CN111715301B - Photocatalyst article - Google Patents
Photocatalyst article Download PDFInfo
- Publication number
- CN111715301B CN111715301B CN201911210828.9A CN201911210828A CN111715301B CN 111715301 B CN111715301 B CN 111715301B CN 201911210828 A CN201911210828 A CN 201911210828A CN 111715301 B CN111715301 B CN 111715301B
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- porous substrate
- coating liquid
- layer
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 182
- 239000000758 substrate Substances 0.000 claims abstract description 119
- 239000002734 clay mineral Substances 0.000 claims abstract description 50
- 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 49
- 238000004381 surface treatment Methods 0.000 claims abstract description 41
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 37
- 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 9
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 120
- 239000000463 material Substances 0.000 claims description 41
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 33
- 239000004745 nonwoven fabric Substances 0.000 claims description 17
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 48
- 238000000576 coating method Methods 0.000 description 148
- 239000011248 coating agent Substances 0.000 description 145
- 239000007788 liquid Substances 0.000 description 113
- 239000007789 gas Substances 0.000 description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- 239000003431 cross linking reagent Substances 0.000 description 43
- 238000002360 preparation method Methods 0.000 description 41
- 239000003463 adsorbent Substances 0.000 description 36
- 239000007787 solid Substances 0.000 description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000004744 fabric Substances 0.000 description 28
- 238000012360 testing method Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 25
- 238000010998 test method Methods 0.000 description 24
- 238000003618 dip coating Methods 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 21
- 230000005484 gravity Effects 0.000 description 20
- 239000002002 slurry Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 150000007530 organic bases Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000004971 Cross linker Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 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
- 238000005259 measurement Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 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 3
- 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
- 230000003100 immobilizing effect Effects 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008199 coating composition Substances 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
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 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 2
- 238000000034 method Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013043 chemical agent Substances 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
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229940030980 inova Drugs 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
- 238000002156 mixing 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
- 239000005416 organic matter Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 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
- 230000008569 process Effects 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
- 210000002268 wool Anatomy 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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 application relate to photocatalyst articles. The purpose is to obtain a photocatalyst article having excellent catalytic activity with respect to the surrounding atmosphere. The photocatalyst article according to the embodiment comprises a porous substrate, and a surface treatment unit provided on the porous substrate, wherein the surface treatment unit comprises a photocatalyst containing tungsten oxide and at least 1 of ammonium zirconium carbonate or a clay mineral containing smectite.
Description
The present application is based on Japanese patent application 2019-051293 (application date: 2019, 3, 19), and Japanese patent application 2019-192159 (application date: 2019, 10, 21), which are given priority. The present application incorporates the entire contents of these japanese patent applications by reference thereto.
Technical Field
Embodiments of the present application relate to photocatalyst articles.
Background
The photocatalyst generates excited electrons and holes by light, and has a strong oxidizing power. This oxidizing power is used as a catalytic action for decomposition and removal of harmful organic molecules, sterilization, maintenance of hydrophilicity of a substrate, and the like. When the photocatalyst is applied to an inorganic substrate such as a glass substrate, the photocatalyst can exert a catalytic action with respect to the surrounding atmosphere. On the other hand, nonwoven wallpaper, cloth products, and the like are treated with chemical agents, dyed, and the like, and therefore contain many various organic components. Therefore, when a photocatalyst is used for an organic substrate such as a nonwoven fabric, many harmful organic molecules from the organic substrate are adsorbed and decomposed, and thus there is a problem that the catalytic action with respect to the surrounding atmosphere is lowered.
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 article including:
porous base material
And a surface treatment unit provided on the porous substrate, the surface treatment unit including a photocatalyst containing tungsten oxide and at least 1 of ammonium zirconium carbonate and a clay mineral containing smectite.
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 article according to embodiment 1.
Fig. 3 is a schematic diagram showing another configuration of the photocatalyst article according to embodiment 1.
Fig. 4 is a schematic diagram showing another configuration of the photocatalyst article according to embodiment 1.
Fig. 5 is a schematic diagram showing the structure of a photocatalyst product according to embodiment 2.
Fig. 6 is a graph showing the catalytic action of the photocatalyst article according to the embodiment.
Fig. 7 is a graph showing catalytic action of other samples of the photocatalyst article according to the embodiment.
Fig. 8 is a graph showing the catalytic action of the comparative photocatalyst article.
Fig. 9 is a graph showing the catalytic action of the photocatalyst article according to the embodiment.
Fig. 10 is a graph showing the catalytic action of the comparative photocatalyst article.
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 showing the black cloth surface of the result of the transfer test of the photocatalyst article according to the embodiment.
Fig. 14 is a photograph showing the black cloth surface of 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 rate of acetaldehyde.
Detailed Description
The photocatalyst article according to the embodiment includes a porous base material and a surface treatment portion provided on the porous base material. The surface treatment section contains a photocatalyst containing tungsten oxide and at least 1 of clay mineral containing smectite or ammonium zirconium carbonate.
According to the embodiment, by using at least 1 of clay mineral containing smectite or zirconium ammonium carbonate for the surface treatment portion, when using, for example, an organic substrate as the porous substrate, gas emission from the organic substrate can be prevented. In addition, the photocatalyst can be prevented from being brought into contact with an organic component in the organic base material and from emitting, for example, an aldehyde gas generated by a photocatalytic reaction. Thus, a state in which the photocatalytic activity with respect to the surrounding atmosphere is good can be obtained. In addition, the photocatalytic effect is effective in the case of using an organic porous substrate, particularly, nonwoven wallpaper or cloth product as the porous substrate.
The photocatalyst article according to the embodiment can be classified into the following photocatalyst articles according to embodiment 1, embodiment 2, and embodiment 3.
The photocatalyst article according to embodiment 1 comprises a porous substrate and a surface treatment portion provided on the porous substrate, the surface treatment portion including a clay mineral containing smectite and a photocatalyst containing tungsten oxide.
Smectite is a silicate mineral with a layered crystal structure. Examples of smectites (smeites) that can be used in the embodiments include saponite, hectorite, montmorillonite (montmorillonite), and hectorite (stevensite). A high aspect ratio smectite having a shape in which crystals in the form of films are laminated and a smectite having high transparency can be used.
According to embodiment 1, the porous substrate is surface-treated with a smectite having a shape in which crystals in the form of a film are laminated, whereby the porous substrate has excellent barrier properties against organic components. For example, when a photocatalyst is used for an organic base material coated with an aqueous dye obtained by dispersing an acrylic emulsion, the component of the acrylic emulsion, i.e., the organic substance, dissolves out from the organic base material, and covers the photocatalyst. In contrast, if the organic base material is subjected to the smectite treatment, the dissolved organic matter is prevented from contacting the photocatalyst, and deterioration of the photocatalyst performance and emission of aldehyde-based or carboxylic acid-based gas due to the reaction of the organic matter with the photocatalyst are prevented. In addition, the photocatalyst can be prevented from reacting by direct contact with the organic base material. Thus, a photocatalyst article having a good catalytic effect against the surrounding atmosphere can be obtained.
Fig. 1 is a schematic diagram showing the structure of the photocatalyst article according to embodiment 1.
As shown in the figure, the photocatalyst article 10 according to embodiment 1 includes, for example, a porous base material 1 and a surface treatment portion 4 provided on the porous base material 1. The surface treatment section 4 includes a clay mineral layer 2 and a photocatalyst layer 3 sequentially formed on a porous base material 1. When a substrate having a non-uniform surface such as a nonwoven fabric is used as the porous substrate 1, the clay mineral layer 2 does not have to be a uniform layer, and may be scattered on the substrate surface. Similarly, the photocatalyst layer 3 is not necessarily a uniform layer, and may be scattered on the surface of the substrate. In the case where the porous substrate 1 absorbs clay minerals, the clay mineral layer 2 may penetrate into the substrate.
The surface treatment portion 4 may include a region rich in clay mineral containing smectite, a region rich in photocatalyst, and a region where both clay mineral and photocatalyst are mixed. The substance exhibiting the catalytic action is a photocatalyst exposed on the surface treatment portion 4.
As the porous substrate, an organic substrate such as a cloth product, a nonwoven fabric, a woven fabric, a resin film, a resin sheet, or the like, an organic substrate including a paint or dye containing an organic substance, a pigment, a binder, a paste, an oil agent, or the like, a product using at least 1 of them, or the like can be used.
The amount of the smectite to be used in the porous base material may be set to 1.0 to 6.0g/m in terms of solid content 2 . If it exceeds 6.0g/m 2 When the amount of the photocatalyst particles is less than 1.0g/m, the texture and flexibility of the substrate are lost, or the photocatalyst particles immobilized thereon are easily detached 2 However, the weight per unit area, the surface area, the manufacturing process, and the like of the porous substrate vary depending on the porous substrate, and an appropriate range is determined depending on the porous substrate.
The clay mineral layer 2 may be formed by applying a coating liquid containing a smectite by a coating method such as dip coating, gravure coating, spin coating, bar coating, or spin screen coating. For example, if the coating composition is applied to both surfaces of a porous substrate such as dip coating, for example, 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 prevented. In addition, the photocatalyst can be prevented from reacting by contact with the organic base material.
The photocatalyst used in the embodiment may be at least 1 metal oxide selected from titanium oxide, zinc oxide, tungsten oxide, niobium oxide, tin oxide, and the like. In addition, at least 1 of zirconia, platinum, ruthenium, copper, or the like may be added to the photocatalyst.
The amount of the photocatalyst to be used to the porous substrate may be set to 0.2 to 2.0g/m in terms of solid content 2 . If it exceeds 2.0g/m 2 If the particle size is less than 0.2g/m, the particles are liable to fall off, which is a problem 2 However, the catalytic action tends to be insufficient, but the amount varies depending on the weight per unit area, the surface area, the manufacturing process, and the like of the porous substrate, and the appropriate range is determined depending on 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 spin screen coating.
The surface treatment portion may further include 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 organic substances contained in the porous base material. By reacting (immobilizing) ammonium zirconium carbonate with carboxyl groups or hydroxyl groups of water-soluble polymers in a porous substrate such as an organic substrate like a nonwoven fabric, unnecessary gas release or bleeding can be prevented. According to the embodiment, by further including ammonium zirconium carbonate in the surface treatment portion, a photocatalyst product having a better catalytic action with respect to the surrounding atmosphere can be obtained.
The amount of zirconium ammonium carbonate used relative to the porous substrate is based on ZrO 2 Can be set to 0.1 to 10.0g/m in terms of solid content 2 . If it exceeds 10.0g/m 2 If the softness of the base material is lost, the base material becomes a state where the softness is less than 0.1g/m 2 Although immobilization tends to be insufficient, the preferable range is not limited, and varies depending on the weight per unit area, surface area, manufacturing history, and the like of the porous substrate.
Here, zrO 2 The conversion means that firstly, the ammonium zirconium carbonate solution is weighed and then the dry solids are completely evaporated, and the weight of the evaporated dry solids is divided by (NH) 4 ) 2 [Zr(CO 3 ) 2 (OH) 2 ]Molecular weight 281.33 of (2) and multiplying by ZrO 2 Molecular weight 123.22 of (C) to determine the evaporation of dry solid ammonium zirconium carbonate into ZrO 2 Weight conversion value of (2). The amount of adhesion per unit area (solid component amount) can be calculated using the weight conversion value as the weight of the solid component.
Adipic acid dihydrazide is used as an adsorbent for adsorbing harmful organic molecules such as formaldehyde. According to the embodiment, by using adipic dihydrazide in the surface treatment portion, a photocatalyst product having a better catalytic action with respect to the surrounding atmosphere can be obtained.
The amount of adipic acid dihydrazide to be used in the porous substrate may be set to 0.5 to 15.0g/m in terms of solid content 2 . If it exceeds 15.0g/m 2 If the content is less than 0.1g/m, the powder may be produced 2 However, the preferred range is not limited, and is different depending on the weight per unit area, the surface area, the manufacturing process, and the like of the porous substrate.
Fig. 2 to 4 show model diagrams showing other configurations of the photocatalyst article according to embodiment 1.
In the case where ammonium zirconium carbonate is applied, for example, as shown in fig. 2, the crosslinking agent layer 5 containing ammonium zirconium carbonate may be formed before the clay mineral layer 2 is formed on the porous base material 1. The obtained photocatalyst article 20 comprises a crosslinking agent layer 5, a clay mineral layer 2, and a photocatalyst layer 3, which are formed in this order on a porous substrate 1, as a surface treatment portion 4-1.
In the case where 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.
In the case of applying adipic acid dihydrazide, 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 substrate. The obtained photocatalyst article 30 comprises, as the surface treatment section 4-2, the adsorbent layer 6, the clay mineral layer 2, and the photocatalyst layer 3 which are formed in this order on the porous base material 1. In the case where the porous base material 1 absorbs the adsorbent or the clay mineral, the adsorbent layer 6 or the clay mineral layer 2 may penetrate into the porous base material.
In the case where both the cross-linking agent layer and the adsorbent layer are applied, for example, as shown in fig. 4, the cross-linking agent layer 5 and the adsorbent layer 6 may be formed sequentially, or the adsorbent layer 6 and the cross-linking agent layer 5 may be formed sequentially, before the clay mineral layer is formed on the porous base material 1. The obtained photocatalyst article 40 has a cross-linking agent layer 5, an adsorbent layer 6, a clay mineral layer 2, and a photocatalyst layer 3 laminated in this order on a porous substrate 1 as surface treatment sections 4-3. In the case where 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 penetrate into the porous base material. Instead of forming the crosslinking agent layer 5 and the adsorbent layer 6, a coating liquid obtained by mixing the crosslinking agent and the adsorbent may be used to form a layer containing both the crosslinking agent and the adsorbent, not shown.
The cross-linking agent layer may be disposed closer to the porous substrate than the adsorbent layer because it reacts with carboxyl groups, hydroxyl groups, or the like of the water-soluble polymer in the porous substrate. By further comprising ammonium zirconium carbonate and adipic acid dihydrazide, a photocatalyst article having a further good catalytic effect with respect to the surrounding atmosphere can be obtained. In addition, when the porous substrate becomes difficult to be impregnated with the adsorbent layer 6 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 crosslinking agent layer and the adsorbent layer may be formed by applying a coating liquid containing a crosslinking agent and a coating liquid containing an adsorbent by using a coating method such as dip coating, gravure coating, spin coating, bar coating, or spray coating, respectively. For example, if the coating composition is applied to both surfaces of a porous substrate such as dip coating, for example, 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 photocatalyst can be inhibited from reacting in contact with the organic base material.
Fig. 5 is a schematic diagram showing the structure of the photocatalyst article according to embodiment 2.
The photocatalyst article 50 according to embodiment 2 includes a porous substrate 1, and a surface treatment portion 4-4 provided on the porous substrate 1, and as the surface treatment portion 4-4, a cross-linking agent layer 5 and a photocatalyst layer 3 containing tungsten oxide are laminated in this order. When a substrate having a non-uniform surface such as a nonwoven fabric is used as the porous substrate 1, the cross-linking agent layer 5 does not have to be a uniform layer, and may be scattered on the substrate surface. Similarly, the photocatalyst layer 3 is not necessarily a uniform layer, and may be scattered on the surface of the substrate. In the case where the porous substrate absorbs the crosslinking agent, the crosslinking agent layer 5 may penetrate into the porous substrate.
In the surface treatment portion 4, there may be a region rich in ammonium zirconium carbonate, a region rich in photocatalyst, and a region where both ammonium zirconium carbonate and photocatalyst are mixed. The substance exhibiting the catalytic action is a photocatalyst exposed on the surface treatment portion 4.
According to embodiment 2, when a crosslinking agent containing ammonium zirconium carbonate is used, the porous substrate, for example, carboxyl groups, hydroxyl groups, or the like of a water-soluble polymer in the organic substrate is reacted with ammonium zirconium carbonate to be insoluble, whereby the porous substrate can be prevented from releasing or bleeding out unnecessary gas. By preventing the reaction between the photocatalyst and the porous substrate in this manner, a photocatalyst product having a good catalytic effect with respect to the surrounding atmosphere can be obtained.
The porous substrate, the surface treatment unit, the crosslinking agent layer, the photocatalyst layer containing tungsten oxide, and the like used in embodiment 2 are the same as those used in embodiment 1. The amount of ammonium zirconium carbonate, the photocatalyst layer, and the like used for the porous substrate was the same as in embodiment 1.
The photocatalyst article according to embodiment 3 comprises a porous substrate and a surface treatment portion provided on the porous substrate, wherein the surface treatment portion comprises a clay mineral containing smectite and a photocatalyst containing tungsten oxide. Further, in the photocatalyst product, the volume of the chamber was 0.5L, light was irradiated from the white fluorescent lamp FL20SW, UV light of 380nm or less was cut off by a CLAREX UV cut-off filter N-169 (Nitto resin Co., ltd.) and the illuminance was set to 6000 lux, and acetaldehyde concentration of 10ppm was reduced by 60% or more in 2 hours under conditions of normal temperature, normal pressure and humidity of 20%.
According to embodiment 3, a photocatalyst article having a good catalytic effect with respect to the surrounding atmosphere can be obtained.
The porous base material used in embodiment 3 and the member of the surface treatment section are the same as those used in embodiment 1. The amount of the photocatalyst layer or the like to be used for the porous substrate is the same as that 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 adhered to the porous substrate by the application of the coating liquid is affected by the material of the porous substrate. For example, in the case where the porous substrate 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 adhered so as to cover the surface of the porous substrate. On the other hand, in the case where the porous base material 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 adhered so as to cover 1 fiber constituting the porous base material. In the production process of the photocatalyst article according to the embodiment, the concentration of the coating liquid and the coating amount can be adjusted in consideration of the ease of penetration of the coating liquid into the porous substrate to be used.
As a criterion for the permeability of the coating liquid to the porous substrate, the maximum water absorption amount that the porous substrate 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 substrate W (g/m 2 ) Can be represented by the following formula (1).
F W ＝K/100×W A ×C/100×(D/D 0 ) (1)
F W : amount of solid component to be fixed (g/m 2 )
K: any value exceeding 0 and 100 or less
W A : maximum water absorption capacity (g/m) capable of absorbing pure water 2 )
C: concentration of solid content of coating liquid (wt.%)
D: specific gravity (g/cm) of coating liquid 3 )
D 0 : specific gravity of water (g/cm) 3 )
In which W is A Maximum water absorption capacity (g/m) capable of absorbing pure water per unit area of the porous substrate 2 ) K is an arbitrary value exceeding 0 and not more than 100 selected according to the method of coating or the state of coating of the coating liquid, C is the solid content concentration (wt%) of the coating liquid, and D is the specific gravity (g/cm) of the coating liquid 3 )，D 0 Specific gravity of water (g/cm) 3 )。
The solid content concentration C (wt%) of each coating liquid varies depending on the member used in the coating liquid. In the case of smectite, 0 to 5% by weight. When the solid content concentration C of the coating liquid containing the smectite exceeds 5 wt%, the viscosity tends to be high and water dispersion tends to be difficult, so that the solid content C can be set to 5 wt% or less. In the case of ammonium zirconium carbonate, the process is carried out as ZrO 2 0 to 20% by weight. The solid content concentration C of the coating liquid containing Ammonium Zirconium Carbonate (AZC) exceeds 20 wt% (ZrO) 2 Converted), ammonia odor tends to be strong and the working environment tends to be deteriorated, so that it can be set to 20 wt% or less. In the case of adipic acid dihydrazide, it may be set to 0 to 11% by weight. Since the solubility of adipic Acid Dihydrazide (ADH) with respect to water is 11 wt% at 30 ℃, the solid content concentration C of the coating liquid containing adipic Acid Dihydrazide (ADH) may be set to 11 wt% or less.
The solid content C is preferably 1 to 3% by weight in the case of smectite and ZrO in the case of ammonium zirconium carbonate 2 The conversion may be set to 0.1 to 10% by weight, and in the case of adipic acid dihydrazide, it may be set to 0.1% to the maximum8% by weight.
Hereinafter, embodiments will be specifically described with reference to examples.
Examples
Example 1
Preparation of clay mineral coating liquid 1
The smectite powder was poured into the pure water stirred by the stirrer so as to be 2.8 wt% and stirred for 5 minutes, and then treated with the homogenizer for 15 minutes, and left for 24 hours. This was stirred again with a stirrer and homogenized to obtain a slurry as the clay mineral layer coating liquid 1.
Preparation of photocatalyst coating liquid 1
Preparation of a composition containing 10 wt% WO 3 10 wt% TiO 2 Is diluted with pure water so that the total solid content becomes 2.5 wt%.
Sample preparation
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity capable of absorbing pure water was measured and found to be 0.964g, so that every 1m 2 Maximum water absorption W of (2) A Estimated to be 192.8g/m 2 。
On the non-woven wallpaper, 199g/m was applied by dip coating 2 (in this case, K was 100, and the specific gravity D of the coating liquid was 1.03 g/cm) 3 ) Coating clay mineral coating liquid 1, drying at 150deg.C for 5 min, and adhering 5.6g/m on non-woven wallpaper substrate 2 Is a smectite of (2).
Further, the coating was carried out by dip coating at a rate of 40g/m 2 Coating comprises 1.25% by weight of WO 3 1.25 wt% TiO 2 The photocatalyst coating liquid 1 of (2) was dried at 150℃for 5 minutes to give a photocatalyst of 1.0g/m 2 Cementing to obtain the non-woven wallpaper serving as a photocatalyst product.
The non-woven fabric wallpaper is 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment for 24 hours as a sample. In addition, a sample which had not been pretreated with ultraviolet rays was prepared.
Test method
In the acetaldehyde gas removal test, a sample was placed in a chamber having a volume of 5L, the sample was previously ventilated and adjusted so that the temperature and humidity became 25℃and 20%, and then, acetaldehyde gas was injected into the chamber by a syringe so that the concentration became 10 ppm. For the removal test, an ultraviolet sharp filter (CLAREX UV cut filter N-169) was interposed between the lamp and the chamber, and irradiation of light was performed on the sample surface with 6000lx light using a white fluorescent lamp FL20SW while cutting off UV light of 380nm or less, and concentration measurement of acetaldehyde gas was performed for 2 hours using a photoacoustic multi-gas monitor INNOVA1412i (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 light irradiation time and the residual rate of acetaldehyde.
Fig. 7 is a graph showing the catalytic action of other samples of the photocatalyst article according to the embodiment, and shows the relationship between the light irradiation time and the residual rate of acetaldehyde.
The results of example 1 are shown in fig. 6 as curve 101.
The acetaldehyde gas removal test was performed similarly for a sample that was not pretreated with ultraviolet rays, and the obtained results are shown in fig. 7 as curve 506.
As is clear from fig. 6 and 7, when the smectite and the photocatalyst are applied to the surface treatment part, the residual rate of the acetaldehyde gas becomes 10% or less at 2 hours, and the sample subjected to the pretreatment with ultraviolet rays has a good catalytic effect. However, in the case of the sample which was not pretreated with ultraviolet rays, the residual rate of acetaldehyde gas became 70% or more at 2 hours, and the sufficient catalytic effect could not be confirmed.
Example 2
Preparation of crosslinker coating liquid 1
The cross-linking agent coating liquid is prepared by the following steps of 2 The aqueous solution of ammonium zirconium carbonate was diluted to 1.9% by weight with pure water and stirred with a stirrer.
Preparation of clay mineral coating liquid 1
In the same manner as in example 1, a slurry of a clay mineral layer coating liquid 1 was obtained.
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity capable of absorbing pure water was measured and found to be 0.964g, so that every 1m 2 Maximum water absorption W of (2) A Estimated to be 192.8g/m 2 。
On the non-woven wallpaper, 199g/m was applied by dip coating 2 (in this case, K was 100, and the specific gravity D of the coating liquid was 1.033 g/cm) 3 ) The crosslinking agent coating liquid 1 was applied and dried at 150℃for 5 minutes to immobilize ammonium zirconium carbonate. In this way, the non-woven wallpaper base material is treated with the solid component amount (ZrO 2 Converted) is adhered with 3.8g/m 2 Ammonium zirconium carbonate.
Next, 199g/m was applied by dip coating 2 (in this case, K was 100 and the specific gravity D of the liquid was 1.04 g/cm) 3 ) The same clay mineral coating liquid 1 as in example 1 was applied, dried at 150℃for 5 minutes, and 5.6g/m was adhered to a nonwoven wallpaper substrate 2 Is a smectite of (2).
Further, the coating was carried out by dip coating at a rate of 40g/m 2 Coating contains 1.25% by weight of WO 3 1.25 wt% TiO 2 The photocatalyst coating liquid 1 of (2) was dried at 150℃for 5 minutes to give a photocatalyst of 1.0g/m 2 Cementing to obtain the non-woven wallpaper serving as a photocatalyst product.
The non-woven fabric wallpaper is 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment for 24 hours as a sample. In addition, a sample which had not been subjected to pretreatment was prepared.
Test method
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
The results obtained are shown in fig. 6 as curve 102.
The acetaldehyde gas removal test was performed similarly for a sample that was not pretreated with ultraviolet rays, and the obtained results are shown in fig. 7 as a curve 503.
As is clear from fig. 6 and 7, when the surface treatment section uses a smectite, a photocatalyst, and a crosslinking agent, the residual rate of acetaldehyde gas becomes 10% or less at 2 hours, and the sample subjected to the pretreatment with ultraviolet rays has a good catalytic effect. The sample that was not pretreated with ultraviolet light was found to have a catalytic effect in which the residual rate of acetaldehyde gas was 20% or less at 2 hours.
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 the mixture with a stirrer. The concentration at this time was set to 0.4 wt%.
Preparation of clay mineral coating liquid 1
In the same manner as in example 1, a slurry of a clay mineral layer coating liquid 1 was obtained.
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity capable of absorbing pure water was measured and found to be 0.964g, so that every 1m 2 Maximum water absorption W of (2) A Estimated to be 192.8g/m 2 。
On the non-woven wallpaper, 192.8g/m is coated by dipping 2 (at this time, K was 100, and the specific gravity D of the coating liquid was 1.000g/cm 3 ) The adsorbent coating liquid 1 was applied and dried at 150℃for 5 minutes to immobilize adipic dihydrazide. In this way, 0.8g/m of the nonwoven wallpaper substrate was adhered with the solid content 2 Adipic acid dihydrazide of (a).
Next, 199g/m was applied by dip coating 2 (at this time, the ratio K was 100, and the specific gravity D of the coating liquid was 1.04g/cm 3 ) Coating the same clay mineral coating liquid 1 as in example 1, drying at 150℃for 5 minutes, and then subjecting to nonwoven fabricAdhering 5.6g/m to the cloth wallpaper base material 2 Is a smectite of (2).
Further, the coating was carried out by dip coating at a rate of 40g/m 2 Coating contains 1.25% by weight of WO 3 1.25 wt% TiO 2 The photocatalyst coating liquid 1 of (2) was dried at 150℃for 5 minutes to give a photocatalyst of 1.0g/m 2 Cementing to obtain the non-woven wallpaper serving as a photocatalyst product.
The non-woven fabric wallpaper is 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment for 24 hours as a sample. In addition, a sample which had not been subjected to pretreatment was prepared.
Test method
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
The results obtained are shown in fig. 6 as curve 103.
The acetaldehyde gas removal test was performed similarly for a sample that was not pretreated with ultraviolet rays, and the obtained results are shown as a curve 502 in fig. 7.
As is clear from fig. 6 and 7, when the surface treatment section uses a smectite, a photocatalyst, and an adsorbent, the residual rate of acetaldehyde gas becomes 10% or less at 2 hours, and the sample subjected to the pretreatment with ultraviolet rays has a good catalytic effect. The sample that was not pretreated with ultraviolet light was also found to have a sufficient catalytic effect in that the residual rate of acetaldehyde gas was 10% or less at 2 hours.
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 crosslinker coating liquid 1
A crosslinker coating solution was prepared in the same manner as in example 2.
Preparation of clay mineral coating liquid 1
In the same manner as in example 1, a slurry of a clay mineral layer coating liquid 1 was obtained.
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity capable of absorbing pure water was measured and found to be 0.964g, so that every 1m 2 Maximum water absorption W of (2) A Estimated to be 192.8g/m 2 。
On the non-woven wallpaper, 192.8g/m is coated by dipping 2 (at this time, K was 100, and the specific gravity D of the coating liquid was 1.000g/cm 3 ) The adsorbent coating liquid 1 was applied and dried at 150℃for 5 minutes to immobilize adipic dihydrazide. In this way, 0.8g/m of adipic acid dihydrazide was adhered to the nonwoven wallpaper substrate 2 Adipic acid dihydrazide of (a).
Subsequently, 199g/m of the nonwoven wallpaper was applied by dip coating 2 (in this case, K was 100, and the specific gravity D of the coating liquid was 1.033 g/cm) 3 ) The crosslinking agent coating liquid 1 was applied and dried at 150℃for 5 minutes to immobilize ammonium zirconium carbonate. In this way, the non-woven wallpaper base material is treated with the solid component amount (ZrO 2 Converted), adipic acid dihydrazide, 3.8g/m in terms of solid content 2 。
Next, 199g/m was applied by dip coating 2 (at this time, the ratio K was 100, and the specific gravity D of the coating liquid was 1.04g/cm 3 ) The same clay mineral coating liquid 1 as in example 1 was applied, dried at 150℃for 5 minutes, and 5.6g/m of a nonwoven wallpaper substrate was adhered 2 Is a smectite of (2).
Further, the coating was carried out by dip coating at a rate of 40g/m 2 Coating contains 1.25% by weight of WO 3 1.25 wt% TiO 2 The photocatalyst coating liquid 1 of (2) was dried at 150℃for 5 minutes to give a photocatalyst of 1.0g/m 2 Cementing to obtain the non-woven wallpaper serving as a photocatalyst product.
The non-woven fabric wallpaper is 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment for 24 hours as a sample. In addition, anotherSamples were prepared without pretreatment.
Test method
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
The results obtained are shown in fig. 6 as curve 104.
The acetaldehyde gas removal test was performed similarly for a sample that was not pretreated with ultraviolet rays, and the obtained results are shown in fig. 7 as a curve 504.
As is clear from fig. 6 and 7, when the surface treatment section uses a smectite, a photocatalyst, a crosslinking agent and an adsorbent, the residual rate of acetaldehyde gas becomes 10% or less at 2 hours in the sample subjected to the pretreatment with ultraviolet rays. The sample that was not pretreated with ultraviolet light was found to have a good catalytic effect in that the residual rate of acetaldehyde gas was 10% or less at 2 hours.
Example 5
Preparation of crosslinker coating liquid 1
A crosslinker coating solution was prepared in the same manner as in example 2.
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity capable of absorbing pure water was measured and found to be 0.964g, so that every 1m 2 Maximum water absorption W of (2) A Estimated to be 192.8g/m 2 。
On the non-woven wallpaper, 199g/m was applied by dip coating 2 (in this case, K was 100, and the specific gravity D of the coating liquid was 1.033 g/cm) 3 ) The crosslinking agent coating liquid 1 was applied and dried at 150℃for 5 minutes to immobilize ammonium zirconium carbonate. In this way, the non-woven wallpaper base material is treated with the solid component amount (ZrO 2 Converted) is adhered with 3.8g/m 2 Ammonium zirconium carbonate.
Next, the coating was applied by dip coating at 40g/m 2 The coating contains 1.25 wt% WO 3 1.25 wt% TiO 2 The photocatalyst coating liquid 1 of (2) was dried at 150℃for 5 minutes to give a photocatalyst of 1.0g/m 2 Cementing to obtain the non-woven wallpaper serving as a photocatalyst product.
The non-woven fabric wallpaper is 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment for 24 hours as a sample.
Test method
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
The results obtained are shown in fig. 6 as curve 105.
Example 6
Preparation of a Mixed coating solution 1 of Cross-linking agent and adsorbent
The 19% ammonium zirconium carbonate aqueous solution was diluted with pure water, and adipic acid dihydrazide powder was added thereto and stirred with a stirrer to prepare the aqueous solution. The concentrations at this time were set to 1.9 wt% and 0.4 wt%, respectively.
Preparation of clay mineral coating liquid 1
In the same manner as in example 1, a slurry of a clay mineral layer coating liquid 1 was obtained.
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
A nonwoven wallpaper was prepared as a base material. Fig. 11 shows SEM photographs of the porous substrate used. Fig. 11 is a view of the surface of a nonwoven fabric wallpaper substrate, in which a dye containing a filler (scaly sheet) is applied to a nonwoven fabric substrate containing polyester fibers in natural fibers for decoration, as shown in the figure.
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity capable of absorbing pure water was measured and found to be 0.964g, so that every 1m 2 Maximum water absorption W of (2) A Estimated to be 192.8g/m 2 。
On the nonwoven wallpaper, 196.1g/m of the nonwoven wallpaper was coated by dipping 2 (at this time, K is100, the specific gravity D of the coating liquid was 1.017g/cm 3 ) Coating the cross-linking agent and adsorbent mixed coating solution 1, drying at 150 ℃ for 5 minutes, and immobilizing ammonium zirconium carbonate and adipic dihydrazide. In this way, the non-woven wallpaper base material is treated with the solid component amount (ZrO 2 Converted) is adhered with 3.7g/m 2 Is bound to 0.8g/m based on the solid content of adipic acid dihydrazide 2 Adipic acid dihydrazide of (a).
Next, 199g/m was applied by dip coating 2 (at this time, the ratio K was 100, and the specific gravity D of the liquid was 1.04g/cm 3 ) The same clay mineral coating liquid 1 as in example 1 was applied, dried at 150℃for 5 minutes, and 5.6g/m of a nonwoven wallpaper substrate was adhered 2 Is a smectite of (2).
Further, the coating was carried out by dip coating at a rate of 40g/m 2 Coating contains 1.25% by weight of WO 3 1.25 wt% TiO 2 The photocatalyst coating liquid 1 of (2) was dried at 150℃for 5 minutes to give a photocatalyst of 1.0g/m 2 Cementing to obtain the non-woven wallpaper serving as a photocatalyst product.
An SEM photograph of the surface of the obtained photocatalyst article was observed with an electron microscope, and is shown in fig. 12. As shown in the figure, in the photocatalyst product, a crosslinking agent, an adsorbent, and a photocatalyst penetrating from the surface of the porous base material are provided on each of the natural fibers and the polyester fibers.
The non-woven fabric wallpaper is 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment for 24 hours as a sample. In addition, a sample which had not been subjected to pretreatment was prepared.
Test method 1 (initial value)
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
The results obtained are shown in fig. 6 as curve 106.
The acetaldehyde gas removal test was performed similarly for a sample that was not pretreated with ultraviolet rays, and the obtained results are shown in fig. 7 as a curve 501.
As is clear from fig. 6 and 7, when the surface treatment section uses a smectite, a photocatalyst, a crosslinking agent and an adsorbent, the residual rate of acetaldehyde gas becomes 10% or less at 2 hours in the sample subjected to the pretreatment with ultraviolet rays. The sample that was not pretreated with ultraviolet light was found to have a good catalytic effect in that the residual rate of acetaldehyde gas was 10% or less at 2 hours.
Test method 2
The formaldehyde removal test was performed in the same manner as in example 1, except that formaldehyde gas was injected instead of acetaldehyde gas and a 5L balloon was used, and the concentration of formaldehyde gas was measured for 48 hours in the sample subjected to the ultraviolet pretreatment.
As a result, it was confirmed that the residual formaldehyde rate after 48 hours was less than 10%, and the catalyst had a good catalytic effect.
Test method 3
As a toluene removal test, a toluene gas concentration was measured for 48 hours in a sample subjected to ultraviolet pretreatment in the same manner as in the test method of example 1, except that toluene gas was injected instead of acetaldehyde gas and a 5L air bag was used.
As a result, the residual rate of toluene after 48 hours was 59%. The decomposition rate of toluene was 65% or less, and the catalyst was confirmed.
Comparative example 1-1
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
On a nonwoven wallpaper cut into 50X 100mm, the solid content of the nonwoven wallpaper was 1.0g/m 2 The photocatalyst coating liquid 1 was applied by dip coating, and dried in a drying oven at 120℃for 5 minutes. The non-woven fabric wallpaper is 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment for 24 hours as a sample. In addition, a sample which had not been subjected to pretreatment was prepared.
Test method 1
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
The results obtained are shown in fig. 6 as curve 107.
The acetaldehyde gas removal test was performed similarly for a sample that was not pretreated with ultraviolet rays, and the obtained results are shown as a curve 505 in fig. 7.
As is clear from fig. 6 and 7, when the photocatalyst alone was applied to the surface treatment section, the residual rate of acetaldehyde was about 25% at 2 hours for the sample pretreated with ultraviolet rays, and about 80% at 2 hours for the sample not pretreated with ultraviolet rays, and thus, a sufficient catalytic effect was not obtained.
Test method 2
A48-hour formaldehyde removal test was performed in the same manner as in test method 2 of example 6.
As a result, the residual formaldehyde rate after 48 hours increased to 250% or more.
The increase in formaldehyde is believed to be generated by the organic substrate. It is considered that, when the photocatalyst layer is coated only on the organic substrate, formaldehyde generated from the organic substrate cannot be suppressed, and thus, sufficient catalytic action cannot be obtained.
Test method 3
A48-hour toluene removal test was conducted in the same manner as in test method 3 of example 6.
As a result, the residual rate of toluene after 48 hours was 95%.
Toluene is considered to be hardly decomposed. It is considered that the toluene cannot be reduced when the photocatalyst layer is coated only on the organic substrate, and thus a sufficient catalytic effect cannot be obtained.
Comparative example 2
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
Samples were produced in the same manner as in comparative example 1, except that 50×100mm glass, which is not a porous substrate, was used instead of the nonwoven fabric wallpaper cut into 50×100 mm. In addition, a sample which had not been subjected to pretreatment was prepared.
Test method
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
The results obtained are shown in fig. 8 as curve 108.
The acetaldehyde gas removal test was performed similarly for a sample that was not pretreated with ultraviolet rays, and the obtained results are shown in fig. 7 as curve 507.
As is clear from fig. 6 and 7, when the photocatalyst alone is applied to the surface treatment portion, the residual rate of acetaldehyde gas is about 10% at 2 hours for both the sample pretreated with ultraviolet rays and the sample not pretreated with ultraviolet rays, and a sufficient catalytic effect is obtained for the glass substrate even for the photocatalyst-alone coating liquid 1.
The evaluation of the concentration and the adhering amount of the coating liquid in the surface treatment part and the concentration measurement of the acetaldehyde gas and other gases in examples 1 to 6 and comparative examples 1 and 2 are shown in tables 1 to 1 and 1 to 2 below. In the table, the amount of cement (g/m 2 ) The brackets are shown below the concentration (wt%) of the coating liquid. In the evaluation, the residual rate of acetaldehyde gas after 2 hours was set to be "o" and the residual rate exceeding 20% was set to be "x". Further, the residual ratio of formaldehyde gas after 48 hours was set to be equal to or less than 20%, and the residual ratio exceeding 20% was set to be equal to x. In the case of toluene gas, the residual rate after 48 hours was set to be 60% or less. The case exceeding 60% was set to x.
As shown in Table 1-1, it was found that the residual rate of acetaldehyde gas was 20% or less after 2 hours in each of the photocatalyst articles of examples 1 to 6, and that the catalytic action on the surrounding atmosphere was good even when the organic base material was used. In addition, as for the samples not subjected to pretreatment with ultraviolet rays, as shown in examples 4 and 6, in the case where a smectite, a photocatalyst, a crosslinking agent and an adsorbent were used in the surface treatment section, good catalytic action was confirmed. Further, as shown in examples 2 and 3, even when one of the smectite, the photocatalyst, and the crosslinking agent or the adsorbent was used in the surface treatment section, a sufficient catalytic effect was confirmed. However, as shown in example 1, in the case where smectite, photocatalyst and crosslinking agent were used in the surface treatment section, sufficient catalytic action could not be confirmed.
Fig. 8 is a graph showing the catalytic action of the comparative photocatalyst article, and shows the relationship between the light irradiation time and the residual rate of acetaldehyde.
An example of comparative example 1 as an organic substrate is shown in fig. 8 as curve 107.
As shown in fig. 8, if a photocatalyst is directly applied to an organic substrate, since many harmful organic molecules from the organic substrate are adsorbed and decomposed, the apparent catalytic effect on the surrounding atmosphere is reduced as shown in curve 107. In contrast, even if the photocatalyst is directly applied to the glass substrate, as shown in curve 108, since no harmful organic molecules are generated from the glass substrate, the catalytic action on the surrounding atmosphere is not reduced. Since curve 108 is substantially the same as that of examples 1 to 6, it is considered that the photocatalyst articles of examples 1 to 6 can reduce the generation of harmful organic molecules in the organic substrate as the glass substrate that does not generate harmful organic molecules.
TABLE 1-1
TABLE 1-2
Example 7
Preparation of a Mixed coating solution 2 of Cross-linking agent and adsorbent
The 19% ammonium zirconium carbonate aqueous solution was diluted with pure water, and adipic acid dihydrazide powder was added thereto and stirred with a stirrer to prepare the aqueous solution. The concentrations at this time were set to 3.5 wt% and 5 wt%, respectively.
Preparation of clay mineral coating liquid 1
In the same manner as in example 1, a slurry of a clay mineral layer coating liquid 1 was obtained.
Preparation of photocatalyst coating liquid 1
In the same manner as in example 1, a slurry of the photocatalyst coating liquid 1 was obtained.
Sample preparation
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity capable of absorbing pure water was measured and found to be 0.964g, so that every 1m 2 Maximum water absorption W of (2) A Estimated to be 192.8g/m 2 。
On the non-woven wallpaper, 199.2g/m was coated by dipping 2 (in this case, K was 100, and the specific gravity D of the coating liquid was 1.033 g/cm) 3 ) Coating the cross-linking agent and adsorbent mixed coating solution 2, drying at 150 ℃ for 5 minutes, and immobilizing ammonium zirconium carbonate and adipic dihydrazide. In this way, the non-woven wallpaper base material is treated with the solid component amount (ZrO 2 Converted) is adhered with 7.0g/m 2 Is 10.0g/m of the ammonium zirconium carbonate based on the solid content of adipic acid dihydrazide 2 Adipic acid dihydrazide of (a).
Next, 199g/m was applied by dip coating 2 (at this time, the ratio K was 100, and the specific gravity D of the liquid was 1.04g/cm 3 ) The same clay mineral coating liquid 1 as in example 1 was applied, dried at 150℃for 5 minutes, and 5.6g/m of a nonwoven wallpaper substrate was adhered 2 Is a smectite of (2).
Further, the coating was carried out by dip coating at a rate of 40g/m 2 Coating contains 1.25% by weight of WO 3 1.25 wt% TiO 2 The photocatalyst coating liquid 1 of (2) was dried at 150℃for 5 minutes to give a photocatalyst of 1.0g/m 2 Cementing to obtain the non-woven wallpaper serving as a photocatalyst product.
Test method 1 (initial value)
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours.
Fig. 9 is a graph showing the catalytic action of the photocatalyst product according to the embodiment, and shows the relationship between the light irradiation time and the residual rate of acetaldehyde.
The results obtained are shown in fig. 9 as curve 301.
Test method 2 (7 days later)
The sample with the initial value measured was placed on a desk in an office where a person with a white fluorescent lamp was put in and out for 7 days as a real space test. The illuminance on the sample surface was about 350lx, and the lights were turned off at night and on a holiday. The acetaldehyde gas removal test was performed under the same conditions as in test method 1, and the test was carried out as data after leaving the test space for 7 days.
The results obtained are shown in fig. 9 as curve 302.
Test method 3 (15 days later)
The sample subjected to the test in the actual space for 7 days was further left for 8 days under the same conditions as in test method 2, and the acetaldehyde gas removal test was performed under the same conditions as in test method 1, as data after 15 days of the actual space.
The results obtained are shown in fig. 9 as curve 303.
Comparative examples 1 to 2
Samples similar to comparative example 1-1 were prepared, and acetaldehyde gas removal tests were performed in the same manner as in example 7 for the initial period, after 7 days, and after 15 days.
FIG. 10 is a graph showing the catalytic action of a comparative photocatalyst article, showing the relationship between the irradiation time of light and the residual rate of acetaldehyde.
Initial values are shown in curve 401, 7 days later in curve 402, and 15 days later in curve 403.
As shown in fig. 9, it was found that the photocatalyst article of example 7 had a residual rate of acetaldehyde gas of 30% or less after 2 hours even after 7 days and after 15 days, and had sufficient catalytic action on the surrounding atmosphere and good life characteristics.
On the other hand, as shown in fig. 10, the photocatalyst article of comparative example 1 was found to have an acetaldehyde gas remaining rate exceeding 80% after 2 hours for both 7 days and 15 days, and had a reduced catalytic action on the surrounding atmosphere and poor life characteristics.
Examples 8-1 and 8-2
Preparation of a Mixed coating solution 3 of Cross-linking agent and adsorbent
The 19% ammonium zirconium carbonate aqueous solution was diluted with pure water, and adipic acid dihydrazide powder was added thereto and stirred with a stirrer to prepare the aqueous solution. The concentration at this time was set to 5% by weight (ZrO 2 Converted), 7.5 wt%.
Preparation of clay mineral coating liquid 2
The smectite powder was poured into the pure water stirred by the stirrer so as to be 4% by weight, stirred for 5 minutes, then treated with the homogenizer for 15 minutes and left for 24 hours. This was again stirred with a stirrer to homogenize the slurry, thereby obtaining a slurry as a clay mineral layer coating liquid 2.
Preparation of photocatalyst coating liquid 2
Preparation of 10 wt% of WO in pure water 3 To the slurry of (2), 10% by weight of TiO based on the weight of the slurry was added 2 A photocatalyst. The photocatalyst coating liquid 2 was prepared by diluting it with pure water so that the total solid content became 4.5% by weight.
Sample preparation
For nonwoven wallpaper cut into 50X 100mm, the maximum water absorption capacity of the substrate capable of absorbing pure water was measured in advance and found to be 0.964g, so that 1m of the substrate was used 2 Is based on the water absorption W of the substrate A Estimated to be 192.8g/m 2 。
On the non-woven wallpaper, 28.9g/m of the non-woven wallpaper is coated by dipping 2 (at this time, K was 14.3, and the specific gravity D of the coating liquid was 1.049 g/cm) 3 ) The mixed coating liquid 3 was applied and dried at 170℃for 3 minutes, and zirconium ammonium carbonate and adipic dihydrazide were immobilized. On the non-woven wallpaper base material, the solid component amount (ZrO 2 Converted) is adhered with 1.45g/m 2 Is bound to 2.17g/m based on the solid content of adipic acid dihydrazide 2 Adipic acid dihydrazide of (a).
Next, the mixture was passed through a doctor blade at 62.3g/m 2 (in this case, K was 31, and the specific gravity D of the coating liquid was 1.043 g/cm) 3 ) The clay mineral coating liquid 2 was applied and dried at 170℃for 4 minutes to immobilize the smectite. The non-woven wallpaper is stuck with 2.5g/m 2 Is a smectite of (2).
Further, the nonwoven wallpaper was treated with a doctor blade at 26.5g/m 2 Coating the photocatalyst coating liquid 2, drying at 120deg.C for 3 min to make photocatalyst 1.2g/m 2 Cementing, and manufacturing the non-woven wallpaper of the embodiment 8-1.
In addition, as example 8-2, a doctor blade of 45g/m was used 2 A non-woven wallpaper coated with the photocatalyst coating liquid 2. The drying temperature was set at 120℃and the drying time was set at 5 minutes. The amount of the photocatalyst at this time was 2.0g/m 2 。
For the nonwoven wallpaper of examples 8-1 and 8-2, the nonwoven wallpaper was used in a 20W/m ratio 2 The ultraviolet lamp FL20SBL adjusted in the manner of (1) was subjected to pretreatment for 24 hours to obtain a sample.
Test method
Acetaldehyde gas removal test
The concentration of acetaldehyde gas was measured in the same manner as in example 1 for 2 hours. It was found that the residual rate of acetaldehyde gas was 10% or less in example 8-1 and 5% or less in example 8-2, both of which had good catalytic activity.
Black cloth transfer test method
The surface of the nonwoven wallpaper prepared in the same manner as the sample preparation was rubbed with a black cloth of wool, and the color transferred to the black cloth was observed. By placing a black cloth on the nonwoven wallpaper placed on the flat plate, a load of 3kgf was applied from the surface of the nonwoven wallpaper placed on the flat plate to a circular surface having a diameter of 17mm, and the nonwoven wallpaper was moved 10cm in this state, whereby the nonwoven wallpaper was rubbed against the black cloth. The pressure at this time was 13.2g/mm 2 。
Fig. 13 shows a photograph of the black cloth surface showing the result of the transfer test of the nonwoven wallpaper of example 8-1, and fig. 14 shows a photograph of the black cloth surface showing the result of the transfer test of the nonwoven wallpaper of example 8-2.
In example 8-1, the black cloth was hardly changed, but in example 8-2, it was changed to white. The cause of the white color was confirmed by a portable fluorescent X-ray measuring device (trade name hand-held fluorescent X-ray analyzer DELTA Professional manufactured by Olympus Corporation), and as a result, the photocatalyst component was confirmed. In the case of the porous substrate, 1.2g/m was obtained 2 The amount of the photocatalyst to be adhered was proper, but was 2.0g/m 2 When the amount of photocatalyst sticking is slightly excessive, the amount tends to be slightly excessive.
Example 9 and comparative example 3
Preparation of crosslinker coating liquid 2
19% by weight (ZrO 2 Converted) the aqueous ammonium zirconium carbonate solution was diluted with pure water to prepare a solution having a concentration of 0.75% by weight (ZrO 2 Converted) aqueous solution.
Preparation of photocatalyst coating liquid 3
Will be dispersed with 10 wt% of WO 3 Is diluted with pure water and adjusted so that the solid content becomes 0.5 wt% w.
Sample preparation
As a result of measuring the maximum water absorption capacity capable of absorbing pure water for a pile fabric blank cut into 50X 100mm, 7.94g was found for every 1m 2 Is based on the water absorption W of the substrate A Estimated to be 1588g/m 2 。
On the pile fabric blank, 200g/m of the fabric was impregnated and coated 2 (at this time, K was 12.4, and the specific gravity D of the coating liquid was 1.013g/cm 3 ) The crosslinking agent coating liquid 2 was applied and dried at 150℃for 3 minutes to immobilize ammonium zirconium carbonate. In the pile fabric, the solid content of ammonium zirconium carbonate (ZrO 2 Converted) is adhered with 1.5g/m 2 Ammonium zirconium carbonate.
Next, 200g/m of the above-mentioned pile fabric blank was subjected to a simple gravure test machine 2 Coating photocatalyst coating liquid 3, drying at 120deg.C for 3 min to obtain WO 3 PhotocatalystAt 1.0g/m 2 The pile fabric blank of example 9 was bonded.
A pile fabric blank was produced in the same manner as in example 9, except that the cross-linking agent coating liquid 2 was not applied as in comparative example 3.
The pile fabric blanks of example 9 and comparative example 3 and the Blank (Blank) pile fabric Blank which had not been treated at all were treated at 20W/m 2 The ultraviolet lamp FL20SBL adjusted in this manner was subjected to pretreatment 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, the sample was previously ventilated and adjusted so as to have a humidity of 20% at 25 ℃, and then, acetaldehyde gas was injected into the chamber by a syringe so that the concentration became 10 ppm. For the removal test, an ultraviolet sharp filter (CLAREX UV cut filter N-169) was interposed between the lamp and the chamber, and irradiation of light was performed on the sample surface with a white fluorescent lamp FL20SW so as to become 6000lx while cutting off UV light of 380nm or less, and concentration measurement of acetaldehyde gas was performed for 1 hour using a photoacoustic multi-gas monitor inova 1412i (manufactured by Luma Sense Technologies). The results obtained are shown in fig. 15.
FIG. 15 is a graph showing the relationship between the light irradiation time and the residual rate of acetaldehyde.
In the figure, 501 represents a blank pile fabric, 502 represents the result of comparative example 3, and 503 represents the result of example 9. The pile fabric blank of comparative example 3 coated with the photocatalyst alone had an acetaldehyde residual rate of 90% or more and had no catalytic action as shown in 502, but the pile fabric blank of example 9 coated with the zirconium ammonium carbonate and the photocatalyst had an acetaldehyde gas residual rate of 50% or less as shown in 503, and it was found that the pile fabric blank had a good catalytic action by treatment with zirconium ammonium carbonate.
In tables 1-1 and 1-2, evaluation of the coating liquid concentration and the adhesion amount of the surface treatment part and the concentration measurement of acetaldehyde gas are also shown in examples 7, 8-1, 8-2, 9 and comparative example 3.
While several embodiments of the present invention have been described, 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 are included in the scope and gist of the invention, and are included in the invention described in the claims and their equivalents.
Claims (8)
1. A photocatalyst article, comprising:
porous base material
A surface treatment unit which is provided on the porous substrate and which comprises ammonium zirconium carbonate and a photocatalyst containing tungsten oxide,
the porous substrate is an organic substrate,
the surface treatment section includes:
a layer containing ammonium zirconium carbonate provided on the porous substrate,
A photocatalyst layer containing the photocatalyst and provided on the layer containing ammonium zirconium carbonate, and
And a clay mineral layer provided between the layer containing ammonium zirconium carbonate and the photocatalyst layer and containing a clay mineral containing smectite.
2. The photocatalyst article according to claim 1, further comprising a layer containing adipic acid dihydrazide provided between the layer containing zirconium ammonium carbonate and the clay mineral layer or between the layer containing zirconium ammonium carbonate and the porous substrate.
3. The photocatalyst article of claim 1, wherein the layer comprising ammonium zirconium carbonate further comprises adipic acid dihydrazide.
4. The photocatalyst article according to any one of claims 1 to 3, wherein the porous substrate is a nonwoven fabric.
5. The photocatalyst article according to any one of claims 1 to 3, wherein the porous substrate is wallpaper.
6. The photocatalyst article according to any one of claims 1 to 3, wherein the porous substrate is a wallcovering.
7. The photocatalyst article according to any one of claims 1 to 3, wherein the porous substrate is a nonwoven wallpaper.
8. The use of the photocatalyst article according to any one of claims 1 to 7 for removing acetaldehyde, wherein the photocatalyst article is placed in a chamber having a volume of 0.5L, acetaldehyde having a concentration of 10ppm is introduced into the chamber, light is irradiated with 6000 lux illuminance by a white fluorescent lamp FL20SW, light having a wavelength of 380nm or less is cut off by an ultraviolet cut filter, and the photocatalyst article is left for 2 hours at room temperature, normal pressure and humidity 20%, and then acetaldehyde having a concentration of 60% or more is reduced.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-051293 | 2019-03-19 | ||
| JP2019051293 | 2019-03-19 | ||
| JP2019192159A JP7387380B2 (en) | 2019-03-19 | 2019-10-21 | photocatalyst products |
| JP2019-192159 | 2019-10-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111715301A CN111715301A (en) | 2020-09-29 |
| CN111715301B true CN111715301B (en) | 2023-09-08 |
Family
ID=72563999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911210828.9A Active CN111715301B (en) | 2019-03-19 | 2019-12-02 | Photocatalyst article |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2023126530A (en) |
| CN (1) | CN111715301B (en) |
Families Citing this family (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 |
| JP2023065047A (en) * | 2021-10-27 | 2023-05-12 | シャープ株式会社 | Photocatalyst coating structure, photocatalyst coating member, and photocatalyst coating method |
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
-
2023
- 2023-07-18 JP JP2023116684A patent/JP2023126530A/en active Pending
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023126530A (en) | 2023-09-07 |
| CN111715301A (en) | 2020-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2023126530A (en) | Photocatalysis product | |
| KR20070069165A (en) | Fiber fabric having voc removing function | |
| KR102129422B1 (en) | Beads for air purification, method for preparing the same, and filter using the same | |
| US20070149397A1 (en) | Photocatalytic composite material, method for producing the same and application thereof | |
| CN113439136B (en) | Nanofiber surface | |
| JPH11169724A (en) | Composite particle material having anti-bacterial function | |
| JP2013216596A (en) | Antimicrobial agent, antimicrobial agent dispersion, and antimicrobial-treated product using the same | |
| JP7387380B2 (en) | photocatalyst products | |
| JP4107512B1 (en) | Photocatalyst coating liquid and photocatalyst film forming method | |
| JP2005254128A (en) | Photocatalyst particle and method of immobilizing it, and photocatalytic member | |
| JP2011094252A (en) | Method for fixing photocatalyst particle on fiber surface | |
| JP5358433B2 (en) | Composite, method for producing the same, and composition containing the same | |
| JPH105598A (en) | Photocatalyst powder, photocatalyst body using the same and their production, and environmental cleaning method using them | |
| JP3978636B2 (en) | Coating composition for photocatalyst film formation | |
| WO2005026276A1 (en) | Coating material | |
| JP2000225349A (en) | Filter | |
| KR100482649B1 (en) | Direct adhesion method of photocatalyst on substrate | |
| KR20080014526A (en) | Photocatalytic coating composition for accessory of automobiles and method for coating the same on an object | |
| JP3372451B2 (en) | Photocatalyst-coated metal plate and method for producing the same | |
| JP2002126537A (en) | Metal oxide-based photocatalyst and production of the same | |
| Yin et al. | The improvement of solar photocatalytic activity of ZnO by doping with Er 3+: Y 3 Al 5 O 12 during dye degradation | |
| JP2002285468A (en) | Photocatalyst-supporting fiber | |
| KR20180075719A (en) | Visible Light-responsive Photocatalyst and Visible Light-responsive Photocatalyst Film Using the Same | |
| JP6989419B2 (en) | Photocatalyst dispersion, photocatalyst composite material and photocatalyst device | |
| JP2006281109A (en) | Method for forming photocatalytic film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |