TW201521871A - Photocatalytic coating and method of making same - Google Patents

Abstract

The present invention is aimed at improving the adhesion of a photocatalytic material to a substrate. An embodiment of the present invention relates to a method for making a photocatalytic element comprising: providing a suspension comprising a binder and a photocatalytic material, wherein the weight ratio of the binder to the photocatalytic material is about 0.5 to 2.0 parts binder to about 1 part photocatalytic material; and applying the suspension to a substrate surface.

Description

Photocatalytic coating and method of manufacturing same

Some embodiments relate to a process for producing a substrate having a photocatalytic film containing inorganic particles.

Visible light activated photocatalysts can be used in automated cleaning, air and water purification, and many other interesting applications that typically do not have any non-renewable energy consumption after deployment. This system can be used as a photocatalyst of the available light in the environment (e.g., solar radiation, and indoor or outdoor light) to decompose pollutants (such as dyes, volatile organic compounds and NO _x). With the rapid adoption of anti-UV indoor lighting (such as LEDs and OLEDs), look for indoor applications (eg, in clean homes, public and commercial spaces, especially in restricted areas such as airplanes, public buildings, etc.) A method of deploying a visible light activated photocatalyst in indoor air is essential. In addition, antimicrobial surfaces and automatic cleaning materials can be widely used in food service, transportation, health care and hospitality sectors.

Various methods have been proposed for fixing titanium oxide. See, for example, Patent Documents 1 to 5. There is therefore a need to attach titanium oxide to the surface of the substrate.

Reference list Patent literature

PTL 1: US Patent No. 5,897,958

PTL2: US Patent No. 6,228,480

PTL3: US Patent No. 6,407,033

PTL4: US Patent No. 7,510,595

PTL5: US Reissue Patent No. RE38, 850

The present invention is directed to improving the adhesion of a photocatalytic material to a substrate.

That is, some embodiments of the present invention relate to a method for fabricating a photocatalytic element, comprising: providing a suspension comprising a binder and a photocatalytic material, wherein the weight ratio of the binder to the photocatalytic material is about 0.5 to 2.0 parts of the adhesive to about 1 part of the photocatalytic material; and the suspension is applied to the surface of the substrate.

In some embodiments, applying the suspension to the substrate can further comprise casting the suspension onto the substrate.

In some embodiments, applying the suspension to the substrate can further comprise spin coating the suspension onto the substrate at between about 500 revolutions per minute to about 3000 revolutions per minute for between about 5 seconds and about 30 seconds.

In some embodiments, the method can further comprise surface treating the surface of the substrate.

In some embodiments, the method can further comprise applying a decane coupling agent to the surface of the substrate. The decane coupling agent may be aminopropyltriethoxydecane.

In some embodiments, the method can further comprise adding a binder catalyst material to the suspension. The binder catalyst material can be D25.

In some embodiments, providing the suspension can further comprise dissolving the polyoxynoxy resin in a propylene glycol solvent. The propylene glycol solvent may be propylene glycol methyl ether acetate. Further, the polyoxynoxy resin may be a polyoxyl alkyd resin, a polyoxyl epoxy resin, a polyoxypropylene acrylic resin or a polyoxyethylene polyester resin. Further, the polyoxynoxy resin may be a polyoxymethylene polyester resin. Further, the polyoxyl polyester resin may be KR5230.

In some embodiments, the photocatalytic material may comprise a metal oxide filled with copper oxide. Compound.

In some embodiments, the photocatalytic material can comprise doped or undoped TiO ₂ .

In some embodiments, a method for making a photocatalytic element is provided, comprising: providing a solution comprising 10% KR5230 and 90% propylene glycol monomethyl ether acetate (PGMEA); at 10:1 (w/ w) binder: ratio of photocatalytic material to the solution of photocatalytic copper-filled multiphase titanium oxide material powder; pretreatment of the PET surface by corona treatment; and about 30 to about 2000 to about 2000 rpm The solution was spin coated onto the pretreated PET surface for about 60 seconds.

In some embodiments, a photocatalytic element fabricated in accordance with the above method is provided.

In some embodiments, a photocatalytic element comprising a polyoxymethylene polyester resin and a photocatalytic material, wherein the weight ratio of the resin to the photocatalytic material is between about 0.5 and about 2.0 to about 1 (0.5 to 2 parts resin to 1 part photocatalytic material). The polyoxyl polyester resin may be selected from the group consisting of KR500, KR5230, and KR5235. Further, the photocatalytic material may be selected from the group consisting of a multi-phase titanium oxide filled with a copper oxide, a Sn/C/N-doped titanium oxide filled with a copper oxide, and an unfilled titanium oxide doped.

Further, some embodiments of the present invention relate to a method for fabricating a photocatalytic element, comprising: providing a suspension comprising a binder, a photocatalytic material, a photoinitiator, and an organic solvent, wherein the binder is the photocatalytic material The weight ratio is from about 1.0 to 20 parts of binder to about 1 part of the photocatalytic material; and the suspension is applied to the surface of the substrate.

Furthermore, some embodiments of the present invention relate to a method for fabricating a photocatalytic element, comprising: providing a solution comprising a binder, a photocatalytic material, a photoinitiator, and an organic solvent; providing a binder, a photocatalytic material, and a light a suspension of an initiator and an organic solvent, wherein the weight ratio of the binder to the photocatalytic material in the suspension is about 1.0 to 20 parts of the adhesive to about 1 part of the photocatalytic material; the solution is applied to the surface of the substrate to form an intervening layer on the surface of the substrate; and the suspension is applied to the intervening layer on the surface of the substrate.

In some embodiments, applying the suspension to the substrate can further comprise casting the suspension onto the substrate.

In some embodiments, the method can further comprise surface treating the surface of the substrate. The binder may comprise an ultraviolet curable urethane resin. Further, the ultraviolet curable urethane resin may contain an urethane urethane resin.

In some embodiments, the organic solvent can be a C ₁ -C ₇ ketone.

In some embodiments, the organic solvent can be a C ₁ -C ₇ alcohol.

In some embodiments, the organic solvent may be selected from the group consisting of cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), methyl ethyl ketone (MEK), toluene, acetic acid. Ethyl ester and butyl acetate.

In some embodiments, the suspension may further comprise a dispersing agent. The dispersant may be selected from the group consisting of cationic dispersants, anionic dispersants, and nonionic dispersants.

In some embodiments, the photoinitiator can be selected from the group consisting of IRGACURE 907 and IRGACURE 2022.

In some embodiments, the photocatalytic material can comprise a metal oxide filled with a copper oxide.

In some embodiments, the photocatalytic material can comprise doped or undoped TiO ₂ .

In some embodiments, a method for fabricating a photocatalytic element is provided, comprising: providing 10% by weight of an urethane acrylate resin, less than 1.0% by weight of a photoinitiator, and 90% by weight of cyclopentanone Solution; a photocatalytic copper-filled heterogeneous titanium oxide material powder is added to the solution at a ratio of 5:1 (w/w) binder:photocatalytic material. The surface of the PET is pretreated by corona treatment; and the suspension is cast on the surface of the pretreated PET.

In some embodiments, a method for fabricating a photocatalytic element is provided, comprising: providing 10% by weight of an urethane acrylate resin, less than 1.0% by weight of a photoinitiator, and 90% by weight of cyclopentanone Solution; pre-treating the PET surface by corona treatment; casting the solution onto the pretreated PET surface to form a binder coating on the PET surface; bonding at 5:1 (w/w) Agent: The ratio of photocatalytic material will comprise 10% by weight of urethane acrylate, less than 1.0% by weight of photoinitiator, 90% by weight of cyclopentanone solution and photocatalytic copper-filled multiphase titanium oxide material powder. Provided to the suspension; and the suspension is cast onto the adhesive coating.

In some embodiments, a photocatalytic element fabricated in accordance with the above method is provided.

In some embodiments, a photocatalytic element comprising an urethane urethane resin and a photocatalytic material is provided, wherein a weight ratio of the resin to the photocatalytic material is between about 0.5 and about 10 to about 1 (0.5 to 10 parts of the urethane acrylate resin to 1 part of the photocatalytic material), preferably about 1.5 to about 10 to about 1 (1.5 to 10 parts of the urethane acrylate resin to 1 part of the photocatalytic material). The urethane acrylate resin may be selected from the group consisting of UNIDIC 17806, EBECRYL 8701, EBECRYL 8301, EBECRYL 8405, OC-3021, OC-4021, OC-4122, HC-5619, and UVHC3000. Further, the photocatalytic material may be selected from the group consisting of a multi-phase titanium oxide filled with a copper oxide, a Sn/C/N-doped titanium oxide filled with a copper oxide, and an unfilled titanium oxide doped.

According to the present invention, the adhesion of the photocatalytic material to the substrate can be improved.

8‧‧‧ surroundings

10‧‧‧Photocatalytic components

12‧‧‧Substrate

14‧‧‧Photocatalytic coating

14A‧‧‧First Photocatalytic Coating

14B‧‧‧Second photocatalytic coating

16‧‧‧Undercoat

18‧‧‧ first surface

20‧‧‧ hole

22‧‧‧ Surface

110‧‧‧Photocatalytic components

112‧‧‧Substrate

114‧‧‧Photocatalytic coating

118‧‧‧The first surface of the substrate

120‧‧‧Photocatalytic materials

122‧‧‧Binder

124‧‧‧Intervention layer

126‧‧‧ first surface of the intervention layer

Figure 1 is a schematic representation of an embodiment of the experiment described herein.

2A and 2B are schematic illustrations of embodiments of photocatalytic elements described herein.

3 is a schematic illustration of an embodiment of a photocatalytic element described herein.

4 is a schematic illustration of an embodiment of a photocatalytic element described herein.

Figure 5 is a graph showing the antibacterial (E. coli) activity of the examples (Example A) described herein.

Figure 6 is a graph showing the antibacterial (E. coli) activity of the examples (Example B) described herein.

Figure 7 is a graph showing the antibacterial (E. coli) activity of the examples (Example C) described herein.

Figure 8 is a graph showing the antibacterial (E. coli) activity of the examples (Example D) described herein.

Figure 9 is a graph showing the antibacterial (E. coli) activity of the examples (Example E) described herein.

Figure 10 shows an SEM surface and cross-sectional image of an example (Example A) on a PET substrate.

Figure 11 is a graph showing the antibacterial (E. coli) activity of the examples described herein (Examples AA to AF), photocatalysis with KR5230 as a binder (filled copper oxide (Cu _x O) multiphase TiO ₂ [87] A graph of the effectiveness of the % anatase phase TiO ₂ /13% rutile phase TiO ₂ ] coating. (Photocatalytic filling = 11.8 vol%, 21.1 vol%, and 34.8 vol%)

Figure 12 is a schematic illustration of an embodiment of the experiment described herein.

Figure 13 is a schematic illustration of an embodiment of the experiment described herein.

Figure 14 is a schematic illustration of an embodiment of a photocatalytic element described herein.

Figure 15 is a schematic illustration of an embodiment of a photocatalytic element described herein.

Figure 16 is a graph showing the antibacterial (E. coli) activity of the examples (Examples I and II) described herein.

Figure 17 is a graph showing the antibacterial (E. coli) activity of the examples (Examples 11 to 15) described herein under bright conditions.

Figure 18 is a graph showing the antibacterial (E. coli) activity of the examples (Examples 11 to 15) described herein under dark conditions.

Figure 19 is an SEM surface image of an example (Example 11) on a PET substrate.

Figure 20 is an SEM surface image of an example (Example 11) on a PET substrate.

Figure 21 is an SEM surface image of an example (Example 15) on a PET substrate.

Figure 22 is an SEM surface image of an example (Example 15) on a PET substrate.

Embodiments of the invention are described in more detail below.

The photocatalytic coating described herein may comprise nanoscale inorganic particles dispersed in a polymer resin. The polymer resin can be used as a binder to hold the nanoscale particles to the surface of the substrate to have increased adhesion and scratch resistance. The polymeric resin can be used as a binder to provide a coating with increased hardness to resist damage caused by scratching. The photocatalyst coating can be formed by applying a photocatalytic suspension made of a polymer binder and photocatalyst particles to a substrate. In an embodiment, the photocatalyst particles comprise semiconductor nanoparticles having one or more band gaps associated with absorption in the visible wavelength range. The photocatalyst particles may be doped or filled with copper oxide (for example, a plurality of Cu ¹⁺ and Cu ²⁺ oxides), and the copper oxide provides a coating for deactivating microorganisms such as bacteria or viruses, and decomposing VOCs (volatile organic compounds). Or decomposing one or more functions of the dye in the liquid as an indicator of the retention of photocatalytic activity. A plurality of coatings can be formed on the substrate to provide multiple functions integrated on one substrate.

As shown in FIG. 1, the present invention provides a method (S10) for manufacturing a photocatalytic element, comprising: providing a binder and a photocatalytic material solution, wherein the binder is bonded to the photocatalytic material in an amount of about 0.5 to 2.0 parts. The ratio (weight ratio [w/w]) of the agent to about 1 part of the photocatalytic material is supplied (S12); and the mixture is applied to the substrate (S16). Those skilled in the art will recognize that from 0.5 to 2.0 parts of the binder to one part of the photocatalytic material corresponds to from about 5% to about 35 vol% of the photocatalytic material in the coating, as calculated from the density of the photocatalytic material and the resin. . In some embodiments, 5 to 20 parts of a 10% binder (by weight) solution is provided to 1 part of the photocatalytic material (by weight). In some embodiments, the method further includes processing the surface of the substrate (S14). In some embodiments, the method further comprises drying the applied binder/photocatalytic material suspension on the surface of the substrate to remove the solvent (S18). In some embodiments The solvent is removed substantially completely.

2A shows a photocatalytic element 10 comprising a substrate 12 and a photocatalytic coating 14. In some embodiments, the undercoat layer 16 is interposed between the substrate 12 and the photocatalytic coating layer 14. In some embodiments, the primer layer comprises a decane coupling agent. In some embodiments, the undercoat layer is disposed on the first surface 18 of the substrate 12. In some embodiments, the undercoat layer can be the first portion of the substrate 12. In some embodiments, the first portion is integral with the substrate. In some embodiments, the photocatalytic coating 14 is disposed on or in contact with the undercoat layer 16. As shown in FIG. 2B, in some embodiments, the photocatalytic coating 14 is disposed on the substrate 12, in contact with the substrate 12, or as part of the substrate 12. In some embodiments, the undercoat layer can comprise the treated substrate surface 18.

In FIG. 3, a photocatalytic element 10 is illustrated that includes a substrate 12, a first photocatalytic coating 14A, and a second photocatalytic coating 14B. In some embodiments, the photocatalytic coating 14A is disposed on the substrate 12, in contact with the substrate 12, or as part of the substrate 12. In some embodiments, the second photocatalytic coating 14B is disposed on the first photocatalytic coating 14A, in contact with the first photocatalytic coating 14A, or as part of the first photocatalytic coating 14A. In some embodiments, a plurality of holes 20 are defined within the photocatalytic coating 14B to communicate the surface 22 of the photocatalytic coating 14A with the surrounding environment 8. This provides a plurality of photocatalytic layers (14A and 14B) in contact with the surrounding environment 8.

In FIG. 4, a photocatalytic element 10 is illustrated that includes a substrate 12, an undercoat layer 16, and a plurality of photocatalytic coatings (eg, a first photocatalytic coating 14A and a second photocatalytic coating 14B). In some embodiments, photocatalytic coatings 14A and 14B can be disposed on the undercoat layer 16 in contact with the undercoat layer. As previously described with respect to FIGS. 2A and 2B, in some embodiments, the first photocatalytic coating 14A and the second photocatalytic coating 14B can be disposed on the substrate 12, in contact with the substrate 12, or as part of the substrate 12. In this embodiment, both photocatalytic coatings are in direct communication or contact with the environment 8.

In some embodiments, the photocatalytic material can be comprised of, for example, titanium, tungsten, tantalum, An oxide of an element of tin, zinc or bismuth. In some embodiments, the oxide can be doped or undoped and/or filled or unfilled. In some embodiments, the oxide can have a valence band that is deeper than the valence band of the filled copper material. In some embodiments, the photocatalytic material can be a multiphase composite of photocatalytic materials. In some embodiments, the photocatalytic material can be anatase, rutile, wurtzite, spinel, perovskite, pyrochlore, garnet, zircon, and/or aluminum tialite. Phase material or a mixture thereof. Each of these options is given by its general meaning as understood by those of ordinary skill in the art. The X-ray diffraction pattern that compares a given standard and the resulting sample is one of many methods that can be used to determine if a sample contains a particular phase. Exemplary standards include by the National Institute of Standards and Technology (NIST) (Gaitherburg, MD, USA) and/or the International Centre for Diffraction Data (ICDD), a former powder diffraction standard. Their XRD spectra were provided by the Commission [JCPDS]) (Newtown Square, PA, USA).

In some embodiments, the heterogeneous photocatalytic material comprises an anatase phase and a rutile phase compound. In some embodiments, the heterogeneous photocatalytic material can be titanium oxide. In some embodiments, the anatase phase can range from 2.5% to about 97.5%, from 5% to about 95%, and/or from about 10% to about 90%; and the rutile phase can range from 97.5% to about 2.5%, 95. % to about 5% and/or about 10% to about 90%. Non-limiting examples of suitable materials include, but are not limited to, a TiO ₂ mixture sold by Evonik (Parissipany, NJ, USA) under the trade name P25 (83% anatase TiO ₂ + 17% rutile TiO ₂ ).

In some embodiments, the photocatalytic material comprises a compound having an average particle size between about 10 nm and 100 nm. In some embodiments, the average particle size can be between about 20 nm and about 60 nm.

In some embodiments, the photocatalytic material can be a filled copper oxide (copper oxide [Cu _x O], including Cu ¹⁺ and Cu ²⁺ valence atoms present in the copper oxide) as described in the following) Photocatalytic composites: U.S. Patent Application Serial No. 13/840,859, filed on Mar. U.S. Patent Application Serial No. 61/835,399, filed on Jan. 14, s., and U.S. Patent Application Serial No. 13/741, 191, filed Jan. Incorporated herein by reference in its entirety. In some embodiments, Cu ²⁺ is present more than Cu ¹⁺ (eg, Cu ^{2+ is} greater than 50%). In some embodiments, Cu ²⁺ can be about 50 From about 95% (for example, about 79%), and Cu ¹⁺ may be from about 50% to about 5% (for example, about 21%) of copper oxide. The amount of Cu ²⁺ and/or Cu ¹⁺ may be borrowed. Determined by X-ray absorption fine structure analysis (XAFS).

In some embodiments, the photocatalyst as the photocatalytic material may be an inorganic solid that absorbs ultraviolet or visible light, such as a solid inorganic semiconductor. For some materials, photocatalysis can be attributed to reactive species formed on the surface of the photocatalyst by electron holes generated in the bulk of the photocatalyst due to said absorption of electromagnetic radiation (capable of performing reduction and Oxidation). In some embodiments, the photocatalyst has a conduction band having an energy of from about 1 eV to about 0 eV, from about 0 eV to about -1 eV, or from about -1 eV to about -2 eV, as compared to a standard hydrogen electrode. Some photocatalysts can have a valence band of energy from about 3 eV to about 3.5 eV, from about 2.5 eV to about 3 eV, or from about 2 eV to about 3.5 eV, or from about 3.5 eV to about 5.0 eV, as compared to a standard hydrogen electrode. In some embodiments, the photocatalyst comprises an oxide filled with copper. Suitable copper-filled oxides are described in U.S. Patent Application Serial No. 13/840,859, filed on Mar. And U.S. Provisional Application Serial No. 61/835,399, filed on Jun. 14, 2013, which is hereby incorporated by reference. Copper-filled oxides exhibit an antibacterial effect.

Some photocatalysts can only be activated by light in the UV range (i.e., wavelengths less than 380 nm). This is because of the wide band gap (>3eV) of most semiconductors. However, in recent years, visible light photocatalysts have been synthesized by appropriately selecting materials or modifying existing photocatalysts (Asahi et al., Science, 293: 269-271, 2001, and Abe et al., Journal of the American Chemical Society, 130 (25): 7780-7781, 2008). Visible light The catalyzing agent comprises a photocatalyst that is activated by visible light (e.g., light that is typically detectable by the naked eye, such as a wavelength of at least about 380 nm). In some embodiments, in addition to the visible wavelength, the visible light photocatalyst can also be activated by UV light having a wavelength below 380 nm. Some visible light photocatalysts can have a band gap corresponding to light in the visible range, such as greater than about 1.5 eV, less than about 3.5 eV, about 1.5 eV to about 3.5 eV, about 1.7 eV to about 3.3 eV, or 1.77 eV to 3.27 eV. Bandgap. Some photocatalysts can have a band gap of from about 1.2 eV to about 6.2 eV, from about 1.2 eV to about 1.5 eV, or from about 3.5 eV to about 6.2 electron eV.

Preferably, the photocatalyst contains a metal compound such as an oxide, an oxynitride, an oxynitride or a halide, and more preferably contains a titanium compound, a tin compound or a tungsten compound.

Some photocatalysts include oxide semiconductors (such as TiO ₂ , ZnO, WO ₃ , SnO _{2 ,} etc.) and variants thereof. The expected modifications include doping and/or filling. Other materials such as mis-oxides (SrTiO ₃ , BiVO ₄ ) and some sulfides (CdS, ZnS), nitrides (GaN), and some nitrogen oxides (such as ZnO: GaN) may also exhibit photocatalytic properties. Photocatalysts can be synthesized by those skilled in the art by various methods including solid state reaction, combustion, solvothermal synthesis, flame pyrolysis, plasma synthesis, chemical vapor deposition, physical vapor deposition, ball milling, and the like. High energy grinding.

The average oxidation number or form charge of titanium in the titanium compound is preferably from +1 to +6, more preferably from +2 to +4, still more preferably from +1 to +3. The average oxidation number or form charge of tin in the tin compound is preferably from +2 to +8, more preferably from +1 to +6, still more preferably from +1 to +4. The average oxidation number or form charge of tungsten in the tungsten compound is preferably +1 to +8, more preferably +1 to +6, still more preferably +1 to +4.

More specifically, the photocatalyst preferably contains at least one selected from the group consisting of titanium oxide (IV) (TiO ₂ ), tin (IV) oxide (SnO ₂ ), and tungsten (III) oxide (W ₂ O _{3 ).} ), tungsten (IV) oxide (WO ₂ ) and tungsten (VI) oxide (WO ₃ ). The titanium oxide (IV) (TiO ₂ ) is preferably anatase-type titanium oxide (IV) (TiO ₂ ).

Incidentally, in the present specification, the phrase "photocatalyst contains (or contains) tungsten oxide (VI) (WO ₃ )" includes not only photocatalytic pure tungsten oxide (VI) (WO ₃ ) but also includes The photocatalyst contains a case of tungsten (VI) oxide (WO ₃ ) doped with another element or compound. (The same explanation applies to photocatalysts and co-catalysts other than tungsten oxide.)

In particular, preferably, the photocatalyst contains tungsten (VI) oxide (WO ₃ ) because tungsten oxide (VI) makes it possible to form a photocatalytic element which exhibits sufficient photoactivity under visible light.

In some embodiments, the individual Ti or W compounds can be individual oxides, oxycarbides, oxynitrides, oxyhalides, halides, salts, doped or filled compounds. In some embodiments, the respective Ti or W compound may be TiO ₂ , WO ₃ or Ti(O,C,N) ₂ :Sn, such as Ti(O,C,N) ₂ :Sn, where Ti:Sn The molar ratio is from about 90:10 to about 80:20, from about 85:15 to about 90:10 or about 87:13. A suitable Ti(O,C,N) ₂ :Sn compound is described in U.S. Patent Application Serial No. 13/738,243, filed on Jan. This application is incorporated herein by reference in its entirety. In some embodiments, the respective Ti or W compound can be a nanopowder, a nanoparticle, and or a layer comprising the same. In some embodiments, examples of the photocatalyst may include: a metal oxide such as tungsten (III) oxide (W ₂ O ₃ ), tungsten (IV) oxide (WO ₂ ), tungsten (VI) oxide (WO ₃ ), Zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), tin (II) oxide (SnO), tin (IV) oxide (SnO ₂ ), tin (VI) oxide (SnO ₃ ), cerium (II) oxide (CeO) , cerium (IV) oxide (CeO ₂ ), strontium titanate (SrTiO ₃ ), barium titanate (BaTiO ₃ ), indium (III) oxide (In ₂ O ₃ ), bismuth vanadate (BiVO ₄ ), iron oxide ( III) (Fe ₂ O ₃ ), bismuth (III) oxide (Bi ₂ O ₃ ), copper (I) oxide (Cu ₂ O), copper (II) oxide (CuO), Cu _x O, potassium citrate (KTaO) ₃ ) and potassium citrate (KNbO ₃ ); metal sulfides such as cadmium sulfide (CdS), zinc sulfide (ZnS) and indium sulfide (InS); metal selenides such as cadmium selenate (CdSeO ₄ ) and zinc selenide (ZnSe); and metal nitrides such as gallium nitride (GaN). The Cu _x O is described in U.S. Patent Application Serial No. 13/840,859, the disclosure of which is hereby incorporated by reference. In some embodiments, the photocatalyst comprises TiO ₂ . In some embodiments, the photocatalyst comprises anatase and/or rutile titanium oxide (IV) (TiO ₂ ). In some embodiments, the photocatalyst does not include TiO _x . In some embodiments, the photocatalyst does not include TiO ₂ . In some embodiments, the photocatalyst comprises WO _3.

Any suitable amount of photocatalyst can be used. In some embodiments, the photocatalyst material is from about 0.01 mol% to 100 mol% or at least about 0.01 mol% and less than 100 mol% of the composition. In some embodiments, the photocatalytic material is from about 20 mole percent to about 80 mole percent, from about 30 mole percent to about 70 mole percent, from about 40 mole percent to about 60 mole percent, or about 50% by mole.

Photocatalysts such as TiO ₂ and WO ₃ compounds (eg, nanopowders) can be prepared by a number of different methods including plasma synthesis, such as thermal plasma (DC and including RF inductively coupled plasma (RF-) ICP)), solvothermal, solid state reaction, pyrolysis (spray and flame) and combustion. A radio frequency inductively coupled plasma (eg, thermal) method as described in U.S. Patent No. 8,003,563, the disclosure of which is hereby incorporated by reference in its entirety, may be Precursor in liquid or solid form. Therefore, the RF inductively coupled plasma process is preferred. For example, when preparing a WO ₃ nanopowder, a liquid dispersion of ammonium metatungstate in water (5 wt% to 20 wt% solids in water) can be sprayed into the plasma volume using a two-fluid atomizer. Preferably, the amount of precursor is up to about 20% by weight solids in water. The plasma can be operated with argon, nitrogen and/or oxygen at a plate power of about 25 kW. The particles formed by the condensed vapor from the plasma can then be collected on the filter. In some embodiments, the particle surface area ranges from about 1 m ² /g to about 500 m ² /g, from about 15 m ² /g to 30 m ² /g, or about 20 m ² /g, as measured using BET. In some embodiments, the obtained WO ₃ can be heated from about 200 ° C to about 700 ° C or from about 300 ° C to about 500 ° C.

In some embodiments, the photocatalyst can be doped with at least one naturally occurring element (eg, a non-inert gas element) to improve the activity of the photocatalyst. This element can be referred to as a "dopant." The doped element (dopant) can be provided as a precursor that is usually added during the synthesis. The doped element (dopant) can be an element incorporated into the crystal lattice of the Ti or W compound (eg, substituted or otherwise included in the interstices within the crystal at defined locations within the crystal lattice). In some embodiments, the dopant may be selected from one of more elements including: alkali metals such as lithium (Li), sodium (Na), potassium (K), and cesium (Cs); alkaline earth Metals such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba); noble metals such as gold (Au), silver (Ag), platinum (Pt), rhodium (Rh), iridium (Ir) , palladium (Pd) and ruthenium (Ru); transition metals such as iron (Fe), copper (Cu), zinc (Zn), vanadium (V), titanium (Ti) (for example, for W-based compounds), tungsten (W) (for example, for Ti-based compounds), manganese (Mn), Mo, zirconium (Zr), niobium (Nb), chromium (Cr), cobalt (Co), cerium (Ce), and nickel (Ni); Lanthanide and actinide metals; halogen; Group III elements (Dmitri Mendeleev/Lothar Meyer-style modern periodic table of elements arranged in order of increasing atomic number), including B, Al, Ga, In, and Tl; Elements, including Ca, Si, Ge, Sn; Group V elements such as N, P, As, Bi; and Group VI elements such as S and Se. In some embodiments, the photocatalyst may be doped with at least one element selected from the group consisting of C, N, S, F, Sn, Zn, Mn, Al, Se, Nb, Ni, Zr, Ce, and Fe. In some embodiments, the photocatalyst can be self-doped, for example, Ti ³⁺ replaces Ti ⁴⁺ in the TiO ₂ matrix. The details of a suitable doped photocatalytic material are shown in U.S. Provisional Patent Application Serial No. 61/587,889, which is incorporated herein by reference. In the present specification, a photocatalyst doped with a dopant may be referred to as a "doped photocatalyst".

The term "doping" means that an arbitrarily selected element (dopant) is added to the host compound crystal within a range that does not substantially change the basic crystal structure of the photocatalyst. Whether or not the photocatalyst is doped can be confirmed by, for example, peak shift in XPS (X-ray photoelectron spectroscopy). The method for forming the doped photocatalyst is not particularly limited, and may be, for example, a sol-gel method, a solid phase reaction method, and an ion implantation method.

When the photocatalyst is a doped photocatalyst, the molar ratio of the host compound (compound to be doped) to the dopant in the photocatalyst is not particularly limited, and is preferably 99.9:0.1 to 80:20, more Preferably, it is 99.9: 0.1 to 85:15, further preferably 99.9: 0.1 to 87:13.

Preferably, the doped photocatalyst is doped with at least one selected from the group consisting of: Carbon (C), nitrogen (N), sulfur (S), fluorine (F), tin (Sn), zinc (Zn), manganese (Mn), aluminum (Al), selenium (Se), niobium (Nb), Nickel (Ni), zirconium (Zr), cerium (Ce) and iron (Fe).

The photocatalyst can be p-type or n-type. The p-type photocatalyst can be obtained, for example, by doping a photocatalyst with a high-valent element such as, for example, arsenic (As). The n-type photocatalyst can be obtained, for example, by doping a photocatalyst with a low-valent element such as, for example, boron (B).

In some embodiments, the photocatalytic material may comprise one or more of the following: an n-type UV photocatalytic material, an n-type visible light photocatalytic material, a p-type UV photocatalytic material, and/or a p-type visible light catalytic material. In some embodiments, the n-type visible bandgap semiconductor can be viewed as WO ₃ , Ti(O, C, N) ₂ :Sn or CeO ₂ . In some embodiments, the n-type UV photocatalytic material may be CeO ₂ , TiO ₂ , SnO ₂ , SrTiO ₃ , ATaO ₃ , ANbO _{3 ,} etc.; A = alkali metal ions, wherein A may be Ca, Ba, and/or Sr. In some embodiments, the p-type visible bandgap semiconductor can be viewed as SiC, CuMO ₂ , M=Al, Cr. In some embodiments, the p-type UV photocatalytic material may be ZnIrO ₂ , ZnRhO ₂ , CuO, SnO, NiO, Mn ₂ O ₃ , Co ₃ O _{4 ,} and/or Fe ₂ O ₃ .

In some embodiments, the photocatalyst can be filled with at least one metal. The filled element can be obtained by impregnation (Liu, M., Qiu, X., Miyauchi, M and Hashimoto, K. Cu(II) Oxide Amorphous Nanoclusters Grafted Ti ³⁺ Self-Doped TiO ₂ published in 2011; An Efficient Visible Light Photocatalyst (Chemistry of Materials), photoreduction (Abe et al., Journal of the American Chemical Society, 130 (25): 7780-7781, 2008) and sputtered The post-synthesis method is provided. The filling of the metal on the photocatalyst can be carried out as described in US Patent Publication No. US 2008/0241542, which is incorporated herein by reference in its entirety. From the precious element. In some embodiments, the filled element may be selected from at least one precious element, an oxide, and/or a hydroxide. In some embodiments, the valuable element may be selected from the group consisting of Au, Ag, Pt, Pd, Ir , Ru, Rh or an oxide thereof and/or a hydroxide. In some embodiments, the filler element is selected from the group consisting of transition metals, oxides and/or hydroxides thereof. In some embodiments, the filler elements are Selected from Fe and Cu and Ni or Oxides and hydroxides. In some embodiments, the filler element can be selected from the group consisting of at least one transition metal and at least one noble metal element or individual oxides and hydroxides thereof. In some embodiments, Suitable filled metal oxides are described in U.S. Patent Application Serial No. 13/840,859, filed on Mar. The manner of reference is incorporated.

In some embodiments, the photocatalyst preferably has a refractive index (R1) of from 1.0 to 4.0, more preferably from 1.0 to 3.0, particularly preferably from 1.5 to 2.5, at a wavelength of 589 nm. When the refractive index (R1) of the photocatalyst falls within the range of 1.0 to 4.0, it becomes easier to reduce the refractive index difference from the cocatalyst, and thus it becomes easier to form a translucent layer. It should be noted that the refractive index value of the photocatalyst is a measurement value obtained by an Abbe refractometer according to the "solid sample measurement method" specified by JIS K 0062.

The shape of the photocatalyst is not particularly limited, and the photocatalyst is preferably in the form of particles. Many kinds of photocatalysts are not sufficiently soluble in a solvent. With the particle shape, the photocatalyst can be dispersed in a dispersion medium to produce a dispersion liquid, which can then be used to easily form a layer by coating and drying.

When the photocatalyst is in the form of particles, the average particle size of the photocatalyst is not particularly limited, and is preferably from 5 nm to 1,000 nm, more preferably from 5 nm to 100 nm, still more preferably from 5 nm to 30 nm. When the average particle size of the photocatalyst exceeds 1,000 nm, the total surface area of the photocatalyst becomes small and may not exhibit sufficient photocatalytic activity. On the other hand, when the average particle size of the photocatalyst is lowered to 5 nm or less, particle aggregation tends to occur, and the translucency of the layer containing the photocatalyst may be impaired.

It should be noted that the average particle size of the photocatalyst is a volume-based cumulative distribution diameter (D50) of the photocatalyst particles dispersed in an arbitrary dispersion liquid as determined by dynamic light scattering frequency analysis (FFT-heterodyne method).

The cocatalyst is a substance that accelerates the photocatalytic activity of the photocatalyst. The cocatalyst can be used in combination with the photocatalyst as needed. The cocatalyst can be a cocatalyst that exhibits or does not exhibit photocatalytic activity. In cooperation with the photocatalyst, the cocatalyst can increase the reaction rate of the photocatalyst by 1.2 times or more, preferably 1.5 times or more, further preferably 2.0 times or more, and particularly preferably 3.0, compared with the reaction rate when the photocatalyst is used alone. Multiple or more. The reaction rate of the photocatalyst can be based, for example, on the rate of decomposition of acetaldehyde, a volatile organic compound (VOC). In this document as a whole, the cocatalyst can also be generally referred to as a T binder.

Specifically, the photocatalyst, either alone or with a cocatalyst mixed with or supported by a photocatalyst, is placed in a closed space containing a certain amount of compressed air and acetaldehyde (calibration gas), and is visible light (wavelength 455 nm). Irradiation intensity 200 mW/cm ² ) Irradiation for 1 hour. Next, the acetaldehyde concentration in the closed space before and after the irradiation was compared to calculate a multiple of the increase in the reaction rate of the photocatalyst. For example, when the concentration of acetaldehyde in the enclosed space containing only the photocatalyst becomes 60 ppm after irradiation of the enclosed space containing 80 ppm of acetaldehyde (that is, 20 ppm of acetaldehyde has been decomposed), when the light is filled The acetaldehyde concentration in the closed space of the catalyst and the cocatalyst (mixed with or supported on the photocatalyst) becomes 20 ppm after irradiation with a closed space containing 80 ppm of acetaldehyde (that is, 60 ppm of acetaldehyde has been decomposed), The rate of aldehyde decomposition can be said to have increased by a factor of 3 (a 3-fold increase in photocatalytic activity).

A co-catalyst can be a compound or semiconductor that can be reduced by electron transfer from a conduction band of a photocatalyst. For example, the cocatalyst can have a conduction band with a lower energy than the conduction band of the photocatalyst, or the cocatalyst can have a lowest unoccupied molecular orbital domain with a lower energy than the conduction band of the photocatalyst. When terms such as "lower energy" and "higher energy" are used to compare a semiconductor band or molecular orbital with another band or molecular orbital, it means that the electron is moving to a lower energy band or molecular orbital domain. When energy is lost, and electrons gain energy when they are transferred to a higher energy molecular orbital zone.

The cocatalyst can be simply mixed with the photocatalyst or can be supported on the photocatalyst. In the present specification, a photocatalyst supporting a cocatalyst is referred to as a "supported photocatalyst". As used herein, the term "support" refers to a state in which a substance other than a photocatalyst adheres to a surface of a photocatalyst. This state of adhesion can be observed, for example, by scanning electron microscopy. The method for forming the supported photocatalyst is not particularly limited, and may be, for example, a dipping method, a photoreduction method, or a sputtering. Supported photocatalysts can be formed by the methods described in, for example, U.S. Patent Application Serial No. 2008/0241542. The cocatalyst can be doped with a dopant. The co-catalyst doped with a dopant will be referred to as a doped co-catalyst. The compounds and elements used to dope the cocatalyst are as exemplified above in connection with the photocatalyst.

It is believed that some metal oxides as co-catalysts are capable of reducing O ₂ . For example, it is believed that CeO ₂ can reduce O ₂ gas by electron transfer. In this case, the letter Ce ³⁺ transfers electrons to O ₂ and the result is converted to Ce ⁴⁺ . In the photocatalyst composition, the photocatalyst can transfer electrons to CeO ₂ to convert Ce ⁴⁺ to Ce ³⁺ , and Ce ³⁺ can then reduce O ₂ . Ce ³⁺ may also exist as a result of an equilibrium process involving CeO ₂ and O ₂ and superoxide radical ions (O ₂ ^- ). The O ₂ and superoxide radical ions in this equilibrium process can be adsorbed to the surface of the solid CeO ₂ or present in the atmosphere. C _e ³⁺ may also be present as a result of oxidation and reduction reactions of the ruthenium species in different oxidation states which may be intentionally added or present as impurities.

Xianxin, some co-catalysts may be able to achieve multiple electron reduction of oxygen. For example, some cocatalysts can achieve two electrons, four electrons, six electrons, and/or up to eight electron reductions of oxygen. The co-catalyst stores electrons in the conduction band of the cocatalyst, which can then be used for oxygen reduction.

Some cocatalysts may be capable of converting atmospheric O ₂ to superoxide radical ions. For example, CeO _{2 is} capable of converting atmospheric oxygen into superoxide radical ions. It is believed that some of the balance and/or electron transfer processes described above may contribute to this property of CeO ₂ . This conversion can occur under a variety of conditions, such as environmental conditions, including, for example, normal atmospheric oxygen concentrations, such as from about 10% to about 30%, from about 15% to about 25%, or from about 20% oxygen. Concentration; ambient temperature, such as from about 0 ° C to about 1000 ° C, from about 0 ° C to about 100 ° C, from about 10 ° C to about 50 ° C or from about 20 ° C to about 30 ° C; and pressure, such as from about 0.5 to about 2 atm, about 0.8 Atm to about 1.2 atm or about 1 atm. This conversion can also occur at elevated or reduced temperatures, pressures or oxygen concentrations. Other materials that may be capable of reducing O ₂ or converting atmospheric O ₂ to superoxide radical ions include various other materials such as Ce _x Zr _y O ₂ (where x/y = 0.99-0.01), BaYMn ₂ O _5+δ , And CeO ₂ doped with a lanthanide element, including Ce _x Zr _y La _z O ₂ , Ce _x Zr _y Pr _z O ₂ and Ce _x Sm _y O ₂ .

Some cocatalysts may have a valence band or a highest occupied molecular orbital domain with a higher energy band than the photocatalyst. This allows the holes in the valence band of the photocatalyst to be transferred to the highest occupied molecular orbital or valence band of the cocatalyst. The valence band of the cocatalyst or the hole in the highest occupied molecular orbital domain can then oxidize H ₂ O or OH ^- to OH. . For example, if WO _{3 is} selected as the photocatalyst, examples of the cocatalyst may include anatase TiO ₂ , SrTiO ₃ , KTaO ₃ , SiC, or KNbO ₃ .

In some embodiments, the cocatalyst can be inorganic. In some embodiments, the inorganic cocatalyst can be a binder. In some embodiments, the cocatalyst can be an oxide, such as a metal dioxide, including CeO ₂ , TiO _{2 ,} or the like. A suitable co-catalyst is described in U.S. Patent Application Serial No. 13/738,243, filed on Jan. <RTIgt; In this article.

In some embodiments, examples of the cocatalyst may include copper (I) oxide (Cu ₂ O), copper (II) oxide (CuO), molybdenum (VI) oxide (MoO ₃ ), manganese (III) oxide (Mn _{2 )} O ₃ ), cerium (III) oxide (Y ₂ O ₃ ), cerium (III) oxide (Gd ₂ O ₃ ), anatase and/or rutile titanium oxide (IV) (TiO ₂ ), titanic acid SrTiO ₃ , potassium silicate ( KTaO ₃ ), lanthanum carbide (SiC), potassium citrate (KNbO ₃ ), yttrium oxide (SiO ₂ ), tin (IV) oxide (SnO ₂ ), aluminum oxide (III) (Al ₂ O ₃ ), zirconia (ZrO ₂ ), iron (III) oxide (Fe ₂ O ₃ ), iron (II, III) (Fe ₃ O ₄ ), nickel (II) oxide (NiO), oxidation铌(V)(Nb ₂ O ₅ ), indium oxide (In ₂ O ₅ ), lanthanum oxide (Ta ₂ O ₅ ), cerium (II) oxide (CeO), cerium (IV) oxide (CeO ₂ ), A _r X _t O _s (wherein A is a rare earth element, X is a combination of elements other than rare earth elements or elements other than rare earth elements, r is 1 to 2, t is 0 to 3, and s is 2 to 3), three Hydrated ammonium phosphomolybdate ((NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ]), 12-tungstophosphoric acid (PW ₁₂ O ₄₀ ), tungsten telluride (H ₄ [SiW ₁₂ O ₄₀ ]), phosphomolybdic acid (12MoO ₃ . H ₃ PO ₄ ) and cerium-zirconium composite oxide (Ce _x Zr _y O ₂ ) (y/x = 0.001 to 0.999). In some embodiments, the cocatalyst comprises In ₂ O ₅ , Ta ₂ O ₅ , anatase TiO ₂ , rutile TiO ₂ , a combination of anatase and rutile TiO ₂ , or CeO ₂ . In some embodiments, the cocatalyst comprises TiO ₂ . In some embodiments, the cocatalyst comprises anatase TiO ₂ . In some embodiments, the cocatalyst does not include Cr ₂ O ₃ , CeO ₂ , Al ₂ O _{3 ,} or SiO ₂ . In some embodiments, the cocatalyst does not include Cr ₂ O ₃ . In some embodiments, the cocatalyst does not include CeO ₂ . In some embodiments, the cocatalyst does not include Al ₂ O ₃ . In some embodiments, the cocatalyst does not include SiO ₂ .

In some embodiments, the cocatalyst can be Re _r E _t O _s , Re _r E _t O or Re _r E _t O ₂ , wherein Re is a rare earth element, a combination of E-type elements or elements, and O is oxygen; r is from 1 to 2, such as from about 1 to about 1.5 or from about 1.5 to about 2; s is from 2 to 3, such as from about 2 or about 3; and t is from 0 to 3, such as from about 0.01 to about 1, from about 1 to about 2 or about 2 to about 3. In some embodiments, the cocatalyst can be Re _r O _s , where Re can be a rare earth metal, and r can be greater than or equal to 1 and less than or equal to 2, or can be between 1 and 2, and s can be greater than or equal to 2 and less than or equal to 3, or may be between 2 and 3. Examples of suitable rare earth elements include lanthanum, cerium and lanthanides and actinides. The lanthanide element includes an element having an atomic number of 57 to 71. The lanthanide element includes an element having an atomic number of 89 to 103. In some embodiments, the cocatalyst can be Ce _x Zr _y O ₂ with y/x ratio = 0.001 to 0.999.

The cocatalyst preferably contains at least one selected from the group consisting of ruthenium compounds, copper compounds, potassium compounds, ruthenium compounds, ruthenium compounds, ruthenium compounds, and titanium compounds. More preferably, the cocatalyst contains a ruthenium compound or a copper compound. The average oxidation number or form charge of the ruthenium compound is preferably from +2 to +4. The average oxidation number or form charge of the copper compound is preferably from +1 to +2. In some embodiments, the cocatalyst can be CeO _a (a 2). In some embodiments, the cocatalyst can be CeO. In some embodiments, the cocatalyst can be cerium oxide (CeO ₂ ).

In some embodiments, the cocatalyst contains cerium oxide, more preferably cerium (IV) oxide (CeO ₂ ). This embodiment is suitable for the decomposition of volatile organic compounds (VOCs). When the cocatalyst contains cerium (IV) oxide (CeO ₂ ), it is preferred to dope cerium (IV), preferably tin (Sn). In tin (Sn) doped cerium oxide (IV) (CeO ₂ :Sn), tin (Sn) accounts for preferably 1 mol% to 50 mol%, more preferably 1.5 mol% to 10 mol of the total cocatalyst (CeO ₂ :Sn). %, further preferably from 1.5 mol% to 10 mol%, particularly preferably from 1.5 mol% to 4.5 mol%.

In some embodiments, the photocatalyst can be WO ₃ and the cocatalyst can be CeO _a (a 2).

In some embodiments, the cocatalyst can be a Keggin unit, such as ammonium phosphomolybdate ((NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ]), 12-phosphoric acid, tungstic acid, and phosphomolybdic acid. The overall stability of the Keggin unit allows the metal in the anion to be easily reduced. Depending on the solvent, the acidity of the solution and the charge on the a-Keggin anion, the anion can be reversibly reduced in one or more electron steps.

While not wishing to be bound by theory, it is believed the present invention, CeO ₂ may be useful because of the relative position of the band of such material in combination with tungsten oxide. Furthermore, it is worth noting that the refractive index of CeO ₂ is substantially the same as that of tungsten oxide, from about 90% to about 110%. In another embodiment, from about 95% to about 105%. In some embodiments, the high transparency of the photocatalytic composition can provide a composition/layer/element having a clarity greater than about 50%, 60%, 65%, and/or 70%. The low scattering loss caused by the matching refractive index directly contributes to the production of a transparent composition.

In some embodiments, the cocatalyst contains copper oxide, more preferably copper (I) (Cu ₂ O) and/or copper (II) oxide (CuO). This embodiment is suitable for antimicrobial applications. When the cocatalyst contains copper (I) oxide (Cu ₂ O) and/or copper (II) oxide (CuO), preferably copper (I) oxide (Cu ₂ O) and/or copper (II) oxide ( CuO) is supported on the photocatalyst.

The shape of the cocatalyst is not particularly limited and is described for the photocatalyst. For the same reason, the shape of the cocatalyst is preferably a particle. When the shape of the cocatalyst is a particle, the average particle size of the cocatalyst is not particularly limited, and is preferably from 1 nm to 1,000 nm, more preferably from 1 nm to 100 nm, still more preferably from 1 nm to 30 nm.

The cocatalyst has a refractive index (R2) of preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, particularly preferably from 1.5 to 2.5, at a wavelength of 589 nm. When the refractive index (R2) of the cocatalyst falls within the range of 1.0 to 4.0, it becomes easier to reduce the refractive index difference from the photocatalyst and form an ideal translucent layer.

Examples of the above photocatalyst include a UV-responsive photocatalyst exhibiting photocatalytic activity only for ultraviolet light having a wavelength of less than 380 nm, and a visible light-responsive photocatalyst exhibiting photocatalytic activity also for visible light having a wavelength of 380 nm to 780 nm. In the present invention, the photocatalyst may be a UV-responsive photocatalyst or a visible light-responsive photocatalyst, and is preferably a visible light-responsive photocatalyst. The visible light responsive photocatalyst exhibits some photoactivity to visible light even in the absence of a cocatalyst. In cooperation with the cocatalyst, the visible light responsive photocatalyst can thus exhibit even higher photoactivity to visible light. When the photocatalyst is a visible light responsive photocatalyst, the band gap is, for example, 1.5 eV to 3.5 eV, preferably 1.7 eV to 3.3 eV, more preferably 1.77 eV to 3.27 eV. It should be noted that even when the photocatalyst is a UV-responsive photocatalyst, the photocatalyst can exhibit visible light responsiveness in a particular photocatalyst and co-catalyst combination.

In some embodiments, the photocatalyst is preferably a photocatalyst exhibiting visible light responsiveness. The visible light responsive photocatalyst can also exhibit photocatalytic activity for light sources such as fluorescent lamps and LEDs that emit visible light, and can avoid the use of ultraviolet light that is harmful to the human body.

The photocatalyst may be used singly or as a mixture of two or more. When two or more photocatalysts are used as a mixture, one of the photocatalysts can serve as a cocatalyst for the other photocatalyst. The cocatalyst may also be used singly or as a mixture of two or more.

When a photocatalyst and a cocatalyst are used in combination, any useful ratio of the photocatalyst to the cocatalyst can be used. The ratio of the total photocatalyst to the total catalyst (mole ratio) is preferably 99.5: 0.5 to 16.7: 83.3, more preferably 99.5: 0.5 to 20: 80, further preferably 99.5: 0.5 to 50: 50.

When the photocatalyst content is less than the lower limit of the aforementioned range, the cocatalyst will exceed the amount of the photocatalyst and may not exhibit sufficient photocatalytic activity. On the other hand, when the photocatalyst content exceeds the upper limit of the above range, the amount of the cocatalyst will be insufficient relative to the amount of the photocatalyst, and sufficient photocatalytic activity may not be exhibited.

In the present invention, when a photocatalyst and a cocatalyst are used in combination, the combination of the photocatalyst and the cocatalyst is not particularly limited.

In some embodiments, the photocatalytic material may comprise tungsten oxide and a rare earth oxide in a molar ratio of from about 0.5:1 to 2:1 or about 1:1 (tungsten oxide: rare earth oxide). In some embodiments, the rare earth oxide is cerium oxide (CeO ₂ ). In some embodiments, the photocatalytic composition can include WO ₃ and CeO ₂ having from about 1:5 to about 5:1, from about 1:3 to about 3:1, from about 1:2 to about 2:1, or about Mohr ratio of 1:1 (WO ₃ :CeO ₂ ).

In a preferred embodiment, the photocatalyst contains tungsten (VI) oxide (WO ₃ ) and the cocatalyst contains cerium oxide (IY) (CeO ₂ ). It is excellent in visible light responsiveness and photocatalytic activity and decomposes volatile organic compounds by using tungsten (VI) oxide (WO ₃ ) as a photocatalyst and cerium (IV) oxide (CeO ₂ ) as a cocatalyst. (VOC) is also a particularly good photocatalytic component.

In another preferred embodiment, the photocatalyst contains titanium oxide (IV) (TiO ₂ ) or tin (IV) oxide (SnO ₂ ), and the cocatalyst contains copper (I) oxide (Cu ₂ O) and/or oxidation. Copper (II) (CuO). In this case, the cocatalyst containing copper (I) oxide (Cu ₂ O) and/or copper (II) oxide (CuO) is preferably supported to contain titanium oxide (IV) (TiO ₂ ) or tin oxide (IV). On the photocatalyst of (SnO ₂ ). It is possible to use titanium oxide (IV) (TiO ₂ ) or tin (IV) oxide (SnO ₂ ) as a photocatalyst and copper (I) (Cu ₂ O) and/or copper (II) oxide (CuO) as The cocatalyst forms a photocatalytic element which is excellent in visible light responsiveness and photocatalytic activity and is also particularly excellent in antimicrobial properties. In the present specification, the co-catalyst is supported on a Cu _x O type cocatalyst supported on the photocatalyst TiO ₂ photocatalyst by Cu _x O-TiO ₂ is represented. Similarly, the cocatalyst-supporting type photocatalyst supporting the cocatalyst Cu _x O on the photocatalyst SnO ₂ can be represented by Cu _x O-SnO ₂ . Here, "Cu _x O" is intended to mean a state in which two types of copper oxide CuO (X = 1; copper (II) oxide) and Cu ₂ O (X = 2; copper (I) oxide) are present.

In some embodiments, the binder material can be a polyoxynoxy resin. In some embodiments, the polyoxynoxy resin can be, for example, a polyoxyl alkyd resin, a polyoxyxa epoxy resin, a polyoxypropylene acrylic resin, or a polyoxymethylene polyester resin. In some embodiments, the polyoxyxene resin is a polyoxymethylene polyester resin. In some embodiments, a suitable polyoxymethylene polyester resin may be a commercially available product, for example, KR5230 and/or KR5235 (Shin-Etsu Chemical Co., Ltd, Tokyo, Japan). KR5230 can be from about 4% to about 44% or from about 6% to about 46% or from about 8% to about 48% or from about 10% to about 50% or from about 12% to about 52% or from about 14% to about 54. Poly orthopolyoxyl resin having a poly ortho-oxygen content of about 1% or about 16% to about 56% or the like.

In some embodiments, the binder material can be a decane compound. In some embodiments, the decane compound can be at least one of the following: tetrachlorodecane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, four N-butoxy decane and tetra-butoxy decane; trichlorodecane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, Three second butoxy decane, fluorotrichloro decane, fluorotrimethoxy decane, fluorotriethoxy decane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, Fluorinated tributoxybutane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyl Tri-n-butoxy decane, methyl tri-tert-butoxy decane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxynonane, 2-(three Fluoromethyl)ethyltriethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2-(three Fluoromethyl) Tri-n-butoxy decane, 2-(trifluoromethyl)ethyltri-n-butoxy decane, 2-(perfluoro-n-hexyl)ethyltrichlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethyl Oxydecane, 2- (Perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-hexyl)ethyltriisopropoxydecane, 2- (Perfluoro-n-hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-hexyl)ethyltri-t-butoxydecane, 2-(perfluoro-n-octyl)ethyltrichloromethane, 2- (Perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-propoxydecane, 2 -(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-octyl)ethyltri-second Oxydecane, hydroxymethyltrichlorodecane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane, hydroxymethyltri-n-propoxydecane, hydroxymethyltriisopropoxydecane, hydroxymethyl Tri-n-butoxy decane, hydroxymethyl three-butoxy decane, 3-(methyl) propylene methoxy propyl trichloro decane, 3-(methyl) propylene methoxy propyl trimethoxy decane , 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)propenyloxypropyltri-n-propoxydecane, 3- (Meth) propylene methoxy propyl triisopropoxy decane, 3-(methyl) propylene methoxy propyl tri-n-butoxy decane, 3-(methyl) propylene methoxy propyl tri Dibutoxydecane, 3-mercaptopropyltrichlorodecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxydecane, 3- Mercaptopropyl triisopropoxy decane, 3-mercaptopropyl tri-n-butoxy decane, 3-mercaptopropyl tri-tert-butoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl Triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-tert-butoxy decane, allyl trichloro decane, Allyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy decane, allyl triisopropoxy decane, allyl tri-n-butoxy decane, allyl Three second butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl triisopropoxy decane, phenyl a compound of the formula (1), such as methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, a methyl 2-butoxy decane and a phenyl tri-butoxy decane; Di-n-propoxy decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di-n-butoxy fluorene Alkane, dimethyl dichlorodecane, dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl Di-n-butoxy decane, dimethyldi-second butoxy decane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-positive Octyl)ethyl]dimethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl) Di-n-propoxy decane, (methyl)[2-(perfluoro-n-octyl)ethyl]diisopropoxy decane, (methyl)[2-(perfluoro-n-octyl)ethyl] Di-n-butoxy decane, (methyl) [2-(perfluoro-n-octyl)ethyl] bis-butoxy decane, (methyl) (γ-glycidoxypropyl) dichloro decane, (methyl)(γ-glycidoxypropyl)dimethoxydecane, (methyl)(γ-glycidoxypropyl)diethoxydecane, (methyl)(γ-glycidoxy Propyl) di-n-propoxy decane, (methyl)) (γ-glycidoxypropyl) diisopropoxy decane, (methyl) (γ-glycidoxypropyl) di-n-butyl Oxydecane, (methyl) (gamma-glycoside) Oxypropyl)di-butoxybutane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl) ( 3-mercaptopropyl)diethoxydecane, (methyl)(3-mercaptopropyl)di-n-propoxydecane, (methyl)(3-mercaptopropyl)diisopropoxydecane, (A (3-mercaptopropyl)di-n-butoxydecane, (methyl)(3-mercaptopropyl)di-butoxybutane, (methyl)(vinyl)dichlorodecane, (methyl (vinyl)dimethoxydecane, (meth)(vinyl)diethoxydecane, (methyl)(vinyl)di-n-propoxydecane, (methyl)(vinyl) diiso Propoxy decane, (methyl) (vinyl) di-n-butoxy decane, (methyl) (vinyl) di-butoxy decane, divinyl dichloro decane, divinyl dimethoxy Decane, divinyldiethoxydecane, divinyldi-n-propoxydecane, divinyldiisopropoxydecane, divinyldi-n-butoxydecane, divinyldi-butoxy Decane, diphenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, diphenyldi-n-propoxy a compound of formula (1), such as chlorodimethyl, of decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, and diphenyl bis second butoxy decane; Decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, methoxy Trimethyl decane, ethoxy trimethyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, second butoxy trimethyl decane, Third butoxy trimethyl decane, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (Chloro) (methyl) diphenyl decane, (methoxy) (methyl) diphenyl decane and (ethoxy) (methyl) diphenyl decane.

Here, the formula (1) mentioned above is shown below.

(R ² ) _m -Si-(Y ² ) _4-m (1)

(wherein Y ² is a chlorine atom, a bromine atom, an iodine atom, or a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, and the R ² -based hydrogen atom, a fluorine atom, having 1 to 20 carbon atoms a straight chain, branched or cyclic alkyl group, a linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, An aryl group of 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and m is an integer of 0 to 3).

In some embodiments, the decane compound can be at least one of the following: tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, 3- (A) Acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane,allyltrimethyl Oxy decane, allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimethyl dimethoxy decane, and dimethyl diethoxy decane.

Commercially available products of partial condensates of decane compounds include, for example, (Shin-Etsu Silicones KK) KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X- 21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22- 170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X- 40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218 and KR9706; (Showa Denko KK) glass resin (Glass Resin); (Toray Dow Corning Silicone Co., Ltd.) SH804 , SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416 and SR2420; (Nippon Unicar Co., Ltd.) FZ3711 and FZ3722; (Chisso Corporation) DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PDS-0332, PDS- 1615, PDS-9931 and XMS-5025; (Mitsubishi Chemical Corporation) methyl citrate MS51 and methyl decanoate MS56; (Colcoat Co., Ltd.) ethyl citrate 28, ethyl citrate 40 and hydrazine Acid ethyl ester 48; and (Showa Denko KK) GR100, GR650, GR908 and GR950, (Wacker Chemie AG) SMP100. In the present embodiment, the above decane compound and a partial condensate thereof may be used singly or in combination of two or more kinds.

In some embodiments, a binder catalyst can be added to the binder/photocatalytic suspension. In some embodiments, the binder catalyst can be a titanium alkoxide. A suitable example may be a titanium alkoxide (D25) commercially available from Shin-Etsu Chemical Co., Ltd.

In some embodiments, a photocatalytic suspension comprising a photocatalytic material, a binder, and an organic solvent is provided. In some embodiments, the binder can be dissolved in an organic solvent. In some embodiments, the photocatalytic material is substantially insoluble in the organic solvent. In some embodiments, the organic solvent can be, for example, a hydrocarbon, a ketone, an ester, an ether, or an alcohol.

Examples of the above hydrocarbons include toluene and hydrazine; examples of the above ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone; examples of the above esters include ethyl acetate Ester, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methyl Oxybutyl butyl acetate and ethyl lactate; examples of the above ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran and dioxane; and examples of the above alcohol include 1-hexanol, 4-methyl Base-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono-n-propyl ether . In some embodiments, providing the binder and the photocatalytic material suspension further comprises dissolving the polyfluorene-modified polyester resin in a propylene glycol solvent. In some embodiments, the propylene glycol solvent can be propylene glycol methyl ether acetate. In some embodiments, the propylene glycol solvent is propylene glycol methyl ether acetate.

These organic solvents may be used singly or in combination of two or more kinds.

In some embodiments, the binder-to-photocatalytic material is provided in a ratio of from about 0.5 to about 2.0 parts by weight of the binder (by weight) to about 1 part by weight of the photocatalytic material. Those skilled in the art will recognize that a 1:5 weight ratio can be about 34.8 vol%; and a 1:20 wt% can be about 11.8 vol%. In some embodiments, the binder-to-photocatalytic material is provided in a ratio of from about 0.5 to about 2.0 parts of the binder to about 1 part of the photocatalytic material (by weight). In some embodiments, from about 8 to 12 parts by weight of binder (10% solution binder) to about 1 part of photocatalytic material (eg, about 0.5 parts of binder to about 1 part of photocatalytic material) Provides a binder to the photocatalytic material. Although not wishing to be bound by theory, having a ratio of less than 0.5 parts of binder to about 1 part of the photocatalytic material can result in insufficient adhesion of the photocatalytic material to the surface of the substrate. Those skilled in the art will recognize that suitable methods for assessing adhesion can be by, but not limited to, ASTM D3359. Although not wishing to be bound by theory, having a ratio of greater than 2.0 parts of binder to 1.0 part of photocatalytic material (% by weight) may result in insufficient amount of photocatalytic material to be exposed outside of the surface of the coating.

In some embodiments, a photocatalytic/adhesive material is applied to the substrate. In some embodiments, the substrate can be a thermoplastic polymer. In some embodiments, the substrate can be a thermoset polymer. In some embodiments, the substrate can be any of the following: polyethylene, polypropylene, polyester, polystyrene, polyamido, polyimine, polyfluorene, polyether oxime (PES), Polyacrylate, polyacrylonitrile, polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), ethylene vinyl acetate (EVA), polyvinylidene fluoride (PVDF), polyetheretherketone (PEEK), and/or mixtures thereof. In some embodiments, the substrate can comprise a polyester. In some embodiments, the polyester can be, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN).

In some embodiments, the substrate can comprise a thermoset resin. In some embodiments, the thermosetting resin may comprise a phenolic resin. In some embodiments, the thermosetting resin may comprise polyoxybenzylidene glycol anhydride (bakelite), epoxy/glass fiber, epoxy/carbon fiber, and any fiber reinforced plastic material. In some embodiments, the epoxy-glass fiber composite can be in the form of a stethoscope diaphragm (eg, a commercially available embodiment sold by Littman [3M, Minneapolis, MN]).

In some embodiments, the substrate comprises a polymeric film that is subjected to a pretreatment to increase adhesion between the coating and the substrate. In some embodiments, the pretreated film and or substrate is chemically treated, corona treated, or heat treated to increase adhesion of the coating to the substrate. Commercially available products of suitable chemically treated films include, but are not limited to, 3SAB/3SAC; 3LD4; 4407/4507; 2SABN/2SACN (Mitsubishi Polyester Films, Greer, SC, USA). In some embodiments, the substrate is pretreated with a coupling agent to promote adhesion between the polymer binder and the substrate. In some embodiments, the coupling agent can be any of the previously listed coupling agents. In some embodiments, the coupling agent can be aminopropyl triethoxy decane, allyl trimethoxy decane, (3-aminopropyl) triethoxy decane, 3-aminopropyl (diethoxy) Methyl decane, (3-amino)trimethoxydecylaminopropyltriethoxydecane (APTES). Suitable amounts of coupling agents are described in "A Study of Adhesion of Silicon Dioxide on Polymeric Substrates for Optoelectronic Applications" (Optoelectronic Devices & Properties, ed., Sergiyuenko, Oleg. InTech Europe, Rijeka, Croatia (2011), Chapter 2, 23-40 pages, 26). In some embodiments, applying the mixture to the substrate further comprises spin coating the adhesive-photocatalytic material solution onto the substrate at about 500 revolutions per minute to about 3000 revolutions per minute for about 5 seconds to about 30 seconds. between. In one embodiment, the spin coating can be about 1200 RPM for about 20 seconds.

In some embodiments, applying the mixture to the substrate further comprises casting the mixture on the substrate. A suitable casting procedure is described in U.S. Patent No. 8,283,843 issued toK. In some embodiments, the blade gap can be between 0.5 mils to about 50 mils, between about 2.0 mils to about 35 mils; or between about 3.5 mils to about 20 mils. In some embodiments, the photocatalytic coating can be formed by coating a photocatalytic suspension on a substrate with a wound laboratory rod (Paul N. Gardner Inc.) having a wire size in the range of 0.003 Å to 0.020 。.

In some embodiments, the method further comprises processing the surface of the substrate. In some embodiments, the treatment of the surface further comprises adding additional adhesion material to the surface of the substrate and/or to the photocatalytic layer, and/or placing an additional layer of adhesion material between the surface of the substrate and the photocatalytic layer. In some embodiments, the additional layer can be an undercoat layer between the substrate and the photocatalytic coating. In some embodiments, the primer layer is disposed on or in contact with the surface of the substrate. In some embodiments, the undercoat layer comprises an organic solvent and a decane coupling agent. In some embodiments, the decane coupling agent can include any of the following: amine propyl triethoxy decane, allyl trimethoxy decane, (3-aminopropyl) triethoxy decane, 3-aminopropyl(diethoxy)methylnonane, (3-amino)trimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxylate Baseline, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropene醯oxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(Amino B) 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxy Decane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxy Alkoxy hydrochloride, 3-ureido-propyl triethoxy Silane, 3-mercaptopropionic Propylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxydecylpropyl)tetrasulfide and/or 3-isocyanatepropyltriethoxydecane. In some embodiments, the coupling agent can be amine propyl triethoxy decane (APTES).

In some embodiments, the surface treatment may be by, but not limited to, chemical treatment (eg, acid treatment, alkali treatment, solvent treatment of the surface), ozone treatment, corona treatment, and/or heat treatment of the substrate surface to render the coating Adhesion to the substrate increases. The surface treatment of the substrate is also applied by using sulfuric acid (10 wt% to 60 wt%). Suitable chemically treated films include corona-treated polyester films. In some embodiments, the photocatalytic material comprises Cu _x O that is packed onto the multiphase titanium oxide, for example, P25, available from Evonik. In some embodiments, the photocatalytic material can be any or all of Ti:Sn(C,N,O) ₂ , Cu _x O, P25, SnO ₂ .

In some embodiments, the method comprises drying the binder/photocatalytic suspension on the surface of the substrate at a time and temperature sufficient to remove substantially all of the solvent. In some embodiments, the drying is performed at a temperature for a period of time to partially cure the adhesive without deforming the substrate. For example, in one embodiment, a PET substrate having a photocatalytic coating thereon can be dried at 110 ° C for about 1 hour in an ambient atmosphere.

In some embodiments, a method for fabricating a photocatalytic element comprises: providing a KR-5230 (10 wt%) / PGMEA (90 wt%) solution; and using a 10: 1 (w/w) binder: photocatalytic ratio to light Catalyzing the Cu _x O/heterogeneous TiO ₂ mixed powder to the solution; pretreating the PET surface by corona treatment; and spin coating the solution onto the pretreated PET surface at about 20 to 80 rps for about 30 to 60 seconds.

In some embodiments, the heterogeneous TiO ₂ comprises anatase phase TiO ₂ and rutile phase TiO ₂ . In some embodiments, the heterogeneous TiO ₂ comprises from about 50% to about 90% anatase phase TiO ₂ and from about 50% to about 10% rutile phase TiO ₂ . In some embodiments, the heterogeneous TiO ₂ comprises, for example, about 83% anatase phase TiO ₂ available from Evonik and about 17% rutile phase TiO ₂ (P25).

In some embodiments, the photocatalytic element can be fabricated according to the methods described above. In some embodiments, the photocatalytic element comprises a polyoxymethylene polyester resin and a photocatalytic material, wherein the ratio of resin to photocatalytic material is between about 0.5 and about 2.0 to about 1 (eg, 1:2). In some embodiments, the polyoxymethylene polyester resin is selected from the group consisting of KR500, KR5230, and KR5235. In some embodiments, the photocatalytic material can be selected from the previously described oxides that are doped or undoped, filled or unfilled. In some embodiments, the photocatalytic material may be filled with copper oxide (Cu _x O) of the multi-phase titanium oxide (e.g., P25), filled with copper oxide (Cu _x O) of Sn / C / N-doped titanium oxide (Ti :Sn(CNO) ₂ ) and/or unfilled Ti:Sn(C,N,O) ₂ .

In some embodiments, the nominal thickness of the plurality of photocatalytic materials disposed in or on the coated surface can be measured by a quartz crystal microbalance that measures the mass deposited thereon, and can be about 0.0001 nm to about 2 nm or from about 0.001 nm to about 0.75 nm. In some embodiments, the photocatalytic coating comprises a binder matrix and a photocatalytic material. In some embodiments, the photocatalytic coating can be a discontinuous layer that defines pores or voids between islands of photocatalytic material.

In some embodiments, the nominal thickness of the coating on the substrate can be between about 0.01 [mu]m and about 1000 [mu]m (1 mm). The nominal thickness can be measured by a stylus surface profiler (Dektek). In some embodiments, the photocatalytic coating can be a discontinuous layer that defines pores or voids between islands of photocatalytic material (see, eg, Figure 10). In some embodiments, the plurality of photocatalytic nanomaterials can have a total mass of from about 1 ng to about 500 ng, from about 10 ng to about 100 ng, or from about 20 ng to about 60 ng, for an area per square centimeter of the surface of the luminescent layer.

In some embodiments, a method for fabricating a photocatalytic element is provided, the method comprising providing a suspension comprising a binder, a photocatalytic material, a photoinitiator, and an organic solvent, wherein the weight ratio of the binder to the photocatalytic material is about 1.0 to 20 parts of the binder to about 1 part of the photocatalytic material; and applying the suspension to the first surface. In some embodiments, the first surface can be a substrate surface. In some embodiments, the first surface can be the surface of at least one intervening layer. In some embodiments, the at least one intervening layer is disposed on the substrate. In some In embodiments, the intervening layer can comprise a binder. In some embodiments, the binder is an organic binder. In some embodiments, the binder can be an organic polymer. In some embodiments, the intervening layer can further comprise a photoinitiator and/or an organic solvent.

In some embodiments, a method for fabricating a photocatalytic element is provided, the method comprising providing a suspension comprising a binder, a photocatalytic material, a photoinitiator, and an organic solvent, wherein the weight ratio of the binder to the photocatalytic material is about 1.0 to 20 parts of the binder to about 1 part of the photocatalytic material; and the suspension is applied to the surface of the substrate.

In some embodiments, a method for fabricating a photocatalytic element is provided, the method comprising: providing a solution comprising a binder, a photocatalytic material, a photoinitiator, and an organic solvent; providing a binder, a photocatalytic material, a photoinitiator And a suspension of the organic solvent, wherein the weight ratio of the binder to the photocatalytic material is from about 1.0 to 20 parts of the binder to about 1 part of the photocatalytic material; the solution is applied to the surface of the substrate to form an intervening layer on the surface of the substrate ( Such as, for example, a binder coating; and applying the suspension to the intervening layer (such as, for example, a binder coating) on the surface of the substrate.

As shown in FIG. 12, the present invention provides a method (S10') for manufacturing a photocatalytic element, comprising: providing a binder and a photocatalytic material solution, wherein the binder and the photocatalytic material are about 1.0 to 20.0 parts. The ratio (weight ratio [w/w]) of the binder to about 1 part of the photocatalytic material is provided (S12'). In some embodiments, 1 to 20 parts of a 10% binder (by weight) solution is provided to 1 part of the photocatalytic material (by weight). In some embodiments, the method further includes processing the surface of the substrate (S14'). In some embodiments, the method comprises applying the suspension to the substrate surface (S16'). In some embodiments, the method includes heating the applied binder/photocatalytic material suspension on the surface of the substrate to remove solvent (S18'). In some embodiments, the method comprises curing the applied binder/photocatalytic material suspension (S20') on the surface of the substrate.

As shown in FIG. 13, the present invention provides a method (S110) for manufacturing a photocatalytic element, which may include providing a binder solution (S112). In some embodiments, the method can include For the adhesive and the photocatalytic material suspension, wherein the binder and the photocatalytic material may provide (S114) a ratio (weight ratio [w/w]) of about 1.0 to 20.0 parts of the binder to about 1 part of the photocatalytic material. In some embodiments, 1 to 20 parts of a 10% binder (by weight) solution is provided to 1 part of the photocatalytic material (by weight). In some embodiments, the method can include processing the substrate surface (S116). In some embodiments, the method can include applying an intervening layer to the substrate surface (S118). In some embodiments, the intervening layer can be a layer comprising a binder. In some embodiments, the binder in the intervening layer is the same as the binder in the photocatalytic suspension. In some embodiments, the method can include heating the applied adhesive solution on the surface of the substrate and/or the applied adhesive/photocatalytic material suspension on the surface of the intervening layer to remove the solvent (S120). In some embodiments, the method comprises curing the binder solution on the surface of the substrate and/or the applied binder/photocatalytic material suspension on the surface of the intervening layer (S122). In some embodiments, the intervening layer can be cured prior to the addition of the photocatalytic suspension. In some embodiments, the intervening layer and the photocatalytic suspension can be cured simultaneously/together.

As shown in FIG. 14, a photocatalytic element 110 comprising a substrate 112 and a photocatalytic coating 114 is shown. In some embodiments, the photocatalytic coating is disposed on the first surface 118 of the substrate 112, in contact with the first surface 118 of the substrate 112, or as part of the first surface 118 of the substrate 112. In some embodiments, the substrate 112 can include a processed substrate surface 118. In some embodiments, the photocatalytic coating 114 includes a photocatalytic material 120 disposed in the binder 122 and/or on the binder 122. In some embodiments, a sufficient amount of photocatalytic material 120 is exposed on the surface of the photocatalytic coating to provide the desired antimicrobial effect.

15 shows a photocatalytic element 110 that includes a substrate 112, a photocatalytic coating 114, and an intervening layer 124. In some embodiments, the intervening layer 124 is disposed on the first surface 118 of the substrate 112, in contact with the first surface 118 of the substrate 112, or as part of the first surface 118 of the substrate 112. In some embodiments, the photocatalytic coating is disposed on the first surface 126 of the intervening layer 124, in contact with the first surface 126 of the intervening layer 124, or is the first surface 126 of the intervening layer 124. portion. In some embodiments, the adhesive, photoinitiator, and/or solvent of the intervening layer can be the same as the photocatalytic coating. In some embodiments, the substrate 112 can include a processed substrate surface 118. In some embodiments, the photocatalytic coating 114 includes a photocatalytic material 120 disposed in the binder 122 and/or on the binder 122. In some embodiments, a sufficient amount of photocatalytic material 120 is exposed on the surface of the photocatalytic coating to provide the desired antimicrobial effect.

In some embodiments, a photocatalytic suspension is provided comprising at least one photocatalytic material, at least one binder, at least one photoinitiator, and at least one organic solvent. In some embodiments, a binder solution is provided comprising at least one binder, at least one photoinitiator, and at least one organic solvent.

In some embodiments, the photocatalytic material can be a photocatalytic material as described above.

In some embodiments, the binder material can be an organic binder/material. In some embodiments, the binder material can be an organic polymer. In some embodiments, the binder material can be a UV curable resin. In some embodiments, the UV curable resin can be a urethane resin. In some embodiments, the UV curable resin does not include ruthenium. In some embodiments, the urethane resin can be a urethane acrylic resin. In some embodiments, the urethane resin can be an urethane urethane resin. In some embodiments, the urethane acrylate resin comprises at least 2, at least 3, and/or at least 5 propylene groups per molecule. In some embodiments, suitable urethane resins can be commercially available products, for example, UNIDIC 17-806 (80% by mass non-volatile content; DIC International (USA), LLC, Parsippany, NJ, USA) Polyfunctional urethane amide); Ebecryl 8701 (aliphatic urethane triacrylate), Ebecryl 8301-R (aliphatic urethane hexaacrylate), Ebecryl 8405 (aliphatic amine group) Formate tetraacrylate) (Allnex USA, Smyrna, GA, USA), OC-3021, OC-4021, OC-4122 (Dymax Oligomers and Coatings, Torrington, CT, USA); HC-5619 (Addison Clearwave Coatings, Inc., St. Charles, IL, USA); and Silfort UVHC3000 (Momentive Performance Materials, Inc., Albany, NY, USA).

In some embodiments, the adhesion is provided in a ratio of from about 1.0 to about 20.0 parts of binder (% by weight), preferably from about 1.5 to about 10.0 parts of binder (% by weight) to about 1 part by weight of photocatalytic material. Agent for photocatalytic materials. Those skilled in the art will recognize that 1:5 wt% can be about 34.8 vol%; and 1:20 wt% can be about 11.8 vol%. In some embodiments, the binder to photocatalytic material is provided in a ratio (by weight) of from about 1.0 to 20.0 parts of binder to about 1 part of the photocatalytic material. In some embodiments, the binder to photocatalytic material is provided at a ratio (by weight) of about 1.7, 2.5, 5.0, and/or 10.0 parts of binder to about 1 part of the photocatalytic material. In some embodiments, the ratio of about 1 to about 12 parts of the photocatalytic material (for example, about 5 parts of the binder to about 1 part of the photocatalytic material) is about 1.5 to 12 parts of the binder (10% of the binder in the solution). Weight gauge) to provide a binder to the photocatalytic material. Although not wishing to be bound by theory, having a ratio of less than 1.0 part binder to about 1 part photocatalytic material can result in insufficient adhesion of the photocatalytic material to the surface of the substrate. Those skilled in the art will recognize that suitable methods for assessing adhesion can be by, but not limited to, ASTM D3359. Although not wishing to be bound by theory, having a ratio (% by weight) of more than 20.0 parts of binder to 1.0 part of the photocatalytic material may result in an insufficient amount of photocatalytic material exposed outside the surface of the coating.

In some embodiments, the photocatalytic suspension further comprises a dispersing agent. In some embodiments, the dispersing agent can be a cationic, anionic, nonionic dispersing agent. In some embodiments, suitable dispersing agents can be commercially available products, for example, Additol XL 203 (cationic dispersant, Allnex USA, Smyrna, GA, USA), Additol XL 251 (anionic dispersant, Allnex USA, Smyrna, GA, US), Additol VWX 6208/60 (polymerized nonionic dispersant, Allnex USA, Smyrna, GA, USA) and Flowlen G700 (mainly polycarboxylic acid, molecular weight M _w = 230, KYOEISHA CHEMICAL Co., LTD, Osaka, JP). In some embodiments, a suitable dispersant can be Disperbyk-110 (copolymer with acid groups) and/or Disperbyk-118 (straight chain copolymer with different polar affinity groups) (BYK USA, Inc., Wallingford, CT, USA).

In some embodiments, the photoinitiator can be alpha ketone, bis-decyl phosphine (BAPO), alpha ketone, and/or combinations and/or mixtures thereof. In some embodiments, a suitable photoinitiator can be 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (IRGACURE 907), Phosphine oxide (phenylbis(2,4,6-trimethylbenzylidene)[IRGACURE 819]) and/or 2-hydroxy-2-methyl-1-phenyl-1-propanone [DAROCUR 1173] . In some embodiments, suitable photoinitiators can be commercially available products, for example, IRGACURE 907 and/or IRGACURE 2022 (20 wt% IRGACURE 819/80% DAROCUR 1173).

In some embodiments, the binder can be dissolved in an organic solvent. In some embodiments, the photocatalytic material is substantially insoluble in the organic solvent. In some embodiments, the organic solvent can be, for example, a hydrocarbon, a ketone, an ester, an ether, or an alcohol.

Examples of the above hydrocarbons, ketones, esters, ethers and alcohols may be each as mentioned above. In some embodiments, the organic solvent may be a C ₁ -C ₇ alcohols. In some embodiments, the organic solvent can be a C ₁ -C ₇ ketone. In some embodiments, the organic solvent may be cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), methyl ethyl ketone (MEK), toluene, ethyl acetate. And / or butyl acetate. In some embodiments, providing the binder and the photocatalytic material suspension further comprises dissolving the urethane resin in a cyclopentanone solvent. These organic solvents may be used singly or in combination of two or more kinds.

In some embodiments, a photocatalytic/adhesive material can be applied to the first surface. In some embodiments, a photocatalytic/adhesive material can be applied to the surface of at least one of the intervening layers. In some embodiments, the intervening layer can comprise any or all of the foregoing materials of the photocatalytic/adhesive suspension other than the photocatalytic material, such as binders, solvents, photoinitiators, and the like, as described earlier. In some embodiments, the intervening layer and the photocatalytic adhesive layer can comprise the same and/or different materials. In some embodiments, the photocatalytic/adhesive material can be applied to the surface of the substrate. In some embodiments, the substrate can be a thermoplastic polymer. In some embodiments, the substrate can be a thermoset polymer. In some embodiments, the substrate can be any of the following: polyethylene, polypropylene, polyester, polystyrene, polyamine, polyphthalamide Amine, polyfluorene, polyether oxime (PES), polyacrylate, polyacrylonitrile, polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC) and/or mixtures thereof. In some embodiments, the substrate can comprise a polyester. In some embodiments, the polyester can be, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN).

In some embodiments, the substrate can comprise a thermoset polymer. In some embodiments, the thermosetting resin may comprise a phenolic resin. In some embodiments, the thermosetting resin may comprise polyoxybenzylidene glycol anhydride (bakelite), epoxy/carbon fibers, and any fiber reinforced plastic sheet. In some embodiments, the epoxy fiberglass composite can be in the form of a stethoscope diaphragm (eg, a commercially available embodiment sold by Littman [3M, Minneapolis, MN]).

In some embodiments, the substrate can comprise a polymeric film that is subjected to a pretreatment to increase adhesion between the coating and the substrate. In some embodiments, the pretreated film and or substrate is chemically treated, corona treated, or heat treated to increase adhesion of the coating to the substrate. Commercially available products of suitable chemically treated films include, but are not limited to, 3SAB/3SAC; 3LD4; 4407/4507; 2SABN/2SACN (Mitsubishi Polyester films, Greer, SC, USA). In some embodiments, the substrate is pretreated with a coupling agent to promote adhesion between the polymer binder and the substrate. In some embodiments, the coupling agent can be amine propyl triethoxy decane, allyl trimethoxy decane, (3-aminopropyl) triethoxy decane, 3-aminopropyl (diethoxy) ) methyl decane and / or (3-amino) trimethoxy decane.

In some embodiments, applying the mixture to the intervening layer and/or the substrate further comprises spin coating the adhesive-photocatalytic material solution onto the substrate at about 500 revolutions per minute to about 3000 revolutions per minute for about 5 seconds to about 30 seconds. Between seconds. In one embodiment, the spin coating can be about 1200 rpm for about 20 seconds.

In some embodiments, applying the mixture to the intervening layer and/or the substrate further comprises casting the mixture on the substrate. A suitable casting procedure has been mentioned above.

In some embodiments, the method further comprises treating the surface of the substrate to increase adhesion of the coating to the substrate. In some embodiments, the surface treatment may be by, but not limited to, chemical treatment (eg, acid treatment, alkali treatment, solvent treatment of the surface), ozone treatment, corona treatment, and/or heat treatment of the substrate surface to render the coating Adhesion to the substrate increases. Suitable chemically treated films include corona-treated polyester films. In some embodiments, the photocatalytic material comprises Cu _x O that is filled onto the P25 mixed phase photocatalytic material. In some embodiments, the photocatalytic material can be any or all of Ti:Sn(C,N,O) ₂ , Cu _x O, P25, SnO ₂ .

In some embodiments, the method comprises drying the binder/photocatalytic suspension and/or the intervening layer on the surface of the substrate at a time and temperature sufficient to remove substantially all of the solvent. In some embodiments, the drying is performed at a temperature for a period of time to partially cure the adhesive without deforming the substrate. In some embodiments, the intervening layer is partially cured prior to applying the photocatalytic/adhesive suspension to it. In some embodiments, the intervening layer is substantially completely cured prior to applying the photocatalytic/adhesive suspension to it. For example, in one embodiment, a PET substrate having a photocatalytic coating thereon can be dried at 90 ° C for about 2 minutes in an ambient atmosphere.

In some embodiments, the method comprises curing the adhesive/photocatalytic suspension and/or the intervening layer on the surface of the substrate with UV radiation sufficient to cure the suspension. In some embodiments, the method comprises curing the intervening layer on the surface of the substrate with UV radiation sufficient to cure the intervening layer. In some embodiments, the curing is performed at a UV intensity and time that partially cures the adhesive but does not degrade the UV curable material. In certain embodiments, UV having an energy of 0.2 to 20 J/cm ² and a wavelength in the range of 100 to 400 mn, preferably 200 to 400 nm, can be used to crosslink and cure the adhesive/photocatalytic suspension on the surface of the substrate. liquid. For example, in one embodiment, the UV energy is from about 0.5 J/cm ² to about 1.5 J/cm ² . This UV can be applied by using an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp or the like. For example, in one embodiment, a PET substrate having a urethane binder/photocatalyst/photoinitiator composite coating thereon can be irradiated at about 25 mW/cm ² for about 5 minutes. For example, in another embodiment, a PET substrate having a urethane binder/photocatalyst/photoinitiator composite coating thereon can be irradiated at about 225 mW/cm ² for about 5 minutes. For example, the substrate can be illuminated with a Loctite® Zeta® 7411 UV Flood Curing system or a Dymax UV conveyor system.

In some embodiments, a method for making a photocatalytic element comprises: providing an urethane urethane resin (eg, UNIDEC 17 806) (10% by weight) / organic solvent (cyclopentanone) (by weight) 90%) / 0.24wt% photoinitiator (IRGACURE 907) solution; photocatalytic Cu _x O / heterogeneous TiO ₂ mixed powder was added to the solution at a ratio of 5 to 1 (w/w) binder: photocatalytic material The surface of the PET is pretreated by corona treatment; the solution/suspension is cast onto the surface of the pretreated PET; and the adhesive/photocatalytic solution/suspension on the surface of the PET is cured. In some embodiments, a dispersant is added to the binder/solvent/photoinitiator solution/suspension. In some embodiments, the casting solution is cured on the surface of the pretreated PET.

In some embodiments, the heterogeneous TiO ₂ can be each of the materials described above.

In some embodiments, the photocatalytic element can be fabricated according to the methods described above. In some embodiments, the photocatalytic element comprises an urethane urethane resin and a photocatalytic material, wherein the ratio of resin to photocatalytic material is between about 1.0 and about 20.0 to about 1, for example, 20 parts of resin: one part Photocatalytic material. In some embodiments, the urethane acrylate resin may be selected from the group consisting of UNIDIC 17806, EBECRYL 8701, EBECRYL 8301, EBECRYL 8405, OC-3021, OC-4021, OC-4122, HC-5619, and/or UVHC3000. In some embodiments, the photocatalytic material can be selected from the previously described oxides that are doped or undoped, filled or unfilled. In some embodiments, the photocatalytic material can be filled with copper (Cu _x O) P25, filled with copper (Cu _x O) Ti:Sn(CNO) ₂ and/or unfilled with Ti:Sn(C,N,O) ₂ .

In some embodiments, the nominal thickness of the plurality of photocatalytic materials disposed in or on the coated surface can be quantified by a quartz crystal microbalance that measures the mass deposited thereon It can range from about 0.0001 nm to about 2 nm or from about 0.001 nm to about 0.75 nm. In some embodiments, the photocatalytic coating comprises a binder matrix and a photocatalytic material. In some embodiments, the photocatalytic coating can be a discontinuous layer that defines pores or voids between islands of photocatalytic material.

In some embodiments, the plurality of photocatalytic nanomaterials can have a total mass of from about 1 ng to about 500 ng, from about 10 ng to about 100 ng, or from about 20 ng to about 60 ng, for an area per square centimeter of the surface of the luminescent layer.

In some embodiments, the photocatalytic coating can have a thickness of between about 100 nm to about 10 microns. In some embodiments in which the catalytic layer is disposed on the surface of the substrate, the photocatalytic coating can have a thickness of between about 100 nm to about 10 microns.

In some embodiments in which the photocatalytic material/adhesive layer is used in combination with the adhesive layer, the adhesive layer is substantially free of photocatalytic material, and the intervening adhesive layer is disposed between the photocatalytic material/adhesive and the substrate. The catalyzed/adhesive layer can be thinner. In some embodiments, the photocatalytic/adhesive layer can be between about 50 nm, 75 nm, 100 nm to about 250 nm, 300 nm, 400 nm, and/or about 500 nm.

In some embodiments, the photocatalytic coating is characterized by about at least 35%, at least 45%, at least 55%, at least 65%, at least 75%, at least 80%, at least 90%, at least 95%, at least 97% or At least 99% adhesive adhesion. In some embodiments, greater than 65% (0B); between about 35% to about 65% (1B); between about 15% and 35% (2B); between about 5% and 15% ( 3B); less than about 5% (4B); and substantially no photocatalytic material is removed from the thin film coating (5B). The term adhesive refers to the percentage of coating remaining on the substrate after the standard tape removal test method for measuring adhesion. One method of determining adhesion is by the procedure described in ASTM-D3359. In some embodiments, the layer is characterized by a hardness test of at least 2H, at least 3H, at least 4H. One method of determining surface hardness (scratch resistance) is by the procedure described in ASTM-3363.

Instance

Embodiments of the photocatalytic elements described herein improve adhesion of the photocatalytic material to the substrate. The benefits are further illustrated by the following examples, which are intended to be illustrative of the embodiments of the invention, but are not intended to limit the scope or the basic principles.

Example 1 (P-CAT (Cu _x O/TiO ₂ :Sn) coating on PET substrate)

A commercially available PET (polybutylene terephthalate) film (Eplastics Inc. San Diego, CA USA) having a thickness of about 120 μm was used as a substrate for the photocatalytic coating. The substrate was cut into pieces having a size of 7.5 cm by 5 cm. The cut PET substrate was cleaned in the order of soap and water, acetone and methanol, and then dried.

By mixing modified polyoxyl polyether resin (sold by ShinEtsu Silicones, JAPAN under the trade name KR5230 or "KR-5230") and PGMEA (propylene glycol monomethyl ether acetate, reagent >99.5%, Sigma-Aldrich) A binder solution containing 10% by weight of a polyfluorene-modified polyester resin was obtained. The mixing was carried out with a planetary centrifugal mixer (THINKY AR-310) at about 2000 rpm for 2 minutes for mixing, followed by about 2200 rpm for about 1 minute for defoaming.

To prepare a coating suspension, one part by weight of IiSn(CNO) ₂ photocatalytic powder and 10 parts by weight of a binder solution (10% by weight of polyfluorene-modified polyester resin dissolved in PGMEA) KR-5230)) mixed. Photocatalytic powders are prepared as described in the following: US Patent Application No. 13/840,859, filed on March 15, 2013; and US Provisional Application No. 61/835,399, filed on Jun. 14, 2013; U.S. Patent Application Serial No. 13/741, 191, filed on Aug. 1, the entire disclosure of which is hereby incorporated by reference. The photocatalytic catalyst (P catalyst) powder comprises titanium oxide filled with copper oxide doped with carbon, nitrogen and tin to increase light absorption in the visible range. The nominal copper content in the P catalyst was 1 wt%. 1 gm of the photocatalytic powder was dispersed in a binder solution (about 10 gm, 10% solution) by holding the glass bottle containing the mixture in the sonication bath for about one hour. The resulting suspension was passed through a coaxial filter with a stainless steel screen having an opening of 30 microns.

Prior to coating, the cleaned PET substrate is subjected to a corona discharge treatment to increase the hydrophilicity of the substrate surface to achieve good wettability of the coating suspension. A corona treatment apparatus (TEWC-4AX, KASUGA DENKI Inc. JAPAN) was used by performing two scans at a discharge power of 100 W and a scan speed of 0.5 m/sec.

Coating of the substrate (Ex-1) was performed on the prepared PET substrate by spin coating at about 1200 rpm for about 20 seconds using a spin coater (SCS 6800 series, Specialty Coating System).

Additional examples (Ex-1') were prepared in a manner similar to that of Ex-1 except for the following: the method described in U.S. Patent No. 8,283,843, issued Jan. A doctor blade and a belt caster (AFA-II, MTI Corporation) formed a photocatalytic coating on the prepared PET substrate by tape casting. The gap of the doctor blade is maintained in the range of 3 mils to 20 mils (one mil equals 1/1000 inch or 25.4 micrometers). The PET substrate having the photocatalytic coating was dried at 110 ° C for about 1 hour in an ambient atmosphere. Additional examples (Ex-A to Ex-F) were prepared in a manner similar to Ex-1 except that the wt% of the binder solution and the ratio of photocatalytic material to binder solution will vary as indicated in Table 1. .

An additional example (Ex-G) was prepared in a manner similar to Ex-1 except that the substrate was a 2.5 cm diameter disc of the stethoscope diaphragm substrate. Stethoscope commercially available membrane (3M, Minneapolis, MN, USA, Littmann ^TM) as the substrate for the photocatalytic coating. The suspension was made of multi-phase TiO ₂ (P25) filled with copper oxide, and a 10 wt% KR5230 binder solution in PGMEA was applied to the separator by spin coating at 1000 rpm for 20 seconds, followed by ambient atmosphere. Dry at 110 ° C for 1 hour.

Adhesion

The adhesion of the photocatalytic coating was evaluated by following the procedure described in ASM-D3359.

The coating hardness was evaluated by following the procedure described in ASTM-3363.

Percentage of removal: 0B>65%; 1B: 35% to 65%; 2B: 15% to 35%; 3B: 5% to 15%; 4B<5%; 5B: 0%

Antibacterial efficacy

Antibacterial efficacy was assessed by following procedures.

The substrate (1" x 2" glass slide) was prepared by sequential application of 70% IPA (isopropyl alcohol), 100% ethanol (EtOH), followed by drying in air. Ex-1 was dispersed in 100% EtOH at a concentration of 2 mg/mL, and then about 100 μL of this suspension was applied to the substrate, followed by drying. The application process was repeated 5 times to obtain about 1 mg of Ex-1 on the substrate. The substrate was then dried at room temperature. The coated substrate was placed in a glass dish having a water immersion filter paper for maintaining moisture, and a glass spacer was inserted between the substrate and the filter paper to separate them.

Escherichia coli (ATCC 8739) was streaked onto a 10 cm diameter Petri dish containing about 20 ml of LB (latent culture medium/Luria medium) agar and incubated overnight at about 37 °C. For each experiment, a single colony was picked to inoculate approximately 3 mL of nutrient medium and the inoculated culture was incubated at approximately 37 °C for approximately 16 hours to produce an overnight culture (~10 ⁹ cells/mL). Fresh log phase cultures of overnight cultures were obtained by diluting overnight cultures 100-fold, inoculating another 5 cm Petri dish with LB agar and incubating at about 37 °C for about 2.5 hours. The fresh culture was diluted 50-fold with 0.85% physiological saline, which gave a cell suspension of about 2 x 10 ⁶ cells/mL. 50 μL of this cell suspension was pipetted onto each of the deposited glass substrates. A plastic film (20 mm x 40 mm) sterilized (in 70%, followed by 100% EtOH) was placed over the suspension to evenly disperse under the film. The sample was kept in the dark (Cu _x O-dark) or then irradiated under blue LED light (455 nm, 10 mW/cm ² ) (Cu _x O-bright). At selected time points, for example, 30 minute/60 minute increments, the samples were placed in 10 mL of 0.85% physiological saline and vortexed to wash away the bacteria. The rinse-off suspension was retained, and then serially diluted with 0.85% physiological saline, and then the suspension was spread on LB agar and incubated overnight at about 37 ° C to determine living cells according to colony forming units/samples. The number.

Figures 5 to 9 show the antibacterial (E. coli) efficacy of a photocatalytic coating filled with a P-catalyst as described in Table 1 on a PET substrate (Figure 5 - Sample Example A, Figure 6 - Sample Example B, etc.) . The trend is as follows: as the binder content increases, the adhesion increases, and the antibacterial efficacy does not change significantly. In order to obtain good antibacterial performance while maintaining good adhesion of the photocatalytic coating to the substrate, more than 75 vol% of the binder filling is advantageous.

Figure 10 shows the surface and cross-sectional morphology of a photocatalytic coating on a PET substrate using a polyoxymethylene-modified polyester resin as a binder. The coating thickness is about 10 microns.

Example 2 (P catalyst (Cu _x O/TiO ₂ ) coating on PET substrate)

A photocatalytic coating (Examples AA, AB, AC, AD, AE, AF) comprising a filled copper-titanium oxide and a polyfluorene-modified polyester as a binder was formed on the PET substrate by following the same processing procedure. One gram of titanium oxide powder P25 (Evonik Deggusa Corp, Parischipany, NJ, USA) filled with 1 wt% of Cu _x O was used instead of the photocatalytic material of Example 1 described above. Table 2 shows the adhesion, hardness and antibacterial efficacy as a complete kill time for E. coli. Figure 11 shows the contact time of the bacterial number versus the photocatalytic coating with varying photocatalytic material filling.

RT: room temperature

Example 3 (P catalyst (Cu _x O/SnO ₂ ) coating on PET substrate)

A photocatalytic coating comprising a copper-filled tin oxide and a polyfluorene-modified polyester as a binder was formed on the PET substrate by following the same procedure as described above. The copper content in the photocatalytic powder is 1% by weight of tin oxide. Figure 11 shows the antimicrobial efficacy of a photocatalytic coating on a PET substrate.

Example 4 (P catalyst (Cu _x O/TiO ₂ ) coating with a polyoxyl oligomer as a binder on a polymer bottle)

A photocatalytic coating comprising copper titanate filled on the water bottle is implemented. The coating suspension consists of a multi-phase titanium oxide (Cu _x O/P25) powder filled with copper oxide dispersed in a polyoxyxene oligomer (KR-500, ShinEtshu Silicones, JAPAN) and 2% by weight relative to KR-500. A catalyst (D-25) consisting of the procedure of Example 1 was followed. First, a water bottle made of PMMA was coated with an undercoat layer composed of a decane coupling agent for promoting adhesion between PMMA and KR-500. The synthesis of decane coupling agents is listed below.

Decaneization procedure: A 70:30 vol% mixture of ethanol and MiliQ (MQ) water was prepared as a solvent for the decane reaction. From this, a 7.5 wt% solution of aminopropyltriethoxydecane (APTES) was prepared. The pH of the solution was adjusted to 5.5 by the addition of concentrated acetic acid. Stirring the reaction while hydrolyzing 1 hour.

The interior of the vessel was filled with the decane mixture and allowed to stand for 30 minutes. The container is then rinsed with a large amount of MQ water and the container is allowed to dry before subsequent coating.

(APTES)

The P catalyst coating was applied to a PMMA bottle coated with a primer by dip coating with a suspension and then spinning at about 400 rpm for about 5 minutes to remove the additional coating suspension to obtain a uniform coating. The coated bottle was cured under ambient atmosphere and temperature for about 12 hours.

Example 5 (Photocatalytic coating with inorganic binder)

A commercially available inorganic sol is used as a binder to replace a polyoxyl resin including vermiculite, alumina, zirconia, and titania sol. The vermiculite sol (SNOWTEX-O, Nissan Chemicals, JAPAN) was mixed with a photocatalytic powder consisting of the filled copper titania as mentioned in Example 2 by a sonication probe for 30 minutes. The photocatalytic material filling varies in the range of 5.6 to 37.4 vol%. The photocatalytic suspension was applied to a PET substrate by spin coating at a spin rate of 1200 rpm. The coating was dried at 110 ° C for 1 hour to remove the solvent and water in the vermiculite sol to obtain a coating having good adhesion to the PET substrate.

Example I (P catalyst (Cu _x O/TiO ₂ ) coating on PET substrate)

A commercially available PET (polybutylene terephthalate) film (Eplastics Inc. San Diego, CA USA) having a thickness of about 120 μm was used as a substrate for the photocatalytic coating. Cut the substrate into a paper size. The cut PET substrate was cleaned with acetone and then dried.

By mixing about 1 g of UV curable acrylate adhesive (sold by DIC corporation, JAPAN under the trade name Unidic 17806), about 24 mg of photoinitiator A binder solution containing 10% by weight of a UV curable hard coat layer was prepared (sold under the trade name Irgacure 907) and about 10 g of cyclopentanone (reagent > 99.5%, Sigma-Aldrich). The mixing was carried out with a planetary centrifugal mixer (THINKY AR-310) at about 2000 rpm for 2 minutes for mixing, followed by about 2200 rpm for about 1 minute for defoaming.

To make a coating suspension, one part by weight of Cu _x O/P25 photocatalytic powder (about 0.2 g) and 5 parts by weight of binder solution (10 wt% of acrylamide in cyclopentanone) Formate) mixed. Photocatalytic powders are prepared as described in each of the following: US Patent Application No. 13/840,859, filed on March 15, 2013; and US Provisional Application No. 61/835,399, filed on Jun. 14, 2013; U.S. Patent Application Serial No. 13/741,191, filed Jan. The photocatalytic catalyst (P catalyst) powder comprises titanium oxide filled with copper oxide doped with carbon, nitrogen and tin to increase light absorption in the visible range. The nominal copper content in the P catalyst was 1 wt%. The 0.2 gm photocatalytic powder is dispersed in the binder solution (about 1 gm, 10) by holding the glass bottle containing the mixture in the sonication bath for about half an hour, followed by probe sonication for about 20 to 30 minutes. % solution). The resulting suspension was passed through a filter with an opening of 5 microns.

Prior to coating, the cleaned PET substrate is subjected to a corona discharge treatment to increase the hydrophilicity of the substrate surface to achieve good wettability of the coating suspension. A corona treatment apparatus (TEWC-4AX, KASUGA DENKI Inc. JAPAN) was used by performing two scans at a discharge power of 100 W and a scan speed of 0.5 m/sec.

The method described in U.S. Patent No. 8,283,843, issued to theU. Coating of the substrate (Ex-I) was performed on the prepared PET substrate. The gap of the doctor blade is maintained in the range of 3 mils to 20 mils (one mil equals 1/1000 inch or 25.4 micrometers). The PET substrate with the photocatalytic coating was dried under ambient atmosphere, followed by preheating at 90 ° C to 100 ° C for about 2 minutes, followed by UV curing under a Loctite® Zeta® 7411 UV overflow curing system. The UV light energy was monitored by a ZETA 7011-A dosimeter-radiometer with an energy intensity of about 25 mw/cm ² . Additional examples (Ex-II, Ex-III, and Ex-IV) were prepared in a manner similar to Ex-I except that the ratio of binder to P catalyst was different and varied as indicated in Table 4.

Additional examples (Ex-11 to Ex-15) were prepared in a manner similar to Ex-I except that the following dispersants were added to the binder/photoinitiator/cyclopentanone and as indicated in Table 6. The amount of change.

Example V (P Catalyst (Cu _x O/TiO ₂ ) Coating / Interposer / PET Substrate Example)

The substrate of Example V was prepared as described in Example I above.

The adhesive solution intervening in the first layer and the second layer of photocatalyst/adhesive was prepared in a manner similar to the adhesive layer described in Example I, except as described in Table 3 below.

The first or intervening layer is applied to the prepared substrate in a manner similar to that described in Example I above.

A second or photocatalytic layer is then placed over the first layer of coating. The gap of the doctor blade is maintained in the range of 1 mil to 3 mils. The PET substrate having the first polymeric coating and the second polymeric coating is dried in an ambient atmosphere and then preheated at 90 ° C to 100 ° C for about 2 minutes. The dried dual coated substrate was then UV cured under a Loctite® Zeta® 7411 UV Overflow Curing System. The UV light energy was monitored by a ZETA 7011-A dosimeter-radiometer with an energy intensity of about 25 mw/cm ² .

Turbidity and transparency

The turbidity and transmittance were evaluated on an Ultrascan Pro following the procedure described in the ASTM-D1003 standard.

Adhesion

The adhesion of the photocatalytic coating was evaluated by following the procedure described in ASM-D3359.

Percentage of removal: 0B>65%; 1B: 35% to 65%; 2B: 15% to 35%; 3B: 5% to 15%; 4B<5%; 5B: 0%

hardness

The coating hardness was evaluated by following the procedure described in ASTM-3363.

Solvent resistance (friction test)

The friction test was evaluated by following the procedure described in ASTM-D5402, using solvents including IPA, EtOH, and bleach. Cloth clean room synthetic rag. Perform a double rub until the maximum of 200 times.

Figure 16 is a graph showing the antibacterial (E. coli) activity of the examples (Examples I and II) described herein.

Figure 17 is a graph showing the antibacterial (E. coli) activity of the examples (Examples 11 to 15) described herein under bright conditions.

Figure 18 is a graph showing the antibacterial (E. coli) activity of the examples (Examples 11 to 15) described herein under dark conditions.

The difference between pre-test and post-test data may be due to different test points.

19 and 20 are SEM photographs of Example 11. 21 and 22 are SEM photographs of Example 15. These SEM photographs depict the uniformity of dispersion of the photocatalytic material in or on the surface of the cured binder/photocatalyst.

Unless otherwise indicated, all numbers expressing quantities of ingredients, such as molecular weight, reaction conditions, and the like, used in the specification and claims are to be understood as being modified by the term "about" in all instances. Accordingly, the numerical parameters set forth in the specification and the appended claims are to be construed as an At the very least, and not as an attempt to limit the application of the scope of the invention to the scope of the claims, each numerical parameter should be construed in the

In the description of the embodiments, unless otherwise indicated herein or clearly contradicted by context The terms "a" and "the" and the like are used in the context of the singular and plural. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted. The use of any and all examples or exemplary language, such as "such as" The language in the specification should not be construed as indicating that any non-claimed elements are essential to the embodiments.

The grouping of alternative elements or embodiments disclosed herein is not to be construed as limiting. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is contemplated that one or more members of a group may be included in or deleted from the group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is considered to contain the group as modified, thus satisfying the written description of all Markush groups used in the scope of the appended claims.

Specific embodiments are described herein, including the best mode known to the inventors to carry out the invention. Of course, variations of the described embodiments will become apparent to those skilled in the art upon reading the description. The inventors intend for the skilled artisan to employ such variations as appropriate, and the inventors intend to practice the embodiments in a manner different from those specifically described herein. Accordingly, the technical solution includes all modifications and equivalents of the subject matter described in the scope of the claims. Further, any combination of all possible variations of the above-described elements is contemplated unless otherwise indicated herein or otherwise clearly contradicted.

In sum, it should be understood that the embodiments disclosed herein are illustrative of the principles of the claims. Other modifications that may be used are within the scope of the patent application. Thus, by way of example, and not limitation, Therefore, the scope of the patent application is not limited to the embodiments as shown and described.

The present application is based on U.S. Provisional Application No. 61/899,423, filed on Nov. 4, 2013, U.S. Provisional Application No. 61/931,387, filed on Jan. 24, 2014, and U.S. Provisional Application No. 62/007,489, the entire contents of each of which is incorporated herein by reference.

In addition, each of the above-mentioned U.S. Patent No. 5,897,958, U.S. Patent No. 6,228,480, U.S. Patent No. 6,407,033, U.S. Patent No. 7,510,595, and U.S. Reissue Patent No. RE38,850 are also incorporated by reference in their entirety. The way is incorporated in this article.

Claims (24)

A method for fabricating a photocatalytic element, comprising: providing a suspension comprising a binder and a photocatalytic material, wherein the weight ratio of the binder to the photocatalytic material is from about 0.5 to 2.0 parts of binder to about 1 part of light a catalytic material; and applying the suspension to the surface of the substrate. The method of claim 1, further comprising applying a decane coupling agent to the surface of the substrate. The method of claim 2, wherein the decane coupling agent is aminopropyltriethoxydecane. The method of any one of claims 1 to 3, further comprising adding a binder catalyst material to the suspension. The method of claim 4, wherein the binder catalyst material is D25. The method of any one of claims 1 to 5, wherein providing the suspension further comprises dissolving the polyoxyxylene resin in a propylene glycol solvent. The method of claim 6, wherein the polyoxynoxy resin is a polyoxyl alkyd resin, a polyoxymethylene epoxy resin, a polyoxypropylene acrylic resin or a polyoxyethylene polyester resin. The method of claim 7, wherein the polyoxyxylene resin is a polyoxymethylene polyester resin. The method of any one of claims 1 to 8, wherein the photocatalytic material comprises a metal oxide filled with copper oxide. A method for producing a photocatalytic element, comprising: providing a solution comprising 10% KR5230 and 90% propylene glycol monomethyl ether acetate (PGMEA); 10:1 (w/w) binder: photocatalysis a ratio of materials to the photocatalytic copper-filled multiphase titanium oxide material powder is added to the solution; The PET surface is pretreated by corona treatment; and the solution is spin coated onto the pretreated PET surface at about 100 to about 2000 rpm for about 30 to about 60 seconds. A photocatalytic element comprising a polyoxymethylene polyester resin and a photocatalytic material, wherein the weight ratio of the resin to the photocatalytic material is between about 0.5 and about 2.0 to about 1. The photocatalytic element of claim 11, wherein the polyoxymethylene polyester resin is selected from the group consisting of KR500, KR5230, and KR5235. A method for producing a photocatalytic element, comprising: providing a suspension comprising a binder, a photocatalytic material, a photoinitiator, and an organic solvent, wherein the weight ratio of the binder to the photocatalytic material is about 1.0 to 20 parts by weight The binder is applied to about 1 part of the photocatalytic material; and the suspension is applied to the surface of the substrate. The method of claim 13, wherein the binder comprises an ultraviolet curable urethane resin. The method of claim 13 or 14, wherein the organic solvent is a C ₁ -C ₇ ketone. The method of claim 13 or 14, wherein the organic solvent is a C ₁ -C ₇ alcohol. The method of claim 13 or 14, wherein the organic solvent is selected from the group consisting of cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), methyl ethyl ketone (MEK) , toluene, ethyl acetate and butyl acetate. The method of any one of claims 13 to 17, wherein the suspension further comprises a dispersing agent. The method of claim 18, wherein the dispersing agent is selected from the group consisting of a cationic dispersing agent, an anionic dispersing agent, and a nonionic dispersing agent. The method of any one of claims 13 to 19, wherein the photoinitiator is selected from the group consisting of IRGACURE 907 and IRGACURE 2022. The method of any one of claims 13 to 20, wherein the photocatalytic material comprises a fill A metal oxide of copper oxide. A method for producing a photocatalytic element, comprising: providing a solution comprising 10% by weight of urethane acrylate resin, less than 1.0% by weight of photoinitiator, and 90% by weight of cyclopentanone; w/w) binder: ratio of photocatalytic material, a photocatalytic copper-filled multiphase titanium oxide material powder is added to the solution; the surface of the PET is pretreated by corona treatment; and the suspension is cast in a belt The pretreated PET surface. A photocatalytic element comprising an urethane urethane resin and a photocatalytic material, wherein the weight ratio of the resin to the photocatalytic material is between about 0.5 and about 10 to about 1. The photocatalytic element according to claim 23, wherein the urethane acrylate resin is selected from the group consisting of UNIDIC 17806, EBECRYL 8701, EBECRYL 8301, EBECRYL 8405, OC-3021, OC-4021, OC-4122, HC-5619, and UVHC3000. .