CN111715301A - Photocatalyst product - Google Patents
Photocatalyst product Download PDFInfo
- Publication number
- CN111715301A CN111715301A CN201911210828.9A CN201911210828A CN111715301A CN 111715301 A CN111715301 A CN 111715301A CN 201911210828 A CN201911210828 A CN 201911210828A CN 111715301 A CN111715301 A CN 111715301A
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- CN
- China
- Prior art keywords
- photocatalyst
- layer
- coating liquid
- clay mineral
- zirconium carbonate
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 195
- 239000000758 substrate Substances 0.000 claims abstract description 111
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims abstract description 59
- 239000002734 clay mineral Substances 0.000 claims abstract description 54
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 42
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 128
- 239000000463 material Substances 0.000 claims description 47
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 34
- 239000004744 fabric Substances 0.000 claims description 30
- 238000004381 surface treatment Methods 0.000 claims description 25
- 239000004745 nonwoven fabric Substances 0.000 claims description 20
- 238000005286 illumination Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 43
- 239000012298 atmosphere Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 description 151
- 239000011248 coating agent Substances 0.000 description 148
- 239000007788 liquid Substances 0.000 description 115
- 239000007789 gas Substances 0.000 description 66
- 239000000047 product Substances 0.000 description 56
- 239000003431 cross linking reagent Substances 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- 238000002360 preparation method Methods 0.000 description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 39
- 239000003463 adsorbent Substances 0.000 description 35
- 239000007787 solid Substances 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 26
- 238000012360 testing method Methods 0.000 description 26
- 238000010998 test method Methods 0.000 description 25
- 238000007598 dipping method Methods 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 21
- 239000002002 slurry Substances 0.000 description 21
- 230000005484 gravity Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 150000007530 organic bases Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 238000003618 dip coating Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 4
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229940030980 inova Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007777 rotary screen coating Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
Abstract
Embodiments of the present invention relate to photocatalyst articles. The object is to obtain a photocatalyst article having a good catalytic action with respect to the surrounding atmosphere. The photocatalyst product according to an embodiment includes a porous substrate, and a surface-treated portion provided on the porous substrate and containing at least 1 of ammonium zirconium carbonate or a clay mineral containing smectite, and a photocatalyst containing tungsten oxide.
Description
The application takes Japanese patent application 2019 and 051293 (application date: 3 and 19 in 2019) and Japanese patent application 2019 and 192159 (application date: 10 and 21 in 2019) as the basis, and the application enjoys the priority. The present application incorporates the entire contents of these applications by referring to these japanese patent applications.
Technical Field
Embodiments of the present invention relate to photocatalyst articles.
Background
The photocatalyst generates excited electrons and holes by light, and has a strong oxidizing power. The oxidation force is utilized as a catalytic action for decomposition and removal of harmful organic molecules, sterilization, maintenance of hydrophilicity of a base material, and the like. When the photocatalyst is applied to an inorganic substrate such as a glass substrate, it can exhibit a catalytic action with respect to the ambient atmosphere. On the other hand, nonwoven wallpaper, cloth products, and the like contain various organic components because they are treated with chemicals, dyed, and the like. Therefore, when a photocatalyst is applied to an organic substrate such as a nonwoven fabric, many harmful organic molecules derived from the organic substrate are adsorbed and decomposed, and thus there is a problem that the catalytic action with respect to the ambient atmosphere is reduced.
Disclosure of Invention
An object of an embodiment of the present invention is to obtain a photocatalyst article having a good catalytic effect with respect to the surrounding atmosphere.
According to an embodiment, there is provided a photocatalyst product including:
porous base material, and
and a surface treatment section provided on the porous base material, the surface treatment section including at least 1 of ammonium zirconium carbonate or a smectite-containing clay mineral and a photocatalyst containing tungsten oxide.
Drawings
Fig. 1 is a schematic diagram showing the structure of a photocatalyst product according to embodiment 1.
Fig. 2 is a schematic diagram showing another configuration of the photocatalyst product according to embodiment 1.
Fig. 3 is a schematic diagram showing another configuration of the photocatalyst product according to embodiment 1.
Fig. 4 is a schematic diagram showing another configuration of the photocatalyst product according to embodiment 1.
Fig. 5 is a schematic diagram showing the structure of the photocatalyst product according to embodiment 2.
Fig. 6 is a graph showing the catalytic action of the photocatalyst product according to the embodiment.
Fig. 7 is a graph showing the catalytic action of another sample of the photocatalyst product according to the embodiment.
Fig. 8 is a graph showing the catalytic action of comparative photocatalyst articles.
Fig. 9 is a graph showing the catalytic action of the photocatalyst product according to the embodiment.
Fig. 10 is a graph showing the catalytic action of comparative photocatalyst articles.
Fig. 11 is an SEM photograph of the surface of the porous substrate used in the embodiment.
Fig. 12 is an SEM photograph of the surface of the photocatalyst article according to the embodiment.
Fig. 13 is a photograph of a black cloth surface showing the result of a transfer test of the photocatalyst product according to the embodiment.
Fig. 14 is a photograph of a black cloth surface showing the result of a photocatalyst transfer test of the photocatalyst product according to the embodiment.
Fig. 15 is a graph showing the relationship between the light irradiation time and the residual acetaldehyde rate.
Detailed Description
The photocatalyst product according to the embodiment includes a porous substrate and a surface treatment portion provided on the porous substrate. The surface treatment section includes at least 1 of a clay mineral containing smectite or ammonium zirconium carbonate, and a photocatalyst containing tungsten oxide.
According to the embodiment, by using at least 1 of the clay mineral containing the smectite and the ammonium zirconium carbonate for the surface treatment portion, for example, in the case of using an organic base material as the porous base material, gas emission from the organic base material can be prevented. In addition, it is possible to prevent the emission of, for example, aldehyde-based gas generated by the photocatalytic reaction in which the photocatalyst comes into contact with the organic component in the organic base material. This makes it possible to obtain a state in which the photocatalytic action of the photocatalyst with respect to the ambient atmosphere is good. Further, the photocatalytic action is effective for the case where an organic porous substrate, particularly a nonwoven wallpaper or fabric product, is used as the porous substrate.
The photocatalyst products according to the embodiments can be classified into those according to embodiments 1, 2, and 3 below.
The photocatalyst product according to embodiment 1 includes a porous base material and a surface-treated portion provided on the porous base material and containing a clay mineral containing a smectite and a photocatalyst containing tungsten oxide.
Smectites are silicate minerals with a layered crystal structure. Examples of the smectite (smectite) that can be used in the embodiment include saponite, hectorite, montmorillonite (montmorillonite), and stevensite. A smectite having a shape in which thin film crystals are laminated with a high aspect ratio or a smectite having high transparency can be used.
According to embodiment 1, the porous base material is surface-treated with a smectite having a shape in which thin film crystals are laminated, whereby the barrier property of the porous base material against organic components is improved. For example, when a photocatalyst is used in an organic base material coated with an aqueous dye obtained by dispersing an acrylic emulsion, an organic substance as a component of the acrylic emulsion is eluted from the organic base material to cover the photocatalyst. In contrast, if the organic base material is treated with the smectite, the eluted organic substance is prevented from coming into contact with the photocatalyst, and the deterioration of the photocatalyst performance and the emission of aldehyde-based or carboxylic acid-based gas due to the reaction between the organic substance and the photocatalyst are prevented. In addition, the photocatalyst can be prevented from reacting by directly contacting the organic substrate. Thus, a photocatalyst product having a good catalytic action with respect to the ambient atmosphere can be obtained.
Fig. 1 is a schematic diagram showing a configuration of a photocatalyst product according to embodiment 1.
As shown in the drawing, the photocatalyst product 10 according to embodiment 1 includes, for example, a porous substrate 1 and a surface treatment section 4 provided on the porous substrate 1. The surface treatment section 4 includes a clay mineral layer 2 and a photocatalyst layer 3 formed in this order on the porous substrate 1. When a substrate having an uneven surface such as a nonwoven fabric is used as the porous substrate 1, the clay mineral layer 2 does not need to be a uniform layer and may be dispersed on the surface of the substrate. Similarly, the photocatalyst layer 3 does not need to be a uniform layer, and may be dispersed on the surface of the substrate. When the porous substrate 1 absorbs the clay mineral, the clay mineral layer 2 may penetrate into the substrate.
The surface-treated portion 4 may include a region rich in clay minerals containing smectite, a region rich in photocatalyst, and a region in which both clay minerals and photocatalyst are mixed. The substance exhibiting the catalytic action is a photocatalyst exposed on the surface-treated part 4.
As the porous substrate, there can be used an organic substrate such as a cloth product, a nonwoven fabric, a woven fabric, a resin film, or a resin sheet, an organic substrate containing a coating material containing an organic substance, a dye, a pigment, a binder, a paste, or an oil agent, and a product using at least 1 of them.
The amount of smectite used in the porous base material can be set to 1.0 to 6.0g/m in terms of solid content2. If it exceeds 6.0g/m2It becomes soft and soft as a base materialThe photocatalyst particles fixed thereon are easily dropped, and the amount of the photocatalyst particles is less than 1.0g/m2The coating tends to be uneven, and thus the effect tends to be insufficient, but an appropriate range is determined depending on the porous substrate, depending on the weight per unit area, the surface area, the production process, and the like of the porous substrate.
The clay mineral layer 2 can be formed by applying a coating liquid containing smectite by, for example, a coating method such as dip coating, gravure coating, spin coating, bar coating, or rotary screen coating. For example, if the photocatalyst is applied to both surfaces of a porous substrate, such as by dip coating, when the porous substrate is an organic substrate and the photocatalyst product is stored in a roll form or stacked, gas emission from the back surface of the organic substrate can be prevented. In addition, the photocatalyst can be prevented from reacting by contacting with the organic substrate.
The photocatalyst used in the embodiment may be at least 1 metal oxide of titanium oxide, zinc oxide, tungsten oxide, niobium oxide, tin oxide, or the like. In addition, at least 1 kind of zirconia, platinum, ruthenium, copper, or the like may be added to the photocatalyst.
The amount of the photocatalyst used in the porous substrate may be set to 0.2 to 2.0g/m in terms of solid content2. If it exceeds 2.0g/m2If the amount of the organic solvent is less than 0.2g/m, problems such as change in color tone and easy falling-off of particles may occur2The catalytic action tends to be insufficient, but the appropriate range is determined depending on the porous substrate, depending on the weight per unit area, the surface area, the production process, and the like of the porous substrate.
The photocatalyst layer 3 can be formed by applying a photocatalyst-containing slurry by a coating method such as dip coating, gravure coating, spin coating, bar coating, or rotary screen coating.
The surface-treated part may further contain at least 1 of ammonium zirconium carbonate or adipic acid dihydrazide.
Ammonium zirconium carbonate is considered to be used as a crosslinking agent for crosslinking an organic material contained in the porous base material. By making ammonium zirconium carbonate react with a carboxyl group or a hydroxyl group of a water-soluble polymer in an organic substrate such as a porous substrate, for example, a nonwoven fabric, and insolubilizing (immobilizing) the resultant, it is possible to prevent the release or exudation of an unnecessary gas. According to the embodiment, by further including ammonium zirconium carbonate in the surface treatment portion, a photocatalyst product having a better catalytic effect with respect to the ambient atmosphere can be obtained.
The amount of ammonium zirconium carbonate used is based on the amount of ZrO in the porous base material2Can be set to 0.1 to 10.0g/m in terms of solid content2. If it exceeds 10.0g/m2When the amount of the polymer particles is less than 0.1g/m, the flexibility of the substrate is lost2The immobilization tends to be insufficient, but the preferable range is not limited depending on the weight per unit area, the surface area, the production process, and the like of the porous base material.
Here, ZrO is referred to2The conversion is that firstly, ammonium zirconium carbonate solution is weighed, completely evaporated and dried, and the weight of the evaporated and dried solid is divided by (NH)4)2[Zr(CO3)2(OH)2]281.33 and multiplied by ZrO2Molecular weight of 123.22, to determine the amount of ammonium zirconium carbonate evaporated to dryness into ZrO2Is calculated as a weight of (c). The amount of fixation per unit area (amount of solid content) can be calculated by using the converted weight as the weight of the solid content.
Adipic acid dihydrazide is used as an adsorbent for adsorbing harmful organic molecules such as formaldehyde. According to the embodiment, by using adipic acid dihydrazide in the surface treatment portion, a photocatalyst product having a better catalytic action with respect to the ambient atmosphere can be obtained.
The amount of adipic acid dihydrazide used for the porous base material may be set to 0.5 to 15.0g/m in terms of solid content2. If it exceeds 15.0g/m2If the amount is less than 0.1g/m, it causes generation of powdery substances2However, the preferable range is not limited, and varies depending on the weight per unit area, the surface area, the production process, and the like of the porous base material.
Fig. 2 to 4 are schematic diagrams showing other configurations of the photocatalyst product according to embodiment 1.
When ammonium zirconium carbonate is used, for example, as shown in fig. 2, a crosslinking agent layer 5 containing ammonium zirconium carbonate may be formed before the clay mineral layer 2 is formed on the porous substrate 1. The obtained photocatalyst product 20 includes a crosslinking agent layer 5, a clay mineral layer 2, and a photocatalyst layer 3 as a surface treatment portion 4-1, which are formed in this order on a porous substrate 1.
When the porous base material 1 absorbs the crosslinking agent or the clay mineral, the crosslinking agent layer 5 or the clay mineral layer 2 may penetrate into the porous base material.
When adipic acid dihydrazide is used, for example, as shown in fig. 3, the adsorbent layer 6 containing adipic acid dihydrazide may be formed before the clay mineral layer is formed on the porous base material. The obtained photocatalyst product 30 includes an adsorbent layer 6, a clay mineral layer 2, and a photocatalyst layer 3 as surface-treated portions 4-2, which are formed in this order on a porous substrate 1. When the porous substrate 1 absorbs the adsorbent or the clay mineral, the adsorbent layer 6 or the clay mineral layer 2 may penetrate into the porous substrate.
When both the crosslinking agent layer and the adsorbent layer are applied, for example, as shown in fig. 4, the crosslinking agent layer 5 and the adsorbent layer 6 may be formed in this order, or the adsorbent layer 6 and the crosslinking agent layer 5 may be formed in this order, before the clay mineral layer is formed on the porous substrate 1. The obtained photocatalyst product 40 has a crosslinking agent layer 5, an adsorbent layer 6, a clay mineral layer 2, and a photocatalyst layer 3 as surface-treated portions 4-3 laminated in this order on a porous substrate 1. When the porous base material 1 absorbs the crosslinking agent, the adsorbent, or the clay mineral, the crosslinking agent layer 5, the adsorbent layer 6, or the clay mineral layer 2 may permeate into the porous base material. In addition, instead of forming the crosslinking agent layer 5 and the adsorbent layer 6, a coating solution obtained by mixing a crosslinking agent and an adsorbent may be used to form a layer containing both the crosslinking agent and the adsorbent, which is not shown.
The crosslinking agent layer can be provided in the vicinity of the porous base material rather than the adsorbent layer because it reacts with a carboxyl group, a hydroxyl group, or the like of the water-soluble polymer in the porous base material. By further containing ammonium zirconium carbonate and adipic acid dihydrazide, a photocatalyst article having further excellent catalytic action with respect to the surrounding atmosphere can be obtained. In addition, when the adsorbent layer 6 becomes difficult to be impregnated into the porous base material by the crosslinking reaction of the crosslinking agent layer 5, the adsorbent layer 6 and the crosslinking agent layer 5 may be formed in this order.
The cross-linking agent layer and the adsorbent layer can be formed by applying a coating liquid containing a cross-linking agent and a coating liquid containing an adsorbent by a coating method such as dip coating, gravure coating, spin coating, bar coating, or spray coating. For example, if the photocatalyst is applied to both surfaces of a porous substrate, such as by dip coating, when the porous substrate is an organic substrate and the photocatalyst product is stored in a roll form or stacked, the emission of gas from the back surface of the organic substrate can be suppressed. In addition, the reaction of the photocatalyst in contact with the organic substrate can be suppressed.
Fig. 5 is a schematic diagram showing a configuration of a photocatalyst product according to embodiment 2.
The photocatalyst product 50 according to embodiment 2 includes a porous substrate 1 and surface-treated portions 4-4 provided on the porous substrate 1, and a crosslinking agent layer 5 and a photocatalyst layer 3 containing tungsten oxide are sequentially stacked as the surface-treated portions 4-4. When a substrate having an uneven surface such as a nonwoven fabric is used as the porous substrate 1, the crosslinking agent layer 5 does not need to be a uniform layer and may be dispersed on the surface of the substrate. Similarly, the photocatalyst layer 3 does not need to be a uniform layer, and may be dispersed on the surface of the substrate. When the porous base material absorbs the crosslinking agent, the crosslinking agent layer 5 may penetrate into the porous base material.
The surface-treated portion 4 may include a region rich in ammonium zirconium carbonate, a region rich in a photocatalyst, and a region in which both ammonium zirconium carbonate and the photocatalyst are mixed. The substance exhibiting the catalytic action is a photocatalyst exposed on the surface-treated part 4.
According to embodiment 2, when the crosslinking agent containing ammonium zirconium carbonate is used, the porous base material, for example, the carboxyl group or the hydroxyl group of the water-soluble polymer in the organic base material is made to react with ammonium zirconium carbonate and insolubilized, thereby preventing the porous base material from emitting or bleeding out of unnecessary gas. By preventing the photocatalyst from reacting with the porous substrate in this manner, a photocatalyst product having a good catalytic effect with respect to the ambient atmosphere can be obtained.
The porous substrate, the surface-treated portion, the crosslinking agent layer, and the photocatalyst layer containing tungsten oxide used in embodiment 2 are the same as those used in embodiment 1. The amounts of ammonium zirconium carbonate, the photocatalyst layer, and the like used for the porous substrate are the same as those in embodiment 1.
The photocatalyst product according to embodiment 3 includes a porous base material and a surface-treated portion provided on the porous base material, and the surface-treated portion includes a clay mineral containing a smectite and a photocatalyst containing tungsten oxide. Further, in this photocatalyst product, the volume of the chamber was 0.5L, irradiation was performed from a white fluorescent lamp FL20SW, UV light of 380nm or less was cut off by a CLAREX UV cut filter N-169 (the resin industry in the japanese east), the illuminance was set to 6000 lux, and acetaldehyde having a concentration of 10ppm was reduced by 60% or more in 2 hours under the conditions of normal temperature, normal pressure, and a humidity of 20%.
According to embodiment 3, a photocatalyst product having a good catalytic effect with respect to the ambient atmosphere can be obtained.
The porous substrate and the surface-treated part used in embodiment 3 are the same as those used in embodiment 1. The amount of the photocatalyst layer or the like used for the porous substrate is the same as in embodiment 1.
The photocatalyst product according to the embodiment can be produced by applying a coating liquid containing a photocatalyst, adipic acid dihydrazide, ammonium zirconium carbonate, or a clay mineral containing a member such as smectite to a porous substrate. The state of the member fixed to the porous substrate by application of the coating liquid is affected by the material of the porous substrate. For example, when the porous base material is a resin film or a resin sheet, the coating liquid is less likely to penetrate, and the member in the coating liquid can be fixed so as to cover the surface of the porous base material. On the other hand, when the porous substrate is a cloth product, a nonwoven fabric, or a woven fabric, the coating liquid is likely to permeate, and the member in the coating liquid can be fixed so as to cover 1 fiber constituting the porous substrate. From these, in the production process of the photocatalyst product according to the embodiment, the concentration of the coating liquid and the coating amount can be adjusted in consideration of the easy penetration of the coating liquid into the porous base material to be used.
As a criterion for the easy permeability of the coating liquid to the porous substrate, the maximum water absorption amount of the porous substrate that can absorb pure water per unit area can be measured in advance for the porous substrate used. At this time, the amount of adhesion (solid content) F of each coating liquid to the porous substrateW(g/m2) Can be represented by the following formula (1).
FW＝K/100×WA×C/100×(D/D0) (1)
FW: amount of solid component fixed (g/m)2)
K: any value exceeding 0 and not more than 100
WA: can absorb the maximum water absorption capacity (g/m) of pure water2)
C: solid content concentration (% by weight) of coating liquid
D: specific gravity (g/cm) of coating liquid3)
D0: specific gravity (g/cm) of water3)
In the formula, WAThe porous base material has a maximum water absorption capacity (g/m) capable of absorbing pure water per unit area2) K is an arbitrary value selected depending on the method of application or the state of application of the coating liquid, and is more than 0 and 100 or less, C is the solid content concentration (wt%) of the coating liquid, and D is the specific weight (g/cm) of the coating liquid3)，D0Is the specific gravity (g/cm) of water3)。
The solid content concentration C (wt%) of each coating liquid differs depending on the member used in the coating liquid. Covering on the surface of a buildingIn the case of soapstone, the amount of soapstone is 0 to 5 wt%. When the solid content concentration C of the smectite-containing coating liquid exceeds 5 wt%, the viscosity tends to increase and water dispersion tends to become difficult, so that it can be set to 5 wt% or less. In the case of ammonium zirconium carbonate, ZrO2Converted to 0 to 20 wt%. When the solid content concentration C of the coating liquid containing Ammonium Zirconium Carbonate (AZC) exceeds 20 wt% (ZrO)2Conversion), ammonia odor tends to be strong, and the working environment tends to be deteriorated, so that it may be set to 20 wt% or less. In the case of adipic acid dihydrazide, the content may be set to 0 to 11% by weight. Since the solubility of adipic Acid Dihydrazide (ADH) in water is 11 wt% at 30 ℃, the solid content concentration C of the coating liquid containing adipic Acid Dihydrazide (ADH) can be set to 11 wt% or less.
The solid content concentration C is preferably 1 to 3% by weight in the case of smectite, and ZrO in the case of ammonium zirconium carbonate2The content of the acid anhydride in terms of weight can be 0.1 to 10% by weight, and in the case of adipic acid dihydrazide, the content can be 0.1 to 8% by weight.
Hereinafter, embodiments will be described in detail by way of examples.
Examples
Example 1
Preparation of Clay mineral coating liquid 1
The smectite powder was put into pure water stirred by a stirrer so that the smectite powder was 2.8 wt%, stirred for 5 minutes, treated with a homogenizer for 15 minutes, and left to stand for 24 hours. This was again stirred and homogenized by the stirrer to obtain a slurry as the clay mineral layer coating liquid 1.
Preparation of photocatalyst coating liquid 1
Preparation of a composition containing 10% by weight of WO3And 10% by weight of TiO2The slurry of (3) was diluted with pure water so that the total solid content became 2.5 wt%.
Sample preparation
The maximum water absorption of a nonwoven wallpaper cut into 50 × 100mm was measured to be 0.964g, so that the amount of the nonwoven wallpaper was 1m2Is the most important ofLarge water absorption WAEstimated to be 192.8g/m2。
On the nonwoven wallpaper, 199g/m was applied by dipping2(in this case, K is 100, and the specific gravity D of the coating liquid is 1.03g/cm3) Coating clay mineral coating liquid 1, drying at 150 deg.C for 5 min, and sticking 5.6g/m on nonwoven wallpaper substrate2The smectite of (1).
Further, the coating was applied by dipping at a rate of 40g/m2The coating contained 1.25% by weight of WO3And 1.25 wt% TiO2The photocatalyst coating liquid 1 was dried at 150 ℃ for 5 minutes so that the photocatalyst content was 1.0g/m2And (5) adhering to obtain the non-woven wallpaper serving as the photocatalyst product.
The prepared non-woven fabric wallpaper is 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 24 hours to prepare a sample. In addition, a sample which was not subjected to pretreatment with ultraviolet rays was separately prepared.
Test method
In the acetaldehyde gas removal test, a sample was placed in a 5L chamber, and the chamber was purged with air at 25 ℃ and 20% humidity and then injected with a syringe so that the concentration of acetaldehyde gas became 10 ppm. For the removal test, an ultraviolet sharp cut filter (CLAREX UV cut filter N-169) was interposed between the lamp and the chamber, and the sample surface was irradiated with light at 6000lx using a white fluorescent lamp FL20SW while cutting off UV light of 380nm or less, and the concentration of acetaldehyde gas was measured for 2 hours using an optoacoustic multi-gas monitor inova 1412i (manufactured by Luma Sense Technologies).
Fig. 6 is a graph showing the catalytic action of the photocatalyst product according to the embodiment, and shows the relationship between the irradiation time with light and the residual acetaldehyde rate.
Fig. 7 is a graph showing the catalytic action of another sample of the photocatalyst product according to the embodiment, and shows the relationship between the irradiation time with light and the residual acetaldehyde rate.
The results of example 1 are shown in fig. 6 as curve 101.
Fig. 7 shows the result of an acetaldehyde gas removal test performed on a sample which was not pretreated with ultraviolet rays in the same manner as described above, as a curve 506.
As is clear from fig. 6 and 7, when the smectite and the photocatalyst were applied to the surface treatment portion, the acetaldehyde gas remaining rate was 10% or less at 2 hours for the sample pretreated with the ultraviolet ray, and the good catalytic effect was exhibited. However, in the sample which was not pretreated with ultraviolet light, the residual ratio of acetaldehyde gas was 70% or more at 2 hours, and a sufficient catalytic action could not be confirmed.
Example 2
Preparation of Cross-linker coating liquid 1
The cross-linking agent coating liquid is prepared by mixing ZrO2The resulting solution was diluted to 1.9 wt% in terms of 19% aqueous solution of ammonium zirconium carbonate with pure water and stirred with a stirrer.
Preparation of Clay mineral coating liquid 1
A slurry of the clay mineral layer coating liquid 1 was obtained in the same manner as in example 1.
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
The maximum water absorption of a nonwoven wallpaper cut into 50 × 100mm was measured to be 0.964g, so that the amount of the nonwoven wallpaper was 1m2Maximum water absorption W ofAEstimated to be 192.8g/m2。
On the nonwoven wallpaper, 199g/m was applied by dipping2(in this case, K was 100, and the specific gravity D of the coating liquid was 1.033g/cm3) The coating solution 1 was applied and dried at 150 ℃ for 5 minutes to immobilize ammonium zirconium carbonate. In this manner, the amount of the solid component (ZrO) of ammonium zirconium carbonate was added to the nonwoven wallpaper substrate2Conversion) cement has a mass of 3.8g/m2Ammonium zirconium carbonate of (4).
Then, the coating was applied by dipping at 199g/m2(in this case, K is 100, and the specific gravity D of the liquid is 1.04g/cm3) Coating was carried out in the same manner as in example 1The clay mineral coating liquid 1 of (2) was dried at 150 ℃ for 5 minutes to fix 5.6g/m to a nonwoven wallpaper substrate2The smectite of (1).
Further, the coating was applied by dipping at a rate of 40g/m2The coating contained 1.25% by weight of WO3And 1.25 wt% TiO2The photocatalyst coating liquid 1 was dried at 150 ℃ for 5 minutes so that the photocatalyst content was 1.0g/m2And (5) adhering to obtain the non-woven wallpaper serving as the photocatalyst product.
The prepared non-woven fabric wallpaper is 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 24 hours to prepare a sample. In addition, a sample which was not subjected to pretreatment was prepared separately.
Test method
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
The obtained result is shown as a curve 102 in fig. 6.
Fig. 7 shows the results of an acetaldehyde gas removal test performed on a sample which was not pretreated with ultraviolet rays in the same manner as described above.
As is clear from fig. 6 and 7, in the case where the smectite, the photocatalyst and the crosslinking agent were used in the surface treatment portion, the acetaldehyde gas residual ratio was 10% or less at 2 hours for the sample pretreated with the ultraviolet ray, and the catalysis was good. It was confirmed that the sample which had not been pretreated with ultraviolet light had a residual acetaldehyde gas rate of 20% or less at 2 hours, and had a catalytic effect.
Example 3
Preparation of adsorbent coating liquid 1
The adsorbent coating liquid 1 was prepared by adding adipic acid dihydrazide powder to pure water and stirring with a stirrer. The concentration at this time was set to 0.4 wt%.
Preparation of Clay mineral coating liquid 1
A slurry of the clay mineral layer coating liquid 1 was obtained in the same manner as in example 1.
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
The maximum water absorption of a nonwoven wallpaper cut into 50 × 100mm was measured to be 0.964g, so that the amount of the nonwoven wallpaper was 1m2Maximum water absorption W ofAEstimated to be 192.8g/m2。
The non-woven wallpaper was coated with 192.8g/m by dipping2(in this case, K is 100, and the specific gravity D of the coating liquid is 1.000g/cm3) Adsorbent coating liquid 1 was applied and dried at 150 ℃ for 5 minutes to immobilize adipic acid dihydrazide. In this manner, 0.8g/m in solid content was adhered to the nonwoven wallpaper substrate2Adipic acid dihydrazide (2).
Then, the coating was applied by dipping at 199g/m2(in this case, the ratio K was 100, and the specific gravity D of the coating liquid was 1.04g/cm3) The same clay mineral coating liquid 1 as in example 1 was applied, dried at 150 ℃ for 5 minutes, and fixed to a nonwoven wallpaper substrate at 5.6g/m2The smectite of (1).
Further, the coating was applied by dipping at a rate of 40g/m2The coating contained 1.25% by weight of WO3And 1.25 wt% TiO2The photocatalyst coating liquid 1 was dried at 150 ℃ for 5 minutes so that the photocatalyst content was 1.0g/m2And (5) adhering to obtain the non-woven wallpaper serving as the photocatalyst product.
The prepared non-woven fabric wallpaper is 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 24 hours to prepare a sample. In addition, a sample which was not subjected to pretreatment was prepared separately.
Test method
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
The obtained result is shown as a curve 103 in fig. 6.
Fig. 7 shows the result of an acetaldehyde gas removal test performed on a sample which was not pretreated with ultraviolet rays in the same manner as described above, as a curve 502.
As is clear from fig. 6 and 7, in the case where the smectite, the photocatalyst and the adsorbent were used in the surface treatment portion, the acetaldehyde gas remaining rate was 10% or less at 2 hours for the sample pretreated with the ultraviolet ray, and the catalyst effect was good. Even in the sample which had not been pretreated with ultraviolet light, it was confirmed that the residual acetaldehyde gas rate was 10% or less at 2 hours, and that the catalyst effect was sufficient.
Example 4
Preparation of adsorbent coating liquid 1
An adsorbent coating liquid 1 was prepared in the same manner as in example 3.
Preparation of Cross-linker coating liquid 1
A crosslinking agent coating liquid was prepared in the same manner as in example 2.
Preparation of Clay mineral coating liquid 1
A slurry of the clay mineral layer coating liquid 1 was obtained in the same manner as in example 1.
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
The maximum water absorption of a nonwoven wallpaper cut into 50 × 100mm was measured to be 0.964g, so that the amount of the nonwoven wallpaper was 1m2Maximum water absorption W ofAEstimated to be 192.8g/m2。
The non-woven wallpaper was coated with 192.8g/m by dipping2(in this case, K is 100, and the specific gravity D of the coating liquid is 1.000g/cm3) Adsorbent coating liquid 1 was applied and dried at 150 ℃ for 5 minutes to immobilize adipic acid dihydrazide. In this manner, 0.8g/m of adipic acid dihydrazide was inherently present in the nonwoven wallpaper substrate in terms of the solid content thereof2Adipic acid dihydrazide (2).
Then, the nonwoven wallpaper was coated with 199g/m by dipping2(in this case, K was 100, and the specific gravity D of the coating liquid was 1.033g/cm3) Coating the crosslinking agent coating solution 1, drying at 150 ℃ for 5 minutes,ammonium zirconium carbonate was immobilized. In this manner, the amount of the solid component (ZrO) of ammonium zirconium carbonate was added to the nonwoven wallpaper substrate2Converted) based on the solid content of adipic acid dihydrazide 3.8g/m2。
Then, the coating was applied by dipping at 199g/m2(in this case, the ratio K was 100, and the specific gravity D of the coating liquid was 1.04g/cm3) The same clay mineral coating liquid 1 as in example 1 was applied and dried at 150 ℃ for 5 minutes to bond 5.6g/m to a nonwoven wallpaper substrate2The smectite of (1).
Further, the coating was applied by dipping at a rate of 40g/m2The coating contained 1.25% by weight of WO3And 1.25 wt% TiO2The photocatalyst coating liquid 1 was dried at 150 ℃ for 5 minutes so that the photocatalyst content was 1.0g/m2And (5) adhering to obtain the non-woven wallpaper serving as the photocatalyst product.
The prepared non-woven fabric wallpaper is 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 24 hours to prepare a sample. In addition, a sample which was not subjected to pretreatment was prepared separately.
Test method
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
The obtained result is shown as a curve 104 in fig. 6.
Fig. 7 shows the result of an acetaldehyde gas removal test performed on a sample which was not pretreated with ultraviolet rays in the same manner as described above, as a curve 504.
As is clear from fig. 6 and 7, when the smectite, the photocatalyst, the crosslinking agent and the adsorbent were used in the surface treatment portion, the residual ratio of the acetaldehyde gas was 10% or less in the sample pretreated with the ultraviolet ray at 2 hours. In the sample which had not been pretreated with ultraviolet light, it was confirmed that the residual acetaldehyde gas rate was 10% or less at 2 hours, and that the catalyst effect was excellent.
Example 5
Preparation of Cross-linker coating liquid 1
A crosslinking agent coating liquid was prepared in the same manner as in example 2.
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
The maximum water absorption of a nonwoven wallpaper cut into 50 × 100mm was measured to be 0.964g, so that the amount of the nonwoven wallpaper was 1m2Maximum water absorption W ofAEstimated to be 192.8g/m2。
On the nonwoven wallpaper, 199g/m was applied by dipping2(in this case, K was 100, and the specific gravity D of the coating liquid was 1.033g/cm3) The coating solution 1 was applied and dried at 150 ℃ for 5 minutes to immobilize ammonium zirconium carbonate. In this manner, the amount of the solid component (ZrO) of ammonium zirconium carbonate was added to the nonwoven wallpaper substrate2Conversion) cement has a mass of 3.8g/m2Ammonium zirconium carbonate of (4).
Then, the coating was applied by dipping at 40g/m2The coating contained 1.25% by weight of WO3And 1.25 wt% TiO2The photocatalyst coating liquid 1 was dried at 150 ℃ for 5 minutes so that the photocatalyst content was 1.0g/m2And (5) adhering to obtain the non-woven wallpaper serving as the photocatalyst product.
The prepared non-woven fabric wallpaper is 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 24 hours to prepare a sample.
Test method
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
The obtained result is shown as a curve 105 in fig. 6.
Example 6
Preparation of Mixed coating liquid 1 of crosslinking agent and adsorbent
A 19% aqueous solution of ammonium zirconium carbonate was diluted with pure water, and adipic acid dihydrazide powder was added thereto and stirred with a stirrer. The concentrations in this case were set to 1.9 wt% and 0.4 wt%, respectively.
Preparation of Clay mineral coating liquid 1
A slurry of the clay mineral layer coating liquid 1 was obtained in the same manner as in example 1.
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
A nonwoven wallpaper was prepared as a substrate. Fig. 11 shows an SEM photograph of the porous substrate used. Fig. 11 is a view of the surface of a nonwoven wallpaper substrate, in which a dye containing a filler (flake-like sheet) is applied for decoration to a nonwoven substrate containing a polyester fiber as a natural fiber, as shown in the figure.
The maximum water absorption of a nonwoven wallpaper cut into 50 × 100mm was measured to be 0.964g, so that the amount of the nonwoven wallpaper was 1m2Maximum water absorption W ofAEstimated to be 192.8g/m2。
The nonwoven wallpaper was coated by dipping at 196.1g/m2(in this case, K is 100, and the specific gravity D of the coating liquid is 1.017g/cm3) Coating liquid 1, which is a mixture of a crosslinking agent and an adsorbent, was dried at 150 ℃ for 5 minutes to immobilize ammonium zirconium carbonate and adipic acid dihydrazide. In this manner, the amount of the solid component (ZrO) of ammonium zirconium carbonate was added to the nonwoven wallpaper substrate2Conversion) cement has a mass of 3.7g/m2Based on the solid content of adipic acid dihydrazide, the viscosity of the ammonium zirconium carbonate (2) is 0.8g/m2Adipic acid dihydrazide (2).
Then, the coating was applied by dipping at 199g/m2(in this case, the ratio K is 100, and the liquid specific gravity D is 1.04g/cm3) The same clay mineral coating liquid 1 as in example 1 was applied and dried at 150 ℃ for 5 minutes to bond 5.6g/m to a nonwoven wallpaper substrate2The smectite of (1).
Further, the coating was applied by dipping at a rate of 40g/m2The coating contained 1.25% by weight of WO3And 1.25 wt% TiO2The photocatalyst coating liquid 1 was dried at 150 ℃ for 5 minutes so that the photocatalyst content was 1.0g/m2And (5) adhering to obtain the non-woven wallpaper serving as the photocatalyst product.
Fig. 12 shows an SEM photograph of the surface of the obtained photocatalyst product observed with an electron microscope. As shown in the drawing, in the photocatalyst product, a crosslinking agent, an adsorbent, and a photocatalyst that have penetrated from the surface of the porous base material are provided on each of the natural fibers and the polyester fibers.
The prepared non-woven fabric wallpaper is 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 24 hours to prepare a sample. In addition, a sample which was not subjected to pretreatment was prepared separately.
Test method 1 (initial value)
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
The obtained result is shown as a curve 106 in fig. 6.
Fig. 7 shows the result of an acetaldehyde gas removal test performed on a sample which was not pretreated with ultraviolet rays in the same manner as above, as a curve 501.
As is clear from fig. 6 and 7, when the smectite, the photocatalyst, the crosslinking agent and the adsorbent were used in the surface treatment portion, the residual ratio of the acetaldehyde gas was 10% or less in the sample pretreated with the ultraviolet ray at 2 hours. In the sample which had not been pretreated with ultraviolet light, it was confirmed that the residual acetaldehyde gas rate was 10% or less at 2 hours, and that the catalyst effect was excellent.
As the formaldehyde removal test, the concentration of formaldehyde gas was measured for 48 hours for a sample subjected to ultraviolet pretreatment in the same manner as in the test method of example 1, except that formaldehyde gas was injected instead of acetaldehyde gas and a 5L balloon was used.
As a result, it was confirmed that the residual formaldehyde ratio after 48 hours was less than 10%, and that the catalyst effect was excellent.
The toluene removal test was performed in the same manner as the test method of example 1 except that toluene gas was injected instead of acetaldehyde gas and a 5L balloon was used, and the concentration of toluene gas was measured for 48 hours for the sample subjected to ultraviolet pretreatment.
As a result, the toluene remaining rate after 48 hours was 59%. The residual rate of the decomposition of toluene was 65% or less, and the catalytic action was confirmed.
Comparative example 1-1
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
On a nonwoven wallpaper cut into 50 × 100mm, the solid content was 1.0g/m2The photocatalyst coating liquid 1 was applied by dip coating, and dried in a drying oven at 120 ℃ for 5 minutes. The prepared non-woven fabric wallpaper is 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 24 hours to prepare a sample. In addition, a sample which was not subjected to pretreatment was prepared separately.
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
The obtained result is shown as a curve 107 in fig. 6.
Fig. 7 shows the result of an acetaldehyde gas removal test performed on a sample which was not pretreated with ultraviolet rays in the same manner as described above, as a curve 505.
As is clear from fig. 6 and 7, when only the photocatalyst was applied to the surface treatment section, the acetaldehyde residual rate was about 25% at 2 hours for the sample pretreated with ultraviolet light, and the acetaldehyde gas residual rate was about 80% at 2 hours for the sample not pretreated with ultraviolet light, and thus a sufficient catalytic effect was not obtained.
A 48-hour formaldehyde removal test was performed in the same manner as in test method 2 of example 6.
As a result, the residual formaldehyde ratio after 48 hours increased to 250% or more.
The increase in formaldehyde is believed to be due to the organic substrate. It is considered that when the photocatalyst layer is coated only on the organic substrate, the generation of formaldehyde from the organic substrate cannot be suppressed, and therefore, a sufficient catalytic effect cannot be obtained.
A toluene removal test was performed for 48 hours in the same manner as in test method 3 of example 6.
As a result, the toluene remaining rate after 48 hours was 95%.
It is considered that toluene hardly decomposes. It is considered that when the photocatalyst layer is coated only on the organic substrate, toluene cannot be reduced, and therefore a sufficient catalytic effect cannot be obtained.
Comparative example 2
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
A sample was produced in the same manner as in comparative example 1, except that 50 × 100mm glass, which is not a porous base material, was used instead of the nonwoven wallpaper cut into 50 × 100 mm. In addition, a sample which was not subjected to pretreatment was prepared separately.
Test method
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
The obtained result is shown as a curve 108 in fig. 8.
Fig. 7 shows the result of an acetaldehyde gas removal test performed on a sample which was not pretreated with ultraviolet light in the same manner as described above, as a curve 507.
As is clear from fig. 6 and 7, when only the photocatalyst was applied to the surface treatment section, the acetaldehyde gas residual rate was about 10% at 2 hours for both the sample pretreated with ultraviolet light and the sample not pretreated with ultraviolet light, and the glass substrate had a sufficient catalytic effect even with the photocatalyst coating liquid 1 alone.
Further, with respect to examples 1 to 6 and comparative examples 1 and 2, the evaluation of the coating liquid concentration and the amount of adhesion in the surface-treated part, and the measurement of the concentration of acetaldehyde gas and other gases are shown in tables 1-1 and 1-2 below. In the table, the amount of adhesion (g/m)2) The results are shown below the concentration (wt%) of the coating liquid in parentheses, and for the evaluation, the residual ratio of acetaldehyde gas after 2 hours was set to ○, and the residual ratio of acetaldehyde gas after more than 20% was set to ×, the residual ratio of formaldehyde gas after 48 hours was set to ○, and the residual ratio of formaldehyde gas after more than 20% was set to ×, the residual ratio of formaldehyde gas after 48 hours was set to ○, and the residual ratio of formaldehyde gas after more than 60% was set to ×.
As shown in Table 1-1, it was found that the photocatalyst products of examples 1 to 6 all had a residual ratio of acetaldehyde gas of 20% or less after 2 hours, and had a good catalytic action against the ambient atmosphere even when an organic base material was used. In addition, as shown in examples 4 and 6, in the case of using a smectite, a photocatalyst, a crosslinking agent, and an adsorbent in the surface treatment section, a good catalytic effect was confirmed for the sample that was not pretreated with ultraviolet light. In addition, as shown in examples 2 and 3, in the case where the smectite, the photocatalyst, and one of the crosslinking agent or the adsorbent were used in the surface treatment portion, a sufficient catalytic action could also be confirmed. However, as shown in example 1, in the case where the smectite, the photocatalyst and the crosslinking agent were used in the surface-treated portion, a sufficient catalytic action could not be confirmed.
Fig. 8 is a graph showing the catalytic action of the comparative photocatalyst product, and shows the relationship between the irradiation time with light and the residual acetaldehyde rate.
Comparative example 1 is shown in fig. 8 as curve 107 as an example of an organic substrate.
As shown in fig. 8, if the photocatalyst is applied directly to the organic substrate, many harmful organic molecules from the organic substrate are adsorbed and decomposed, so that the apparent catalytic action to the ambient atmosphere is reduced as shown in a curve 107. In contrast, even if the photocatalyst is applied directly to the glass substrate, as shown in curve 108, since no harmful organic molecules are generated from the glass substrate, the catalytic action with respect to the surrounding atmosphere is not reduced. Further, since the curve 108 is substantially the same as those in examples 1 to 6, it is considered that the generation of harmful organic molecules in the organic substrate can be reduced in the photocatalyst articles in examples 1 to 6 as much as in the case of the glass substrate which does not generate harmful organic molecules.
TABLE 1-1
Tables 1 to 2
Example 7
Preparation of Mixed coating liquid 2 of Cross-linking agent and adsorbent
A 19% aqueous solution of ammonium zirconium carbonate was diluted with pure water, and adipic acid dihydrazide powder was added thereto and stirred with a stirrer. The concentrations in this case were 3.5 wt% and 5 wt%, respectively.
Preparation of Clay mineral coating liquid 1
A slurry of the clay mineral layer coating liquid 1 was obtained in the same manner as in example 1.
Preparation of photocatalyst coating liquid 1
A slurry of photocatalyst coating liquid 1 was obtained in the same manner as in example 1.
Sample preparation
The maximum water absorption of a nonwoven wallpaper cut into 50 × 100mm was measured to be 0.964g, so that the amount of the nonwoven wallpaper was 1m2Maximum water absorption W ofAEstimated to be 192.8g/m2。
On the non-woven wallpaper, 199.2g/m was coated by dipping2(in this case, K was 100, and the specific gravity D of the coating liquid was 1.033g/cm3) Mixed coating of coating cross-linking agent and adsorbentLiquid 2 was dried at 150 ℃ for 5 minutes to immobilize ammonium zirconium carbonate and adipic acid dihydrazide. In this manner, the amount of the solid component (ZrO) of ammonium zirconium carbonate was added to the nonwoven wallpaper substrate2Conversion) cement has a mass of 7.0g/m2The ammonium zirconium carbonate (2) has a viscosity of 10.0g/m based on the solid content of adipic acid dihydrazide2Adipic acid dihydrazide (2).
Then, the coating was applied by dipping at 199g/m2(in this case, the ratio K is 100, and the liquid specific gravity D is 1.04g/cm3) The same clay mineral coating liquid 1 as in example 1 was applied and dried at 150 ℃ for 5 minutes to bond 5.6g/m to a nonwoven wallpaper substrate2The smectite of (1).
Further, the coating was applied by dipping at a rate of 40g/m2The coating contained 1.25% by weight of WO3And 1.25 wt% TiO2The photocatalyst coating liquid 1 was dried at 150 ℃ for 5 minutes so that the photocatalyst content was 1.0g/m2And (5) adhering to obtain the non-woven wallpaper serving as the photocatalyst product.
Test method 1 (initial value)
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1.
Fig. 9 is a graph showing the catalytic action of the photocatalyst product according to the embodiment, and shows the relationship between the irradiation time with light and the residual acetaldehyde rate.
The obtained result is shown as a curve 301 in fig. 9.
Test method 2 (after 7 days)
The sample whose initial value was measured was placed on a desk in an office where a white fluorescent lamp was installed and people came in and out for 7 days, and this was used as an actual space test. The illumination on the sample face was about 350lx, and lights were off at night, on a weekday. The acetaldehyde gas removal test was performed under the same conditions as in test method 1, and the data was obtained after leaving the actual space for 7 days.
The obtained result is shown as a curve 302 in fig. 9.
Test method 3 (after 15 days)
The sample subjected to the test of leaving the actual space for 7 days was further left to stand for 8 days under the same conditions as in test method 2, and the acetaldehyde gas removal test was carried out under the same conditions as in test method 1, and the data obtained after leaving the actual space for 15 days were obtained.
The obtained result is shown as a curve 303 in fig. 9.
Comparative examples 1 to 2
The same samples as in comparative example 1-1 were prepared, and acetaldehyde gas removal tests were conducted in the same manner as in example 7 at the initial stage, after 7 days, and after 15 days.
Fig. 10 is a graph showing the catalytic action of comparative photocatalyst products, and shows the relationship between the irradiation time with light and the residual acetaldehyde rate.
The initial value is shown in a curve 401, the value after 7 days is shown in a curve 402, and the value after 15 days is shown in a curve 403.
As shown in fig. 9, it was found that the photocatalyst product according to example 7 had a residual acetaldehyde rate of 30% or less after 2 hours both after 7 days and after 15 days, had a sufficient catalytic effect on the ambient atmosphere, and had good life characteristics.
On the other hand, as shown in fig. 10, it was found that the photocatalyst product according to comparative example 1 had an acetaldehyde gas remaining rate of more than 80% after 2 hours both after 7 days and after 15 days, and had a decreased catalytic action on the ambient atmosphere and a poor life characteristic.
Examples 8-1 and 8-2
Preparation of Mixed coating liquid 3 of crosslinking agent and adsorbent
A 19% aqueous solution of ammonium zirconium carbonate was diluted with pure water, and adipic acid dihydrazide powder was added thereto and stirred with a stirrer. The concentrations at this time were set to 5% by weight (ZrO)2Converted), 7.5 wt%.
Preparation of Clay mineral coating liquid 2
The smectite powder was put into pure water stirred by a stirrer so that the smectite powder became 4% by weight, stirred for 5 minutes, treated with a homogenizer for 15 minutes, and left to stand for 24 hours. The slurry was again stirred and homogenized by a stirrer to obtain a slurry as the clay mineral layer coating liquid 2.
Preparation of photocatalyst coating liquid 2
Preparation of 10% by weight of WO in pure water3The slurry of (4), 10% by weight of TiO is added based on the weight of the slurry2A photocatalyst. This was diluted with pure water so that the total solid content became 4.5 wt%, thereby preparing photocatalyst coating liquid 2.
Sample preparation
The maximum water absorption of the substrate, which was measured for a nonwoven wallpaper cut to 50 × 100mm, was 0.964g, so that the amount of the substrate per 1m was measured2Water absorption W of the substrateAEstimated to be 192.8g/m2。
The nonwoven wallpaper was coated by dipping at 28.9g/m2(in this case, K was 14.3, and the specific gravity D of the coating liquid was 1.049g/cm3) Coating liquid 3 was applied and dried at 170 ℃ for 3 minutes to immobilize ammonium zirconium carbonate and adipic acid dihydrazide. On a nonwoven wallpaper substrate, the amount of the solid component (ZrO) of ammonium zirconium carbonate is used2Conversion) cement has a mass of 1.45g/m2Based on the solid content of adipic acid dihydrazide, the viscosity of the ammonium zirconium carbonate (2.17 g/m)2Adipic acid dihydrazide (2).
Then, the mixture was passed through a doctor blade at 62.3g/m2(in this case, K was 31, and the specific gravity D of the coating liquid was 1.043g/cm3) The coating liquid 2 was applied to the clay mineral, and dried at 170 ℃ for 4 minutes to immobilize the smectite. The non-woven wallpaper was adhered with 2.5g/m2The smectite of (1).
Further, the nonwoven wallpaper was scraped off at a rate of 26.5g/m by a doctor blade2Coating photocatalyst coating liquid 2, drying at 120 deg.C for 3 min to make photocatalyst at 1.2g/m2The nonwoven wallpaper of example 8-1 was prepared by bonding.
In addition, as example 8-2, a doctor blade was used in an amount of 45g/m2A non-woven wallpaper coated with the photocatalyst coating liquid 2. The drying temperature was set to 120 ℃ and the drying time was set to 5 minutes. The amount of the photocatalyst in this case was 2.0g/m2。
The nonwoven fabric wallpapers of examples 8-1 and 8-2 were used at a ratio of 20W/m2By means of the adjusted UV lamp FL20SBLAnd pretreating for 24 hours to obtain a sample.
Test method
Acetaldehyde gas removal test
The acetaldehyde gas concentration was measured for 2 hours in the same manner as in example 1. It was found that the residual ratio of acetaldehyde gas was 10% or less in example 8-1 and 5% or less in example 8-2, and that the catalyst had good catalytic activity.
Black cloth transfer test method
The surface of the nonwoven wallpaper separately produced in the same manner as in the production of the above sample was rubbed with a black wool cloth, and the color transferred to the black cloth was observed. The nonwoven fabric wallpaper was rubbed against the black cloth by placing the black cloth on the nonwoven fabric wallpaper placed on a flat plate, applying a load of 3kgf to a circular surface having a diameter of 17mm from the black cloth, and moving the nonwoven fabric wallpaper 10cm in this state. The pressure at this time was 13.2g/mm2。
FIG. 13 is a photograph showing the surface of a black cloth as a result of a transfer test of the nonwoven fabric wallpaper of example 8-1, and FIG. 14 is a photograph showing the surface of a black cloth as a result of a transfer test of the nonwoven fabric wallpaper of example 8-2.
In example 8-1, the black cloth was hardly changed, but in example 8-2, the change was white. The cause of white color was confirmed by a portable fluorescent X-ray measuring device (DELTA Professional fluorescent X-ray analyzer, trade name manufactured by Olympus Corporation), and the result was confirmed as a photocatalyst component. In the example of the porous substrate, 1.2g/m was found2The amount of the photocatalyst (2) fixed was 2.0g/m2The amount of the photocatalyst fixed tends to be slightly excessive.
Example 9 and comparative example 3
Preparation of Cross-linker coating liquid 2
19 wt% (ZrO) was added2Conversion) ammonium zirconium carbonate aqueous solution was diluted with pure water to prepare 0.75% by weight (ZrO) solution2Converted) of an aqueous solution.
Preparation of photocatalyst coating liquid 3
Will be dispersed with 10 wt% of WO3The slurry of (3) was diluted with pure water and adjusted so that the amount of solid components became 0.5% by weight w.
Sample preparation
The maximum water absorption capacity capable of absorbing pure water was measured for a pile fabric blank cut into 50 × 100mm, and it was 7.94g, so that each 1m2Water absorption W of the substrateAEstimated to 1588g/m2。
The pile fabric blank was coated by dipping at a rate of 200g/m2(in this case, K was 12.4, and the specific gravity D of the coating liquid was 1.013g/cm3) The coating liquid 2 was applied and dried at 150 ℃ for 3 minutes to immobilize ammonium zirconium carbonate. On the pile fabric grey cloth, the solid content (ZrO) of ammonium zirconium carbonate is used2Conversion) cement has a mass of 1.5g/m2Ammonium zirconium carbonate of (4).
Next, the pile fabric blank was subjected to a simple gravure test at a ratio of 200g/m2Coating photocatalyst coating liquid 3, and drying at 120 deg.C for 3 min to obtain WO3The photocatalyst is used at a concentration of 1.0g/m2The resultant fabric was bonded to obtain a pile fabric blank of example 9.
A pile fabric blank was produced in the same manner as in example 9, except that the crosslinking agent coating liquid 2 was not applied as comparative example 3.
The pile fabric of example 9 and comparative example 3 and the pile fabric of Blank (Blank) which had not been treated at all were used in such a manner that the weight of the pile fabric was 20W/m2The ultraviolet lamp FL20SBL thus adjusted was pretreated for 12 hours to prepare a sample.
Acetaldehyde removal test method
In the acetaldehyde gas removal test, a sample was placed in a chamber having a volume of 1.5L, and the chamber was purged with air and adjusted so that the temperature and humidity became 25 ℃ and 20%, and then acetaldehyde gas was injected into the chamber with a syringe so that the concentration thereof became 10 ppm. For the removal test, an ultraviolet sharp cut filter (CLAREX UV cut filter N-169) was interposed between the lamp and the chamber, and the sample surface was irradiated with light at 6000lx using a white fluorescent lamp FL20SW while cutting off UV light of 380nm or less, and the concentration of acetaldehyde gas was measured for 1 hour using an optoacoustic multi-gas monitor inova 1412i (manufactured by Luma Sense Technologies). The obtained results are shown in fig. 15.
Fig. 15 is a graph showing the relationship between the light irradiation time and the residual acetaldehyde rate.
In the figure, 501 denotes a blank pile fabric blank, 502 denotes the results of comparative example 3, and 503 denotes the results of example 9. The fabric blank of comparative example 3, in which only the photocatalyst was applied, had an acetaldehyde residual rate of 90% or more as shown in 502, and no catalytic action, but the fabric blank of example 9, in which ammonium zirconium carbonate and the photocatalyst were applied, had an acetaldehyde gas residual rate of 50% or less as shown in 503, and it was found that the treatment with ammonium zirconium carbonate had a good catalytic action.
In Table 1-1 and Table 1-2, the coating liquid concentration and the amount of adhesion in the surface-treated portions and the evaluation of the measurement of the concentration of acetaldehyde gas are also shown in examples 7, 8-1, 8-2, and 9 and comparative example 3.
Several embodiments of the present invention have been described, but these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments may be implemented in other various forms, and various omissions, substitutions, and changes may be made without departing from the spirit of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalent scope thereof.
Claims (14)
1. A photocatalyst product comprising:
porous base material, and
and a surface treatment section provided on the porous substrate, the surface treatment section including ammonium zirconium carbonate and a photocatalyst containing tungsten oxide.
2. The photocatalyst article of claim 1, wherein the surface treatment further comprises at least 1 of a smectite-containing clay mineral or adipic dihydrazide.
3. The photocatalyst article of claim 1, wherein the surface treatment comprises:
a layer containing ammonium zirconium carbonate provided on the porous substrate, and
a photocatalyst layer containing the photocatalyst disposed on the layer containing ammonium zirconium carbonate.
4. The photocatalyst article of claim 3, further comprising a clay mineral layer disposed between the layer comprising ammonium zirconium carbonate and the photocatalyst layer, comprising a clay mineral comprising smectite.
5. The photocatalyst article of claim 3, further comprising a layer comprising adipic acid dihydrazide disposed between the layer comprising ammonium zirconium carbonate and the photocatalyst layer.
6. The photocatalyst article of claim 3, wherein the layer comprising ammonium zirconium carbonate further comprises adipic acid dihydrazide.
7. The photocatalyst article as set forth in claim 1, wherein in a chamber having a volume of 0.5L into which 10ppm of acetaldehyde is introduced, a white fluorescent lamp FL20SW is used, and light irradiation is performed at 6000 lux illumination while light of 380nm or less is cut off by an ultraviolet cut filter, and 60% or more of acetaldehyde is reduced when the photocatalyst article is left at room temperature, normal pressure, and a humidity of 20% for 2 hours.
8. The photocatalyst article according to any one of claims 1 to 7, wherein the porous substrate is a nonwoven fabric.
9. The photocatalyst article according to any one of claims 1 to 7, wherein the porous substrate is wallpaper.
10. The photocatalyst article according to any one of claims 1 to 7, wherein the porous substrate is a wall cloth.
11. The photocatalyst article according to any one of claims 1 to 7, wherein the porous substrate is a nonwoven wallpaper.
12. A photocatalyst product comprising:
porous base material, and
and a surface treatment section provided on the porous base material, the surface treatment section including a clay mineral containing a smectite and a photocatalyst containing tungsten oxide.
13. The photocatalyst product according to claim 12, wherein the surface-treated portion comprises a clay mineral layer containing a clay mineral containing smectite provided on the porous substrate, and a photocatalyst layer containing the photocatalyst provided on the clay mineral layer.
14. The photocatalyst article as set forth in claim 12, wherein in a chamber having a volume of 0.5L into which 10ppm of acetaldehyde is introduced, a white fluorescent lamp FL20SW is used, and light irradiation is performed at 6000 lux illumination while light of 380nm or less is cut off by an ultraviolet cut filter, and 60% or more of acetaldehyde is reduced when the photocatalyst article is left at room temperature, normal pressure, and a humidity of 20% for 2 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT202100007346A1 (en) * | 2021-03-25 | 2022-09-25 | Nikitex S R L | NON-WOVEN FABRIC FOR THE INTERNAL COVERING OF TRANSPORT MEANS SUITABLE FOR ADSORBING VOLATILE ORGANIC COMPOUNDS |
| CN116020432A (en) * | 2021-10-27 | 2023-04-28 | 夏普株式会社 | Photocatalyst coating structure and photocatalyst coating member |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019207A (en) * | 2009-09-16 | 2011-04-20 | 住友化学株式会社 | Photocatalyst composite and photocatalytic functional product using the same |
| WO2011099510A1 (en) * | 2010-02-12 | 2011-08-18 | 住友化学株式会社 | Precoat solution for underlayer for photocatalyst layer, organic base material having photocatalyst layer attached thereto, and product having photocatalytic function |
| CN102188955A (en) * | 2010-03-03 | 2011-09-21 | 株式会社科特拉 | Optical-regenerable absorption material and use thereof |
| JP2012035151A (en) * | 2010-08-03 | 2012-02-23 | Sumitomo Chemical Co Ltd | Method for manufacturing photocatalyst structure, and photocatalyst functional product |
| CN102481566A (en) * | 2010-07-29 | 2012-05-30 | Toto株式会社 | Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material |
-
2019
- 2019-12-02 CN CN201911210828.9A patent/CN111715301B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019207A (en) * | 2009-09-16 | 2011-04-20 | 住友化学株式会社 | Photocatalyst composite and photocatalytic functional product using the same |
| WO2011099510A1 (en) * | 2010-02-12 | 2011-08-18 | 住友化学株式会社 | Precoat solution for underlayer for photocatalyst layer, organic base material having photocatalyst layer attached thereto, and product having photocatalytic function |
| CN102188955A (en) * | 2010-03-03 | 2011-09-21 | 株式会社科特拉 | Optical-regenerable absorption material and use thereof |
| CN102481566A (en) * | 2010-07-29 | 2012-05-30 | Toto株式会社 | Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material |
| JP2012035151A (en) * | 2010-08-03 | 2012-02-23 | Sumitomo Chemical Co Ltd | Method for manufacturing photocatalyst structure, and photocatalyst functional product |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT202100007346A1 (en) * | 2021-03-25 | 2022-09-25 | Nikitex S R L | NON-WOVEN FABRIC FOR THE INTERNAL COVERING OF TRANSPORT MEANS SUITABLE FOR ADSORBING VOLATILE ORGANIC COMPOUNDS |
| CN116020432A (en) * | 2021-10-27 | 2023-04-28 | 夏普株式会社 | Photocatalyst coating structure and photocatalyst coating member |
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