JP5698810B2 - 冷蔵庫 - Google Patents
冷蔵庫 Download PDFInfo
- Publication number
- JP5698810B2 JP5698810B2 JP2013181141A JP2013181141A JP5698810B2 JP 5698810 B2 JP5698810 B2 JP 5698810B2 JP 2013181141 A JP2013181141 A JP 2013181141A JP 2013181141 A JP2013181141 A JP 2013181141A JP 5698810 B2 JP5698810 B2 JP 5698810B2
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- powder
- tungsten oxide
- tungsten
- photocatalyst
- oxide powder
- Prior art date
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- 239000000843 powder Substances 0.000 claims description 248
- 239000011941 photocatalyst Substances 0.000 claims description 134
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 121
- 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 description 120
- 239000000463 material Substances 0.000 claims description 65
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- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 57
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- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 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
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- 230000001877 deodorizing effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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Description
原料粉末として平均粒径が0.5μmの三酸化タングステン粉末を用意した。この原料粉末をキャリアガス(Ar)と共にRFプラズマに噴霧し、さらに反応ガスとして酸素を75L/minの流量で流した。このようにして、原料粉末を昇華させながら酸化反応させる昇華工程を経て酸化タングステン粉末を作製した。粉末の製造条件を表1に示す。
反応ガスとしてアルゴンを80L/min、空気を5L/minの流量で流し、反応容器内の圧力を30kPaと減圧側に調整する以外は、実施例1と同様の昇華工程を経て酸化タングステン粉末を作製した。得られた酸化タングステン粉末について、実施例1と同様の測定、評価を行った。酸化タングステン粉末の作製条件を表1に、測定、評価結果を表2に示す。比較例1の酸化タングステン粉末はb*およびL*の値が小さく、これによってガス分解性能(ガス残存率)が85%と劣っていることが確認された。
反応ガスとしてアルゴンを80L/min、空気を5L/minの流量で流す以外は、実施例1と同様の昇華工程を実施して酸化タングステン粉末を作製した。実施例2では酸化タングステン粉末を大気中にて450℃×0.25hの条件で熱処理した。実施例3では酸化タングステン粉末を大気中にて550℃×0.5hの条件で熱処理した。得られた酸化タングステン粉末について、実施例1と同様の測定、評価を行った。酸化タングステン粉末の作製条件を表1に、測定、評価結果を表2に示す。実施例2および実施例3による酸化タングステン粉末は、いずれも優れたガス分解性能を示すことが確認された。X線回折結果はいずれも実施例1と同様にピーク分離が困難なパターンであった。
ここでは実施例1と同様の昇華工程を実施した。ただし、プラズマに投入する原料として、FeやMo等の不純物量が多い酸化タングステン粉末を用いた。得られた酸化タングステン粉末について、実施例1と同様の測定、評価を行った。酸化タングステン粉末の作製条件を表1に、測定、評価結果を表2に示す。酸化タングステン粉末は良好なガス分解性能を示すことが確認された。このことから、微量の金属元素を不純物として含んでいても問題がないことが確認された。なお、X線回折結果は実施例1と同様にピーク分離が困難なパターンであった。
反応ガスとしてアルゴンを80L/min、酸素を10L/min、窒素を40L/minの流量で流す以外は、実施例1と同様の昇華工程を実施して酸化タングステン粉末を作製した。このようにして得た酸化タングステン粉末について、実施例1と同様の測定、評価を行った。酸化タングステン粉末の作製条件を表1に、測定、評価結果を表2に示す。L*a*b*表色系による色調やBET比表面積は所定の値を満足していたものの、窒素含有量が500ppmと高いことから、ガス分解性能(ガス残存率)が52%と実施例1に比べて若干低いことが確認された。なお、X線回折結果は実施例1と同様にピーク分離が困難なパターンであった。
実施例2と同様の昇華工程を経て作製した酸化タングステン粉末に、大気中にて1100℃×0.2hの条件で熱処理を施した。このようにして得た酸化タングステン粉末について、実施例1と同様の測定、評価を行った。酸化タングステン粉末の作製条件を表1に、測定、評価結果を表2に示す。酸化タングステン粉末のBET比表面積が5m2/gと小さく、平均粒径が198nmと大きく、その結果としてガス分解性能が低いことが確認された。これは高温での熱処理で粒成長が起こったためと考えられる。
試薬等として市販されている酸化タングステン粉末(レアメタリック社製)を用いて、実施例1と同様の測定、評価を行った。測定評価結果を表2に示す。また、比較例3の酸化タングステン粉末のX線回折結果を図2に示す。L*a*b*表色系による色調を満たしていたものの、BET比表面積が0.7m2/gと小さく、このためにガス分解性能(ガス残存率)は97%と低いことが確認された。
実施例1で得られた酸化タングステン粉末に酸化銅(CuO)粉末の割合が0.5質量%となるように混合した。このようにして得た酸化タングステン粉末について、実施例1と同様のガス分解性能評価を行った。ガス分解性能(ガス残存率)は20%であり、実施例1と同等の高い性能を有することが確認された。このことから、一般的に光触媒性能の向上のために添加される元素(酸化物でもよい)を、不純物の範囲を超えるような量で含んでいても問題がないことが確認された。
実施例1で作製した酸化タングステン粉末を5質量%、コロイダルシリカを0.05質量%の割合で含む水系塗料を作製した。これをガラスに塗布して乾燥させることによって、光触媒被覆層を有するガラスを作製した。このガラスのガス分解性能を前述した方法にしたがって評価したところ、ガス残存率が15%と優れていることが確認された。次に、光触媒被覆層を有するガラスについて、波長550nmの光を照射したときの透過率を測定した。光透過率の測定は島津製作所製UV−Vis分光光度計UV−2550を用いて行った。その結果、膜厚が0.25μmのときに光の透過率は95%であった。
実施例7と同様にして作製した塗料を、冷蔵庫の樹脂部品の表面に塗布した。この樹脂部品について、アセトアルデヒドガスの分解性能と抗菌性能を評価した。アセトアルデヒドガスの分解性能は実施例1と同様にして評価した。抗菌性能は黄色ブドウ球菌を用いて評価した。塗料の塗布面に黄色ブドウ球菌を付着させ、光照射後の菌のコロニー数を測定した。実施例8による樹脂部品は、ガス残存率が18%、48時間後の菌のコロニー数が1200個と良好な結果を示した。これに対し、比較例1の酸化タングステン粉末を用いた塗料を塗布した樹脂部品では、ガス残存率が85%、48時間後の菌のコロニー数が100000個という値しか得られなかった。
実施例7と同様にして作製した塗料を、内装材(コンクリートおよび木材)の表面に塗布した。このような内装材について、アセトアルデヒドガスの分解性能と抗菌性能を評価した。アセトアルデヒドガスの分解性能は実施例1と同様にして評価した。抗菌性能については、黄色ブドウ球菌を入れた水を試料に塗布し、48時間後の菌のコロニー数を調べた。実施例9による内装材は、ガス残存率が18%、48時間後の菌のコロニー数が1200個と良好な結果を示した。これに対し、比較例1の酸化タングステン粉末を用いた塗料を塗布した内装材では、ガス残存率が85%、48時間後の菌のコロニー数が100000個という値しか得られなかった。
Claims (10)
- 可視光応答型光触媒粉末を1質量%以上100質量%以下の範囲で含有する光触媒材料が設けられた部材を備える貯蔵室を具備する冷蔵庫であって、
前記可視光応答型光触媒粉末は、粉末の色をL*a*b*表色系で表したとき、a*が−5以下、b*が−5以上、L*が50以上の色を有し、かつ11〜820m2/gの範囲のBET比表面積を有する酸化タングステン粉末を具備することを特徴とする冷蔵庫。 - 可視光応答型光触媒粉末を1質量%以上100質量%以下の範囲で含有する光触媒材料が設けられた部材を備える貯蔵室を具備する冷蔵庫であって、
前記可視光応答型光触媒粉末は、粉末の色をL*a*b*表色系で表したとき、a*が−5以下、b*が−5以上、L*が50以上の色を有し、かつ1〜75nmの範囲の画像解析による平均粒径(D50)を有する酸化タングステン粉末を具備することを特徴とする冷蔵庫。 - 請求項1または請求項2記載の冷蔵庫において、
前記部材は、前記光触媒材料の塗布層、または前記光触媒材料を0.1質量%以上90質量%以下の範囲で含有する光触媒塗料の塗布層を有することを特徴とする冷蔵庫。 - 請求項1ないし請求項3のいずれか1項記載の冷蔵庫において、
前記酸化タングステン粉末はX線回折法で測定したとき、2θが22.5〜25°の範囲に最強ピークを有し、かつ2θが33〜35°の範囲にピークを有することを特徴とする冷蔵庫。 - 請求項1ないし請求項4のいずれか1項記載の冷蔵庫において、
前記酸化タングステン粉末は、前記L*a*b*表色系におけるa*が−8以下、b*が3以上、L*が65以上の色を有することを特徴とする冷蔵庫。 - 請求項1ないし請求項5のいずれか1項記載の冷蔵庫において、
前記酸化タングステン粉末は20〜820m2/gの範囲のBET比表面積を有することを特徴とする冷蔵庫。 - 請求項1ないし請求項6のいずれか1項記載の冷蔵庫において、
前記酸化タングステン粉末は1〜41nmの範囲の画像解析による平均粒径(D50)を有することを特徴とする冷蔵庫。 - 請求項1ないし請求項7のいずれか1項記載の冷蔵庫において、
前記酸化タングステン粉末は不純物元素としての金属元素の含有量が10質量%以下であることを特徴とする冷蔵庫。 - 請求項1ないし請求項7のいずれか1項記載の冷蔵庫において、
前記酸化タングステン粉末は50質量%以下の範囲の遷移金属元素を含むことを特徴とする冷蔵庫。 - 請求項1ないし請求項9のいずれか1項記載の冷蔵庫において、
前記酸化タングステン粉末の窒素含有量が300ppm以下であることを特徴とする冷蔵庫。
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