size may be measured by X-ray Diffraction (XRD) using Scherer's formula. It is further preferred that the particle size distribution of said nanoparticles is relatively narrow.
- The photocatalytic composition to be dispersed in the polymer resin, whether it is introduced as a powder, a paste or a suspension, may be added to the polymer resin at any given time. In one embodiment not presently claimed the photocatalytic composition is dispersed into the polymer resin immediately prior to the impregnation of overlay sheets or decor papers with polymer resin. Said dispersion process may be aided by a specially designed machine or apparatus.
- Having described the basics aspects of the invention, the following examples are given to illustrate specific embodiments thereof.
- Example 1 is presented as an embodiment of the present invention
- This example illustrates the production of a polymeric surface containing embedded nanoparticles. The particles were applied as dispersion via a spray system onto the freshly impregnated polymeric surface while still wet.
- The following dispersion was used as a feedstock. 30% TiO2 dispersion in water containing particle agglomerates of no bigger size than 80 nm as determined using the Particle Matriz Nanotrack NPA 252. The stock solution was then sprayed onto freshly impregnated melamine paper right after the paper had left the impregnation roller. The dispersion was applied onto the paper using an autojet spray system, pumping the fluid to the nozzles via a low pressure tank whit a pressure of 1.8 bar. The nozzles were pulsejet nozzles with air atomizing tips (air pressure 1.5 bar) placed 35 cm above the freshly impregnated paper right in front of the entrance to the first drying oven.
- The autojet system was set to deliver 30ml fluid/m2 of paper; the paper was then dried in two consecutive heating ovens. This yielded a melamine paper with embedded TiO2 agglomerates of a very small size, penetrating approximately the first couple of hundred micrometers of the melamine paper.
- Example 2 is presented as an example of an embodiment not presently claimed.
- This example illustrates the production of a polymeric surface containing embedded nanoparticles. The particles were applied as dispersion via a spray system onto the polymeric surface after this was dried in the heating oven.
- The same liquid and spray system as used in Example 1 was used in this experiment.
- Example 3 is presented as an example of an embodiment not presently claimed.
- This example illustrates the production of a polymeric surface containing embedded nanoparticles.
- The particles were applied as dispersion via a spray system onto the raw paper before the paper was impregnated with melamine.
- The table below shows the result of different methods to apply the photocatalytic particles:
- Test I: Applying a photocatalytic top layer by impregnation of overlay paper wet-in-wet by spraying.
- Test II: Applying a photocatalytic top layer by impregnation of overlay paper wet-on-dry by spraying.
- Test III: Applying a photocatalytic top layer by impregnation of overlay paper wet-on-dry by spraying on raw overlay paper before melamine impregnation.
- The appearance, the stability and the distribution are evaluated.
Treatment Appearance (a) Stability (b) Distribution (c) Blank - Reference 1 1 - Test I: Wet-in-wet 1 1 1 Test II: Wet-on-dry 2 1 3 Test III: Wet- in-dry 4 4 2 - a) The appearance on a scale from 1-5, as judged by transparency and haziness, where 1 is no visible difference from non-embedded laminate and 5 is very hazy.
- b) The process stability was evaluated on a scale from 1-5, as judged by material lifetime and flexibility, where 1 is no difference from non-embedded laminate and 5 is very sensitive to process changes.
- c) The distribution of embedded particles was evaluated on a scale from 1-5, where 1 is complete homogenous distribution of photocatalytic nanoparticles.
Claims (15)
- Method of manufacturing a sheet comprising photocatalytic nanoparticles, the method comprising the steps of:• impregnating (41, 42) the sheet (10) with a polymer resin, preferably comprising wear resistant particles;• spraying (43, 40) the sheet (10), freshly impregnated with the polymer resin in an uncured and wet state, with an impregnation fluid composition comprising dispersed photocatalytic nanoparticles, wherein the photocatalytic nanoparticles have a cluster or aggregate size of < 100 nm;• drying and/or at least partly curing (44, 45) said impregnated sheet comprising the polymer resin and the impregnation fluid.
- The method as claimed in claim 1, wherein the sheet comprises cellulose fibres.
- The method as claimed in claim 1 or 2, wherein the impregnation fluid composition comprises a solvent comprising water.
- The method as claimed in any one of the preceding claims, wherein the method comprises a step between impregnating and spraying step in which step the polymer resin is partly dried.
- The method as claimed in any one of the preceding claims, wherein said photocatalytic nanoparticles have a crystallinity of at least 50 %.
- The method as claimed in any one of the preceding claims, wherein said nanoparticles have a primary particle size of < 50 nm, such as < 30 nm preferably a primary particle size of < 20 nm such as < 10 nm.
- The method as claimed in any one of the preceding claims, wherein the nanoparticles in said impregnation fluid composition have a cluster or aggregate size of <80 nm, preferably a cluster or aggregate size of < 60 nm, such as < 40 nm, and more preferably a cluster or aggregate size of < 30 nm, such as < 20 nm.
- The method as claimed in any one of the preceding claims, wherein the concentration of said photocatalytic nanoparticle impregnation fluid is > 1 wt%, such as > 5 wt% preferably a concentration of said nanoparticles > 10 wt% such as > 15 wt% and even more preferably a concentration of said nanoparticles > 20 wt% such as > 25 wt%.
- The method as claimed in any one of the preceding claims, wherein the amount of impregnation fluid composition per square meter of the applied surface is in the range 1-200 ml/m2 such as in the range 5-100 ml/m2 and preferably in the range 10-50 ml/m2 such as 20-40 ml/m2.
- The method as claimed in any one of claims 1-2 or 4-9, wherein the impregnation fluid composition comprises the photocatalytic nanoparticles and a solvent, said solvent being selected from water, ethylene glycol, butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol or methoxypropanol or combinations thereof.
- A method of producing a laminate board or panel (1) by arranging a sheet produced according any one of claims 1-4, on a core, preferably an HDF panel, and applying heat and pressure.
- The method as claimed in claim 11, wherein the board is a floorboard.
- The method as claimed in claim 11 or 12, wherein the sheet is an overlay sheet.
- Laminate board or panel produced according to any one of claims 11-13, wherein said photocatalytic nanoparticles are homogenously embedded in the uppermost layer of the panel.
- The laminate board or panel produced as claimed in claim 14, wherein said photocatalytic nanoparticles are homogenously embedded in the final panel at a thickness of > 0.1 µm; > 1 µm; > 10 µm; > 50 µm; > 100 µm; > 500 µm; > 1000 µm.
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MY167029A (en) | 2012-03-20 | 2018-07-31 | Välinge Photocatalytic Ab | Aphotocatalytic composition |
US20160023427A1 (en) * | 2012-05-29 | 2016-01-28 | Niles Nanofabrix | Nanomaterial based fabric reinforced with prepreg methods, and composite articles formed therefrom |
US9375750B2 (en) | 2012-12-21 | 2016-06-28 | Valinge Photocatalytic Ab | Method for coating a building panel and a building panel |
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EA035047B1 (en) * | 2014-07-16 | 2020-04-22 | Велинге Инновейшн Аб | Method to produce a wear resistant foil for a building panel |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3798111A (en) | 1972-03-24 | 1974-03-19 | Mead Corp | Multiple layer decorated paper,laminates prepared therefrom and process |
SK286684B6 (en) * | 1999-01-26 | 2009-03-05 | Kronospan Technical Company Ltd. | Method for impregnating decorative papers |
DE10035924B4 (en) * | 2000-07-21 | 2006-04-27 | Fritz Egger Gmbh & Co | Impregnate and method of making and using the impregnate |
JP2003071967A (en) * | 2001-08-31 | 2003-03-12 | Takiron Co Ltd | Decorative sheet having photocatalyst layer formed thereon as outermost layer |
CA2500244A1 (en) * | 2002-10-03 | 2004-04-15 | Metss Corporation | Electrostatic charge dissipating hard laminate surfaces |
WO2005068181A1 (en) * | 2004-01-16 | 2005-07-28 | Domo Oudenaarde Nv | Photocatalytic particles in floor laminates |
EP2026968A2 (en) * | 2006-06-13 | 2009-02-25 | Flooring Industries Limited, SARL | Method for manufacturing coated panels and coated panel |
CN200958280Y (en) * | 2006-10-20 | 2007-10-10 | 上海丰元木业有限公司 | Floor containing silver |
CN106046911A (en) * | 2007-11-16 | 2016-10-26 | 瓦林格光催化股份有限公司 | Photocatalytic boards or panels and a method of manufacturing thereof |
CN104002357A (en) | 2007-11-19 | 2014-08-27 | 瓦林格创新股份有限公司 | Fibre based panels with a wear resistance surface |
DE102008008808A1 (en) * | 2008-02-12 | 2009-08-13 | Dekor-Kunststoffe Gmbh | Method for producing a scuff-resistant overlay |
EP3470193B1 (en) | 2008-04-07 | 2024-01-24 | Välinge Innovation AB | Method of manufacturing a building panel |
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RU2012134551A (en) | 2014-03-10 |
MX342884B (en) | 2016-10-14 |
ZA201205612B (en) | 2013-09-25 |
WO2011093785A1 (en) | 2011-08-04 |
SG182270A1 (en) | 2012-08-30 |
CA2786676C (en) | 2020-01-14 |
EP3444122A1 (en) | 2019-02-20 |
BR112012017934B1 (en) | 2021-08-17 |
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