WO2017178031A1 - Produit à base de polymère photocatalytique et procédé pour produire un produit à base de polymère photocatalytique - Google Patents

Produit à base de polymère photocatalytique et procédé pour produire un produit à base de polymère photocatalytique Download PDF

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Publication number
WO2017178031A1
WO2017178031A1 PCT/DK2017/050117 DK2017050117W WO2017178031A1 WO 2017178031 A1 WO2017178031 A1 WO 2017178031A1 DK 2017050117 W DK2017050117 W DK 2017050117W WO 2017178031 A1 WO2017178031 A1 WO 2017178031A1
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Prior art keywords
polymer containing
less
containing product
photocatalytic
barrier layer
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Inventor
Henrik Jensen
Simon Lausten ØSTERGAARD
Theis Reenberg
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Photocat AS
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Photocat AS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0217—Pretreatment of the substrate before coating

Definitions

  • PRODUCE A PHOTOCATALYTIC POLYMER CONTAINING PRODUCT
  • the present invention relates to a photocatalytic polymer containing product and a method to produce a photocatalytic polymer containing product.
  • Photocatalytic compounds such as T1O2 can be used to produce smart building materials that can reduce, e.g. the high level of pollutant that poses a threat to the human health in big cities.
  • a common strategy is to apply photocatalytic compounds to building surfaces that are irradiated by the sun light during the day.
  • plastic surfaces that are exposed to sun light for several hours during the day.
  • titanium dioxide powder may be mixed with cement and other binders materials to produce photocatalytic pavement.
  • One drawback of these materials is the large amount of titanium dioxide powder used. Titanium dioxide powder has to be mixed in large quantity so as to achieve acceptable activity towards the reduction of pollutants as not all the titanium dioxide powder is available for photocatalytic reactions.
  • an efficient method to produce photocatalytic materials that are exposed to sunlight for several hours per day could be advantageous.
  • Polymer containing products such as plastic products generally lack protections, thus are quite sensitive to scratches, abrasions and therefore dust and dirt can easily contaminate their surfaces.
  • photocatalytic materials deposited on polymer surfaces may produce degradation due to light induced photocatalytic reactions.
  • An object of the present invention is to provide an alternative to the prior art.
  • the invention in a first aspect relates to a method of producing a photocatalytic polymer containing product, the method comprising : providing a polymer containing product; coating the polymer containing product with an inorganic barrier layer; wherein the inorganic barrier layer forms an internal surface in contact with the polymer containing product and an external surface; modifying the external surface of the inorganic barrier layer by surface treatment; applying a dispersion of inorganic particles to the modified external surface; wherein the inorganic particles of the dispersion of inorganic particles comprises photocatalytic particles.
  • the photocata lytic particles are deposited on the modified external surface of the inorganic layer.
  • the external surface of the inorganic layer is the one not in contact with polymer containing product, i.e. the one exposed to air before the application of the dispersion of inorganic particles.
  • the external surface may be generally the surface opposite to the internal surface in contact with the polymer containing product.
  • an inorganic barrier layer applied on the surface of a polymer containing product shields the polymer containing product from the environment, thus protecting the polymer containing product from abrasion and scratches that may be caused during use.
  • the presence of the inorganic barrier layer avoids direct degradation of the polymer containing surface.
  • the inorganic barrier layer prevents the contact between the photocatalytic particles and the surface of the polymer containing product.
  • the contact between the photocatalytic particles and the surface of the polymer containing product may lead to degradation of the surface due to photocatalytic reaction induced by the (sun)light irradiation.
  • the presence of the inorganic barrier layer ensure separation between the photocatalytic particles and the surface of the polymer containing product thus avoiding photocatalytic degradation of the surface.
  • the surface of the polymer containing product may be coated with an organic layer, e.g. a base coat such as a lacquer layer. Also in this case, if the barrier layer was not present, the photocatalytic nanoparticles upon (sun)light excitation may react with the base coat or any other underlying lacquer layer damaging the surface of the base coat and in turn of the polymer containing product
  • the inorganic barrier layer is not brittle or stiff but flexible so that it can be applied to the surface of the polymer containing product with no negative impact on the surface substrate avoiding potential cracking that would lead to percolation of photocatalytic particles that may produce the undesired above mentioned effects.
  • providing a polymer containing product comprises applying a polymer layer to a sheet as a coating and/or impregnation to provide a polymer containing product.
  • the polymer containing product may be a product consisting of polymer, such as a hard plastic product.
  • the polymer containing product may be a product made of other materials, such a metal, wood, glass or plastic and then coated with a polymer coating.
  • the sheet may be a fiber sheet or paper, for example glass fiber dew, or any other base material for roofing felt to make shingles and roll roofing used in building construction.
  • the sheet may also be a plate of cement fibers.
  • the invention relates to a photocatalytic polymer containing product comprising :
  • the inorganic barrier layer is a continuous inorganic barrier layer.
  • the inorganic layer may be a compact layer.
  • the inorganic layer may be impermeable layer.
  • the inorganic layer may be a layer of silica.
  • the photocatalytic particles have a particle size in the micro and/or nano meter range.
  • Micro meter range is preferably used to indicate that the dimension of the particle in question is in the range of between 1*10 ⁇ 6 and 1000*10 ⁇ 6 meters.
  • Nano meter range is preferably used to indicate that the dimension of the particle in question is in the range of between 1*10 ⁇ 9 and 1000*10 ⁇ 9 meters.
  • Such dimension may be determined as an average particle size, as the geometrical average of the size of the particles, or based on an equivalent diameter determined as the cubic root of mass/density*4/3/n (Pi).
  • the photocatalytic particles may be provided by depositing on the surface on the inorganic barrier layer.
  • the photocatalytic particles may be embedded in the inorganic barrier layer.
  • the photocatalytic particles are titanium dioxide nanoparticles.
  • the surface modification may produce changes of the surface properties.
  • modifying the external surface changes surface properties by exposing chemical functional groups, such as hydroxyl groups, i.e. OH groups.
  • Modifying the external surface of the inorganic barrier layer subsequently to being applied to the polymer containing product may comprise priming the inorganic barrier layer for adherence and/or spreading of photocata lytic nano particles to the surface of the inorganic barrier layer.
  • the priming for adherence of photocata lytic nano particles may be selected from corona exposure, plasma exposure, flame oxidation exposure.
  • the surface treatment may comprise air plasma treatment, such as corona discharge treatments.
  • the surface treatment of the external surface may comprise chemical treatment, flame treatment, oxidation treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment and ion treatment.
  • priming or surface treatment may be extended to one or more surfaces of the polymer containing product before the application of the inorganic barrier layer.
  • the method according to the first aspect further comprises, after coating the polymer containing product with an inorganic barrier layer: drying and/or curing said inorganic barrier layer.
  • drying and/or curing said inorganic barrier layer occurs before modifying the external surface of the inorganic barrier layer by surface treatment.
  • the method according to the first aspect further comprises, after applying a dispersion of inorganic particles to the modified external surface: drying and/or curing the inorganic particles applied to the modified external surface.
  • the method according to the first aspect further comprises: modifying an external surface of the polymer containing product before coating the polymer containing product with an inorganic barrier layer.
  • modifying an external surface of said polymer containing product before coating the polymer containing product with an inorganic barrier layer is a achieve by surface treatment.
  • the surface of polymer containing product to which the inorganic layer is provided as a coating is primed for adherence and/or spreading of the coating, before the coating with the inorganic layer.
  • the priming for adherence and/or spreading of the coating is selected from corona exposure, plasma exposure, flame oxidation exposure.
  • drying and/or curing the inorganic barrier layer is provided by heating, such as forced heating, such as convective heating, e.g. by use of a gas flow where the gas has an elevated temperature (e.g. heated air), exposure to infra-red radiation, ultra violet radiation, microwaves or electron beam.
  • heating such as forced heating, such as convective heating, e.g. by use of a gas flow where the gas has an elevated temperature (e.g. heated air), exposure to infra-red radiation, ultra violet radiation, microwaves or electron beam.
  • Drying and/or curing may be achieved by low temperature steps, e.g. less than 100, such as less 80, for example less than 60, such as less than 40 degree C, for period of times between 5 minutes down to 30 sec.
  • low temperature steps e.g. less than 100, such as less 80, for example less than 60, such as less than 40 degree C, for period of times between 5 minutes down to 30 sec.
  • fast low temperature steps may be used to obtain efficient drying and/or curing.
  • the thickness and material of the inorganic layer used that allows for efficient fast drying and/or curing at low temperature such as less than 70 degree C.
  • drying and/or curing the dispersion of inorganic particles is provided by heating, such as forced heating, such as convective heating, e.g. by use of a gas flow where the gas has an elevated temperature (e.g. heated air), exposure to infra-red radiation, ultra violet radiation,
  • heating such as forced heating, such as convective heating, e.g. by use of a gas flow where the gas has an elevated temperature (e.g. heated air), exposure to infra-red radiation, ultra violet radiation,
  • drying and/or curing may be achieved by exposing said polymer containing product to temperatures less than 100, such as less 80, preferably less than 60, such as less than 40 degree C, for period of times between 5 minutes down to 10 sec, such as less than 4 minutes, less than 3 minutes, less than 2 minutes or less than 1 minutes, such as less than 50 seconds, less than 30 seconds or less than 15 seconds.
  • applying the dispersion of inorganic particles to the modified external surface comprises spraying a dispersion comprising
  • the dispersion of inorganic particles may be an aqueous dispersion.
  • the dispersion is applied to the inorganic barrier layer in an amount of less than 200 ml/m 2 , such as 150 ml/m 2 , for example less than 100 ml/m 2 , preferably less than 50 ml/m 2 , such as less than 40 ml/m 2 , preferably less than 30 ml/m 2 , such as less than 20 ml/m 2 .
  • the photocatalytic particles are embedded in the inorganic barrier layer.
  • coating the polymer containing product with an inorganic barrier layer comprises coating with an inorganic fluid composition
  • the inorganic fluid composition is a solution comprising a solvent, preferably selected from alcohols, water and mixture hereof and an inorganic substance is selected from silicone resin, methyl silicone, methylphenyl silicone, PMSQ silicone and mixtures hereof.
  • the inorganic fluid composition may comprise an of inorganic substance less than 25 wt %, such as between 1 and 10 wt %, preferable in between 4 and 6 wt %, such as 5 wt %.
  • coating the polymer containing product with an inorganic barrier layer provides the inorganic barrier layer with a mass per square meter less than 100 g/m 2 , such as less than 50 g/m 2 , preferably less than 25 g/m 2 .
  • coating the polymer containing product with an inorganic barrier layer provides the inorganic barrier layer with a thickness less than 5.0 ⁇ , such as less than 2.5 ⁇ , preferably less than 1.0 ⁇ , such as less than 0.75 ⁇ , preferably less than 0.5 ⁇ , such as less than 0.25 ⁇ .
  • the photocatalytic particles may be embedded in the inorganic barrier layer.
  • the photocatalytic particles are deposited on an outer surface of the inorganic barrier layer. In some further embodiments, the photocatalytic particles are embedded in the inorganic barrier layer and deposited on an outer surface of the inorganic barrier layer.
  • the photocatalytic polymer containing product may be used as a consumable plastic product.
  • the polymer containing product may have the form of a foil that is then coated by the inorganic barrier layer on which photocatalytic particles are deposited.
  • polymer containing product may be furniture foils, outdoor weather resistant foils, polycarbonate (PC) foils, Polyvinyl chloride (PVC) foils, PMMA, polyurethane (PU), Acrylic foils, such as Poly(methyl methacrylate) (PMMA) foils and flexible floors, such as luxury Vinyl Tile (LVT) floor.
  • PC polycarbonate
  • PVC Polyvinyl chloride
  • PU polyurethane
  • Acrylic foils such as Poly(methyl methacrylate) (PMMA) foils
  • flexible floors such as Luxury Vinyl Tile (LVT) floor.
  • LVT Luxury Vinyl Tile
  • the photocatalytic polymer containing product may thus be foils, such as semi- transparent foils that can be attached to windows or fagades so as to provide a photocatalytic surface on a photocatalytic degradable substrate through the use of an inorganic barrier layer.
  • the photocatalytic particles may be discrete particles.
  • the inorganic barrier layer is a continuous inorganic barrier layer.
  • the photocata lytic particles such as titanium dioxide nanoparticles, may be in an amount of 10 g/m 2 or less, such as 5 g/m 2 or less, preferably 3 g/m 2 or less, more preferably 2 g/m 2 or less, most preferably 1 g/m 2 or less.
  • the photocata lytic particles such as titanium dioxide nanoparticles, may have a primary size less than 50 nm, preferably less than 30 nm, more preferably less than 20 nm.
  • the photocata lytic particles such as titanium dioxide nanoparticles, may have an agglomerate size of less than 300 nm, less than 200 nm, less than 100 nm, such as less than 80 nm preferably an aggregate size of less than 60 nm such as of less than 40 nm and even more preferably an aggregate less than 30 nm such as less than 20 nm.
  • the photocatalytic particles such as titanium dioxide nanoparticles, are in anatase phase.
  • Figures 1 illustrates schematically a photocatalytic polymer containing product according to a some embodiments of the invention wherein photocatalytic nano particles are embedded in an inorganic barrier layer.
  • Figure 2 illustrates schematically a photocatalytic polymer containing product according to a some other embodiments of the invention wherein photocatalytic nano particles are deposited onto an inorganic barrier layer.
  • Figure 3 illustrates schematically a photocata lytic polymer containing product according to further embodiments in which the polymer containing product comprises a sheet coated by a polymer coating.
  • Figure 4 is a flow-chart of a method of producing photocata lytic polymer containing product according to some embodiments of the invention.
  • Figure 5 is a schematic drawing of the steps of the method of producing a photocata lytic polymer containing product, according to some embodiments of the invention.
  • Figure 6 shows polymer containing foils tests related to the photocatalytic air purifying properties tested according to the NOx degrading properties after ISO 22197-1 before and after 300 hours of accelerated weathering according to EN 1297: 2004.
  • FIGS 1-3 schematically illustrating a photocatalytic polymer containing product comprising a polymer containing product 26 and an inorganic barrier layer 24 coated onto said polymer containing product 26.
  • the polymer containing product 26 may be in the form of a sheet impregnated with polymer, or in general a matrix comprising polymer (not shown) or may be in the form of a sheet to which polymer is applied as a layer/coating, e.g. figure 3.
  • the product 25 and the layer/coating of polymer 27 forms the polymer containing product 26.
  • the inorganic barrier layer 24 may comprise photocatalytic particles 22, such as photocatalytic titanium dioxide nanoparticles, having a particle size in the micro- and/or nano meter range.
  • the photocatalytic particles 22 may be embedded in the inorganic barrier layer 24, and as illustrated in figure 2, the photocatalytic particles 22 may be deposited on the outer or external surface (opposite to the surface facing towards the layer in contact with the polymer containing product) of the inorganic barrier layer 24.
  • a combination of this may be used in connection with the present invention in which the photocatalytic particles 22 are embedded in the inorganic barrier layer 24 and deposited on the outer surface of the inorganic barrier layer 24.
  • a barrier layer applied on the surface of the polymer containing product 26 shields the polymer containing product from the surrounding environment.
  • the polymer containing product according to the invention is a roofing felt.
  • the polymer containing product according to the invention is a consumable plastic product.
  • the photocatalytic particles are discrete particles. However, agglomerates of photocatalytic particles may also be used.
  • the inorganic barrier layer 24 is a continuous inorganic barrier layer, preferably in the meaning that the inorganic barrier layer 24 covers fully the polymer containing product with no direct exposure of the surface of the polymer containing product 26.
  • the photocatalytic particles such as titanium dioxide nanoparticles, are in an amount of 10 g/m 2 or less, such as 5 g/m 2 or less, preferably 3 g/m 2 or less, more preferably 2 g/m 2 or less, most preferably 1 g/m 2 or less.
  • the area used in characterizing the amount is typically the outer or external surface area of the inorganic barrier layer 24.
  • the photocatalytic particles such as titanium dioxide nanoparticles, have preferably a primary size less than 50 nm, preferably less than 30 nm, more preferably less than 20 nm.
  • the photocatalytic particles such as titanium dioxide nanoparticles
  • the photocatalytic particles preferably have an agglomerate size of less than 300 nm, less than 200 nm, less than 100 nm, such as less than 80 nm preferably an aggregate size of less than 60 nm such as of less than 40 nm and even more preferably an aggregate less than 30 nm such as less than 20 nm.
  • the photocatalytic particles such as titanium dioxide nanoparticles, are in anatase phase.
  • FIG. 4 illustrating in a flow chart a method of producing a photocatalytic polymer containing product according to a preferred embodiment of the invention wherein :
  • - SI refers to one or more steps of
  • said inorganic barrier layer forms an internal surface in contact with said polymer containing product (26) and an external surface;
  • FIG. 5 is a schematic drawing of the steps of the method of producing polymer containing product according to an embodiment.
  • the schematic drawing of figure 5 shows:
  • - S3 providing a polymer containing product by either coating a product, such as a fiber cement with a polymer material or proving a product consisting of polymer, such as polycarbonate;
  • - S4 optionally performing an organic coating onto the surface of the polymer containing product, for example an acrylic coating or PU coating;
  • the coating of the polymer containing product 26 with an inorganic barrier layer 24 is done. It is noted that a priming or surface treatment may be applied prior to the coating with an inorganic barrier layer to ensure adherence of the inorganic barrier layer 24 to the polymer containing product 26.
  • depositing of photocatalytic particles are to be deposited on the surface of the inorganic barrier layer 24, this is typically carried out subsequently to the application of the inorganic barrier layer. Again, a priming or surface treatment may be used prior to application of the photocatalytic particles e.g. to ensure adherence. These steps may be carried out as sprinkling.
  • drying in between the process illustrated e.g. in figure 5 may be advantageous.
  • the polymer containing product 26 may need to cool, cure, dry, heated or other setting process prior to e.g. being rolled into a coil.
  • the photocatalytic particles are deposited on to the surface of the inorganic barrier layer, this can be carried out before a rolling up step.
  • Coating the polymer containing product comprises: sprinkling, roll application or brush application said polymer containing product with an inorganic liquid composition being harden-able, cure-able, and/or setting-able.
  • the photocatalytic particles 22 may be in the inorganic liquid composition or be applied onto the surface of the inorganic barrier layer 24.
  • Such a sprinkling can be air assisted sprinkling, hydraulic assisted sprinkling where the inorganic liquid composition is made into a stream of droplets directed towards the polymer containing product by use of gas or hydraulic.
  • the droplets may be formed by use of ultra sound.
  • the inorganic barrier layer 24 subsequently to being applied to said polymer containing product (26) is dried and/or cured.
  • drying and/or curing may be provided by heating, such as forced heating, such as convective heating, e.g. by use of a gas flow where the gas has an elevated temperature (e.g. heated air), exposure to infra-red radiation, ultra violet radiation.
  • the inorganic barrier layer 24 is preferably, subsequently to being applied to the polymer containing product 26, primed or surface treated for adherence and/or spreading (or at least improvements thereof) of photocatalytic nano particles to the surface of the inorganic barrier layer 24 but also to create a better wetting of the surface to avoid excess amount of wetting agent to be used.
  • the Contact Angle (CA) between water and the corona treated barrier layer surface is preferable lower than 60 °, 40 °, 20 °, 10 °.
  • Such priming of surface treatment for adherence of photocatalytic nano particles may be selected from corona exposure, plasma exposure, flame oxidation exposure. Priming may typically include, after the barrier layer is dried, hardened or in general set, a corona treatment e.g. to provide
  • the photocatalytic particles 22 are provided by depositing on the surface on the inorganic barrier layer 24.
  • Such depositing may comprise spraying a dispersion comprising photocatalytic titanium dioxide nanoparticles onto said inorganic barrier layer 24.
  • a dispersion is preferably an aqueous dispersion.
  • the surface of the polymer containing product 26 to which the inorganic layer 24 is provided e.g. as a coating may preferably be primed for adherence and/or spreading of the coating.
  • Such as priming for adherence and/or spreading may be selected from corona exposure, plasma exposure, flame oxidation exposure.
  • the dispersion comprises:
  • co-solvents preferably alcohol, such as isopropanol up to 15 wt%, more preferably up to 10 wt%;
  • photocata lytic titanium dioxide nanoparticles in the range between 15 wt% and 2.5 wt%, such as 10 wt% or 5wt%;
  • the dispersion stable such as a dispersion agent, and preferably
  • the dispersion is preferably applied to the inorganic barrier layer in an amount of less than 200 ml/m 2 , such as 150 ml/m 2 , for example less than 100 ml/m 2 , preferably less than 50 ml/m 2 , such as less than 40 ml/m 2 , preferably less than 30 ml/m 2 , such as less than 20 ml/m 2
  • the photocatalytic particles 22 are embedded in the inorganic barrier layer 24.
  • a liquid containing photocatalytic nano particles 22, and the inorganic substances forming the bulk of the inorganic layer is applied to the surface of the polymer containing product 26. If a priming for adherence and/or spreading is used, this priming is carrier out prior to application of the liquid.
  • the inorganic fluid composition which at least partially forms the inorganic barrier layer, is typically a solution comprising a solvent and an inorganic substance is selected from silicone resin, methyl silicone, methylphenyl silicone, PMSQ silicone and mixtures hereof.
  • the solvent can be for example alcohols, water and mixture hereof.
  • the amount of inorganic substance in said inorganic fluid composition is less than 25 wt %, such as between 1 and 10 wt %, preferable in between 4 and 6 wt %, such as 5 wt %.
  • the inorganic particles 25 are preferably selected from silica particles, alumina particles, and/or amorphous Ti02 particles.
  • the size of the inorganic particles is preferably smaller than 250 nm, such as smaller than 100 nm, preferably smaller than 50 nm, such as smaller than 25 nm.
  • the weight ratio the inorganic particles 25 to the amount of inorganic matter in inorganic liquid composition is in the range of preferably 1 : 10, such as 1:4, preferably 1: 2, such as 1 : 1, preferably 2: 1, such as 4: 1, preferably 10: 1.
  • the coating provided by the inorganic barrier layer is typically provided so that the inorganic barrier layer 24 has a mass per square meter less than 100 g/m2, such as less than 50 g/m2, preferably less than 25 g/m2, for example less than 10 g/m2, such as less than 1 g/m2.
  • the coating is typically coated to provide the inorganic barrier layer 24 with a thickness less than 5.0 ⁇ , such as less than 2.5 ⁇ , preferably less than 1.0 pm, such as less than 0.75 ⁇ , preferably less than 0.5 ⁇ , such as less than 0.25 ⁇ , for example less than 0.10 ⁇ , such as less than 0.01 ⁇ .
  • the coating is typically coated to provide the inorganic barrier layer having a thickness of one or more monolayers, such as few monolayers.
  • the samples was treated with a corona equipment yielding a hydrophilic surface prepared (primed) for the final coating of the photocatalytic T1O2 particles.
  • the photocatalytic T1O2 particles were for both samples coated with a coating bar yielding a thickness of appr. 50 g/m2.
  • the samples was dried at ambient conditions.
  • a dispersion comprising 1.25 % of titanium dioxide nanoparticles with an average particle size in the dispersions (measured by Volume with Nanotrac NPA 252) measured to 27 nm was used. Less than 10 wt% of the solvent was isopropanol and the density was 1.04 g/ml.
  • the photocatalytic T1O2 dispersion was added 0.3 ml_ of non-ionic surfactant as wetting agent per liter of photocatalytic T1O2 dispersion.
  • a polymeric product comprising : a fiber sheet 20, a polymeric layer 21 deposited onto the fiber sheet 20 and an inorganic barrier layer 24 deposited onto the polymeric layer 21.
  • Photocatalytic titanium dioxide nanoparticles 22 are deposited and thus located in/on the inorganic barrier layer 24 alternatively or in combination thereto, photocatalytic particles may be embedded in the inorganic barrier layer.
  • the inorganic barrier layer is made from a resin, such as silicone resin.
  • the polymeric product is preferably made by a process similar to what is disclosed herein.
  • the inorganic barrier layer is exposed to a corona treatment in order to generate OH-cites where e.g. T1O2 can react with to create chemical bonding between the inorganic barrier layer 24 and the
  • photocatalytic substance 22 may be used instead of flame treatment.
  • Inorganic barrier layer :
  • the inorganic barrier layer is an inorganic silicone resin with good compatibility to organic resins.
  • the inorganic barrier layer is therefore suited for adhering and making chemical bonds to an organic substrate, such as a polymer layer or a polymeric surface.
  • the inorganic barrier layer can be dissolved in different solvents.
  • the weight percentage of silicon resin in the inorganic barrier layer fluid is in the range 0-25 %, 1-10 %, preferably 5%.
  • the inorganic barrier layer may include inorganic particles. The inorganic particles is in one preferred example added to improve the scratch resistance, wear resistance, strength of the layer.
  • the inorganic particles are preferably silica particles, alumina particles,
  • the size of the inorganic particles is preferably smaller than 250 nm, 100 nm, 50 nm, 25 nm.
  • the inorganic barrier layer is applied with for example a roll, brush, spray (air, hydraulic, ultrasonic).
  • the inorganic barrier layer is preferably dried and or cured.
  • the drying and or curing could preferably be done with heat, forced heat, such as convective heating, e.g. by use of a gas flow where the gas has an elevated temperature (e.g. heated air), IR, UV.
  • the inorganic barrier layer is preferably treated such as to be primed for the TI02 to adhere to the inorganic barrier layer.
  • the priming could preferably be done with corona, plasma, flame oxidation.
  • the inorganic barrier layer is typically applied with a quantity of less than 100 g/m2, 50 g/m2, 25 g/m2 such as the final thickness of the inorganic barrier layer is less than 5,0; 2,5 ⁇ , 1.0 ⁇ ; 0.75 ⁇ ; 0.5 ⁇ ; 0.25 ⁇ .
  • the thickness of the inorganic barrier layer 24 is as little as possible with a thickness approaching a mono layer.
  • an upper limit of the inorganic barrier layer 24 is less than 100 g/m 2 (produced by use of an applicator bar of approximately 100 micro meter) with 20 wt% silicone resin in iso propanol. This typically provides 20 g/m 2 and a thickness of 20 micro meter.
  • a lower limit of the inorganic barrier layer 24 is less than : 10 g/m 2 (produced by use of an applicator bar of approximately 10 micro meter) with 2.5 wt% silicone resin in iso propanol. This typically provides a thickness of 250 nm (0.25 micro meter)
  • a lower limit of the inorganic barrier layer 24 is less than 75 nano meter.
  • the thickness of the inorganic barrier layer is less 20 micro meter, such as less than 10 micro meter, such as less than 5 micro meter, preferably less than 1 micro meter, such as less than 0.5 micro meter, preferably less than 0.25 micro meter.
  • the thickness preferably refers to the thickness of the dried and/or cured inorganic barrier layer 24.
  • inorganic barrier layer 24 is useable in connection with the present invention, it has been found that a relatively thick layer may cause mud cracking, delamination and/or other undesired effects. It is therefore preferred to make the barrier layer relatively thin. Further, as handling of the inorganic barrier layer may involve bending, rolling and other mechanical handlings, the inorganic barrier layer could advantageously be made flexible enough to withstand such mechanical handlings.
  • Example 1
  • Two different plastic foils also referred as plast foils, were produced using an 'Automatic Film Applicator', comprising a base foil with PMMA top layer and a laminated foil with MMA top layer.
  • the samples were made with a 15 ⁇ application bar.
  • a methylphenyl silicone resin was used as inorganic barrier layer using a 5 wt% silicone resin in iso propanol.
  • After application the samples were cured and dried by forced drying (2 min at 60 °C). Afterwards the samples were surface corona treated (20 W/m 2 ) until the contact angle with water was lower than 20°. Afterwards the photocatalytic dispersion was applied with a 15 ⁇ application bar.
  • the photocatalytic dispersion comprising 1.25 % of titanium dioxide nanoparticles with an average particle size in the dispersions (measured by Volume with Nanotrac NPA 252) measured to 27 nm was used. Less than 10 wt% of the solvent was isopropanol and the density was 1.04 g/ml.
  • To the photocatalytic T1O2 dispersion 0.3 mL of non-ionic surfactant as wetting agent per liter of photocatalytic T1O2 dispersion was added. The photocatalytic coating was dried for 2 min at 60 °C. After drying the samples were ready to be rolled up.
  • a pilot scale production was performed producing photocatalytic composite fagade sheets.
  • the substrate was a fibre cement based material with an organic acrylic coating.
  • the inorganic barrier layer which was a 5 % methylphenyl silicone resin.
  • the silicon resin was cured by IR and forced heated air at a temperature of 90 °C for 30 sec. at a line speed of 3-4 m/min.
  • the barrier layer was surface corona treated at 1000W 6m/min and until the contact angle with water was lower than 20°.
  • the photocatalytic dispersion was applied with a roll coater. Approximately 10g/m 2 was applied by a roll coater at a line speed of appr. 10 m/min. After application of the
  • photocatalytic dispersion the product was dried under the same conditions as before. Hereafter the products were ready to be collected and packed.
  • the photocatalytic dispersion comprising 1.25 % of titanium dioxide nanoparticles with an average particle size in the dispersions (measured by Volume with Nanotrac NPA 252) measured to 27 nm was used. Less than 10 wt% of the solvent was isopropanol and the density was 1.04 g/ml.
  • the photocatalytic T1O2 dispersion was added 0.3 ml_ of non-ionic surfactant as wetting agent per liter of photocatalytic T1O2 dispersion.
  • ISO 22197-1 test procedure The NOx degrading performance of the sample was tested according to ISO 22197-1.
  • the initial concentration of NO was 1.0 ppm and the flow of NO gas over the sample was 3 l/min.
  • the concentrations of NO, NO2 and NOx was analysed with a Horiba APNA NOx analyser model 370.
  • the test cell was purchased from an accredited institute.
  • the light intensity was 1.0 mW/cm 2 UVA measured with a PMA 2110 UVA detector and the relative humidity was kept constant at 45% ⁇ 5 %.
  • the sample sizes in the test were 49x99mm 2 .
  • EN 1297: 2004 Test Procedure The EN 1297 :2004 test weathering procedure consists of a dry cycle followed by a wet spray cycle.
  • the dry cycle is 300 min of 45 W/cm2 ⁇ 5 w/cm 2 UVA (340 nm) and a chamber temperature of 60 °C (BST).
  • the wet spray cycle is 60 min of spraying de-ionized water (max conductivity of 500 MS/m) at a flow rate of 10 ⁇ 3 l/min/m 2 with an initial temperature of the water of 25 ⁇ 5 °C.
  • the test is continued by repeating step 4 and 5 for a predetermined number of hours.
  • the data in the figure 6 shows that the inorganic barrier layer and the
  • photocatalytic treatment is a robust and durable treatment where the particles are bonded to the inorganic barrier layer and not washed off after 300 hours of accelerated ageing. From the data in Figure 6 it is statistically not possible to detect a difference in the photocatalytic activity before and after 300 hrs of accelerated weathering for all four samples.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un produit à base de polymère photocatalytique et un procédé pour produire un produit à base de polymère photocatalytique.
PCT/DK2017/050117 2016-04-13 2017-04-11 Produit à base de polymère photocatalytique et procédé pour produire un produit à base de polymère photocatalytique Ceased WO2017178031A1 (fr)

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DKPA201670228 2016-04-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115218318A (zh) * 2022-03-25 2022-10-21 广州奥松电子股份有限公司 光催化空气净化装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004021425A1 (de) * 2004-04-30 2005-11-24 Institut für Neue Materialien Gemeinnützige GmbH Verwendung photokatalytischer TiO2-Schichten zur Funktionalisierung von Substraten
US20130011684A1 (en) * 2011-07-05 2013-01-10 Valinge Photocatalytic Ab Coated wood products and method of producing coated wood products
WO2014098762A1 (fr) * 2012-12-21 2014-06-26 Välinge Photocatalytic Ab Procédé de revêtement d'un panneau de construction et un panneau de construction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004021425A1 (de) * 2004-04-30 2005-11-24 Institut für Neue Materialien Gemeinnützige GmbH Verwendung photokatalytischer TiO2-Schichten zur Funktionalisierung von Substraten
US20130011684A1 (en) * 2011-07-05 2013-01-10 Valinge Photocatalytic Ab Coated wood products and method of producing coated wood products
WO2014098762A1 (fr) * 2012-12-21 2014-06-26 Välinge Photocatalytic Ab Procédé de revêtement d'un panneau de construction et un panneau de construction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115218318A (zh) * 2022-03-25 2022-10-21 广州奥松电子股份有限公司 光催化空气净化装置

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