JP3371104B2 - Photocatalyst-coated composite member excellent in photocatalytic activity and light resistance and method for producing the same - Google Patents
Photocatalyst-coated composite member excellent in photocatalytic activity and light resistance and method for producing the sameInfo
- Publication number
- JP3371104B2 JP3371104B2 JP2000083903A JP2000083903A JP3371104B2 JP 3371104 B2 JP3371104 B2 JP 3371104B2 JP 2000083903 A JP2000083903 A JP 2000083903A JP 2000083903 A JP2000083903 A JP 2000083903A JP 3371104 B2 JP3371104 B2 JP 3371104B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- coating film
- zeolite
- particles
- coated
- 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.)
- Expired - Fee Related
Links
- 239000011941 photocatalyst Substances 0.000 title claims description 90
- 230000001699 photocatalysis Effects 0.000 title claims description 42
- 239000002131 composite material Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 239000002245 particle Substances 0.000 claims description 92
- 239000011248 coating agent Substances 0.000 claims description 87
- 238000000576 coating method Methods 0.000 claims description 87
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 50
- 239000010457 zeolite Substances 0.000 claims description 50
- 229910021536 Zeolite Inorganic materials 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000002987 primer (paints) Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000000049 pigment Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000004567 concrete Substances 0.000 description 6
- -1 for example Substances 0.000 description 6
- 238000013032 photocatalytic reaction Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機物，ＳＯｘ，ＮＯ
ｘ等を分解し、抗菌にも有効な光触媒作用をもち、有機
樹脂との組合せでも耐光性に優れた複合部材に関する。The present invention relates to organic matter, SOx, NO
The present invention relates to a composite member that decomposes x and the like, has a photocatalytic effect that is also effective as an antibacterial agent, and has excellent light resistance even when combined with an organic resin.
【０００２】[0002]
【従来の技術】ＴｉＯ2を初めとする光触媒は、光照射
で活性化し、有機物，ＳＯｘ，ＮＯｘ等を分解する作用
を呈する。この作用を活用し、光触媒粒子を配合した塗
膜を基材表面に設けることにより，各種材料に光触媒活
性を付与することが検討されている。光触媒活性が付与
された複合部材は，大都市周辺，工場地帯等の煤煙，排
ガス等で汚染された大気に起因する表面汚れを分解し、
長期にわたって美観を保持する。この種の光触媒被覆複
合部材において、光触媒粒子を分散させる塗膜のバイン
ダに有機物を使用すると、光触媒反応で生成したＯ2 -，
・ＯＨ等の活性酸素で有機塗膜が分解され、チョーキン
グによる塗膜剥離が生じる虞がある。 2. Description of the Related Art Photocatalysts such as TiO 2 are activated by light irradiation and exhibit a function of decomposing organic substances, SOx, NOx and the like. Utilizing this effect, it has been studied to provide a photocatalytic activity to various materials by providing a coating film containing photocatalyst particles on the surface of a substrate. The composite material with photocatalytic activity decomposes surface stains caused by the atmosphere contaminated with soot, exhaust gas, etc. around large cities, factory areas, etc.
Maintains aesthetics over a long period of time. In this type of photocatalyst coating composite member, the use of organic substances in the binder of the coating to disperse the photocatalyst particles, O 2 generated by the photocatalytic reaction -,
The organic coating film may be decomposed by active oxygen such as OH, and the coating film may peel due to choking.
【０００３】有機塗膜の分解を抑えるため、光触媒粒子
の配合量を減らしても、満足できる耐光性及び光触媒活
性が得られない。そのため、シリカ系等の無機材料がベ
ース樹脂として一般的に使用されている（特開平７−１
１３２７２号公報、特開平８−１６４３３４号公報、Ｗ
Ｏ９６／２９３７５号等参照）。また、有機系塗膜でも
比較的安定なフッ素樹脂をベースとするとき塗膜の分解
が抑制されるため、フッ素樹脂をベースとしてアナター
ゼ型ＴｉＯ2粒子を分散させた塗膜が知られている（特
開平７−１７１４０８号公報）。Even if the amount of the photocatalyst particles is reduced to suppress the decomposition of the organic coating film, satisfactory light resistance and photocatalytic activity cannot be obtained. Therefore, an inorganic material such as silica is generally used as the base resin (Japanese Patent Laid-Open No. 7-1).
13272, JP-A-8-164334, W
O96 / 29375, etc.). Further, even in an organic coating film, decomposition of the coating film is suppressed when it is based on a relatively stable fluororesin. Therefore, a coating film in which anatase type TiO 2 particles are dispersed based on the fluororesin is known ( JP-A-7-171408).
【０００４】[0004]
【発明が解決しようとする課題】無機材料をバインダと
する光触媒塗膜をもつ複合部材は、長期間にわたって光
照射に曝される建材等として使用されてもチョーキング
を発生せず、美観が長期間維持される。しかし、光触媒
粒子を担持する樹脂や要分解成分との接触を促進させ、
或いは光触媒粒子周囲に要分解成分の濃度を高めるもの
でなく、要分解成分と光触媒粒子が接触したときに始め
て光触媒反応が生じるため、使用すると分解能が低く濃
度の低いホルムアルデヒドの分解，脱ＳＯｘ，脱ＮＯｘ
等では改善の余地がある。A composite member having a photocatalytic coating film containing an inorganic material as a binder does not cause chalking even if it is used as a building material exposed to light irradiation for a long period of time and has a long-term aesthetic appearance. Maintained. However, it promotes contact with the resin carrying the photocatalyst particles and components that require decomposition,
Alternatively, the concentration of the decomposition-requiring component is not increased around the photocatalyst particles, and the photocatalytic reaction occurs only when the decomposition-requiring component and the photocatalyst particles come into contact. NOx
There is room for improvement.
【０００５】活性炭，ゼオライト等の吸着剤と共に光触
媒粒子を難分解性バインダで基体に担持させるとき、雰
囲気中の要分解成分が吸着剤で優先的に補集され、光触
媒粒子の分解能が向上する。しかし、光触媒粒子及び吸
着剤を塗膜に均一分散させることが難しく、しかも両者
がバインダで覆われてしまうと触媒作用及び吸着作用が
著しく低下する。更には、光触媒粒子を分散させた無機
塗膜が形成された金属板等では、加工性に劣ることも難
点である。たとえば、無機塗膜に光触媒粒子を分散させ
て光触媒活性を付与した塗装鋼板に曲げ加工を施すと、
クラックが発生しやすく、塗膜も鋼板表面から剥離しや
すい。他方、フッ素樹脂に光触媒粒子を分散させた塗膜
は、耐光性が不足しがちである。耐光性及び光触媒活性
の双方を満足させるために、光触媒粒子の周囲をシリカ
でコーティングすることにより光触媒粒子と有機塗膜と
の直接接触を防止する方法も考えられるが、この場合に
は光触媒粒子の光触媒活性が低下する。When the photocatalyst particles are supported on the substrate together with the adsorbent such as activated carbon or zeolite by the hardly decomposable binder, the components to be decomposed in the atmosphere are preferentially collected by the adsorbent, and the resolution of the photocatalyst particles is improved. However, it is difficult to uniformly disperse the photocatalyst particles and the adsorbent in the coating film, and when both are covered with the binder, the catalytic action and the adsorbing action are significantly reduced. Further, a metal plate or the like having an inorganic coating film in which photocatalyst particles are dispersed is inferior in workability. For example, when bending the coated steel sheet with photocatalytic activity by dispersing photocatalytic particles in an inorganic coating film,
Cracks easily occur and the coating film also easily peels off from the steel sheet surface. On the other hand, a coating film in which photocatalyst particles are dispersed in a fluororesin tends to have insufficient light resistance. In order to satisfy both the light resistance and the photocatalytic activity, a method of preventing the direct contact between the photocatalyst particles and the organic coating film by coating the periphery of the photocatalyst particles with silica is also considered, but in this case, Photocatalytic activity is reduced.
【０００６】[0006]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、ゼオライトで被
覆した光触媒粒子を塗膜に分散させることにより、光触
媒活性を高めると共に、バインダとして使用されている
塗膜の分解を抑制し、耐光性に優れた光触媒被覆複合部
材を提供することを目的とする。本発明の光触媒被覆複
合部材は、その目的を達成するため、ゼオライトで被覆
された光触媒粒子が分散した無機又は有機の光触媒塗膜
が基材表面に形成されていることを特徴とする。Means for Solving the Problems The present invention has been devised to solve such a problem. By dispersing photocatalyst particles coated with zeolite in a coating film, the photocatalytic activity is increased, and An object of the present invention is to provide a photocatalyst-coated composite member that suppresses decomposition of a coating film used as a binder and has excellent light resistance. In order to achieve the object, the photocatalyst-coated composite member of the present invention is characterized in that an inorganic or organic photocatalytic coating film in which photocatalyst particles coated with zeolite are dispersed is formed on the surface of a substrate.
【０００７】ゼオライトで被覆された光触媒粒子として
は、たとえば膜厚５ｎｍ〜５μｍのゼオライト皮膜で覆
われた光触媒粒子が使用され、５〜８０質量％の割合で
光触媒塗膜に分散させることが好ましい。基材には、金
属，ガラス，タイル，合成樹脂，パーティクルボード，
石膏，コンクリート等が使用される。金属性基体として
は、普通鋼板，めっき鋼板，ステンレス鋼板，アルミニ
ウム板，アルミニウム合金板等がある。ゼオライトで被
覆された光触媒粒子が分散した光触媒塗膜は、顔料を含
むプライマ塗膜を基材表面に形成した後、ゼオライトで
被覆された光触媒粒子を含む有機樹脂塗料をプライマ塗
膜の上に塗布し、熱処理により形成される。或いは、プ
ライマ層を省略し，基材表面に光触媒塗膜を直接形成し
てもよい。As the photocatalyst particles coated with zeolite, for example, photocatalyst particles coated with a zeolite film having a film thickness of 5 nm to 5 μm are used, and it is preferable to disperse the photocatalyst particles in the photocatalyst coating film at a ratio of 5 to 80% by mass. The base material is metal, glass, tile, synthetic resin, particle board,
Gypsum, concrete, etc. are used. Examples of the metallic substrate include ordinary steel plates, plated steel plates, stainless steel plates, aluminum plates, aluminum alloy plates and the like. A photocatalytic coating in which photocatalytic particles coated with zeolite are dispersed is formed by forming a primer coating containing pigment on the surface of the substrate, and then applying an organic resin coating containing photocatalytic particles coated with zeolite on the primer coating. Formed by heat treatment. Alternatively, the photocatalytic coating film may be directly formed on the surface of the base material without the primer layer.
【０００８】[0008]
【作用】光触媒粒子は，紫外線照射によって励起され、
有機物を分解する光触媒活性を呈する。そのため、有機
樹脂を用いて塗膜を形成すると、樹脂自体が酸化分解さ
れ、チョーキングが発生する。本発明者等は、光触媒反
応に起因したチョーキングを抑制する方法を検討する過
程で、ゼオライトで被覆された光触媒粒子を有機樹脂塗
膜に分散させると、光触媒活性を維持したまま有機樹脂
の分解が抑制されることを見出した。これは、次のよう
に推察される。[Function] Photocatalyst particles are excited by ultraviolet irradiation,
It exhibits photocatalytic activity to decompose organic substances. Therefore, when a coating film is formed using an organic resin, the resin itself is oxidatively decomposed and choking occurs. The present inventors, in the process of investigating the method of suppressing choking due to the photocatalytic reaction, when the photocatalyst particles coated with zeolite are dispersed in the organic resin coating film, the decomposition of the organic resin is maintained while maintaining the photocatalytic activity. It was found to be suppressed. This is guessed as follows.
【０００９】ゼオライトは、一般式Ｍx/mＡｌxＳｉ
(1-x)Ｏ2・ｎＨ2Ｏ（Ｍは陽イオン，ｍは陽イオンＭの価
数，ｎは空孔中に吸着された水分子の個数）で表される
アルミノケイ酸塩の結晶であり、ガス状成分を選択的に
吸着透過させる分子サイズ（５〜１３Å）の空孔を結晶
内部にもつモレキュラーシーブとして知られている。そ
のため、光触媒粒子の表面にゼオライト膜を設けても、
雰囲気中のホルムアルデヒド，ＳＯｘ，ＮＯｘ等はゼオ
ライト膜を透過し、光触媒粒子の表面に到達する。むし
ろ、ホルムアルデヒド，ＳＯｘ，ＮＯｘ等が雰囲気中か
ら優先的にゼオライト膜に吸着され、光触媒粒子に接触
する機会が増加し、光触媒活性が向上する。Zeolites have the general formula M x / m Al x Si
Aluminosilicate crystal represented by (1-x) O 2 · nH 2 O (M is a cation, m is a valence of the cation M, and n is the number of water molecules adsorbed in the holes) It is known as a molecular sieve having pores of a molecular size (5 to 13Å) that selectively adsorbs and permeates a gaseous component inside the crystal. Therefore, even if a zeolite film is provided on the surface of the photocatalyst particles,
Formaldehyde, SOx, NOx, etc. in the atmosphere pass through the zeolite membrane and reach the surface of the photocatalyst particles. Rather, formaldehyde, SOx, NOx, etc. are preferentially adsorbed on the zeolite membrane from the atmosphere, increasing the chances of contacting with the photocatalyst particles and improving the photocatalytic activity.
【００１０】ゼオライト膜を設けることにより光触媒活
性が向上する作用は、無機塗膜及び有機塗膜の何れでも
有効に機能する。有機塗膜では、更にゼオライト膜の形
成によって耐チョーキング性が改善される。すなわち、
光触媒粒子の表面で発生したラジカルは、移動可能距離
が非常に短く、光触媒粒子の表面がゼオライト膜で覆わ
れているため、塗膜を構成する有機樹脂まで到達しな
い。この点、シリカで被覆した光触媒粒子を分散させた
塗膜では、光触媒粒子と要分解成分との接触がシリカで
妨げられ、光触媒活性が低下する。The action of improving the photocatalytic activity by providing the zeolite membrane effectively functions in both the inorganic coating film and the organic coating film. In the organic coating film, the choking resistance is further improved by forming the zeolite film. That is,
The radicals generated on the surface of the photocatalyst particles do not reach the organic resin forming the coating film because the movable distance is very short and the surface of the photocatalyst particles is covered with the zeolite film. In this respect, in the coating film in which the photocatalyst particles coated with silica are dispersed, the contact between the photocatalyst particles and the components to be decomposed is prevented by the silica, and the photocatalytic activity is lowered.
【００１１】[0011]
【実施の形態】本発明に従った光触媒被覆複合部材は、
たとえば図１に示すように、金属，ガラス，タイル，合
成樹脂，パーティクルボード，石膏，コンクリート等の
基材１の表面に、必要に応じてプライマ層２を介して光
触媒塗膜３を設けている。プライマ層２は光触媒塗膜３
の密着性を向上させるために設けられるが、光触媒反応
の影響を受けにくい金属製等の無機質基材１ではプライ
マ層２を省略することも可能である（図２）。BEST MODE FOR CARRYING OUT THE INVENTION A photocatalyst-coated composite member according to the present invention comprises:
For example, as shown in FIG. 1, a photocatalyst coating film 3 is provided on the surface of a base material 1 such as metal, glass, tile, synthetic resin, particle board, gypsum, concrete, etc. via a primer layer 2 if necessary. . The primer layer 2 is a photocatalytic coating film 3
The primer layer 2 may be omitted in the inorganic base material 1 made of metal or the like, which is provided to improve the adhesiveness of the material, but is not easily affected by the photocatalytic reaction (FIG. 2).
【００１２】基材１として使用される金属製基板には、
普通鋼板，亜鉛めっき鋼板，アルミめっき鋼板等の各種
めっき鋼板，ステンレス鋼板，アルミニウム板，アルミ
ニウム合金板等がある。金属製基板を使用する場合、必
要に応じてアルカリ脱脂，クロメート処理，リン酸塩処
理等の前処理が施される。プライマ層２は、防錆顔料，
体質顔料，白色顔料等を有機樹脂に分散させた塗料を基
材１に塗布し，焼き付けることにより形成される。プラ
イマ層２は，光触媒塗膜３の密着性及び耐食性を改善す
る。有機樹脂としては、ポリエステル樹脂，アクリル樹
脂，エポキシ樹脂，ウレタン樹脂等が使用される。な
お、耐食性に優れ且つ光触媒塗膜３との密着性も良好な
金属製基板を使用する場合には、プライマ層２を省略す
ることもできる。The metal substrate used as the base material 1 includes
There are various plated steel plates such as ordinary steel plate, galvanized steel plate, aluminum plated steel plate, stainless steel plate, aluminum plate, aluminum alloy plate, etc. When using a metal substrate, pretreatment such as alkali degreasing, chromate treatment, and phosphate treatment is performed as necessary. The primer layer 2 is a rust preventive pigment,
It is formed by applying a coating material in which an extender pigment, a white pigment and the like are dispersed in an organic resin to the base material 1 and baking it. The primer layer 2 improves the adhesion and corrosion resistance of the photocatalytic coating film 3. As the organic resin, polyester resin, acrylic resin, epoxy resin, urethane resin or the like is used. The primer layer 2 may be omitted when a metal substrate having excellent corrosion resistance and good adhesion to the photocatalyst coating film 3 is used.
【００１３】光触媒塗膜３は、ゼオライト膜５で被覆さ
れた光触媒粒子４を分散させた塗料を静電吹付けやロー
ルコート等により塗布し、焼き付けることにより形成さ
れる。シリカ，アルミナ等の無機バインダを使用する場
合には４００℃以下で焼き付けられ、有機バインダを使
用する場合には２００℃以下の低温焼付けも可能であ
る。有機バインダには、ポリエステル樹脂，アクリル樹
脂，エポキシ樹脂，ウレタン樹脂，フッ化ビニリデン樹
脂，シリコーン樹脂等がある。光触媒粒子４としては、
ＴｉＯ2，ＺｎＯ，ＷＯ3，ＦｅＴｉＯ3，ＳｒＴｉＯ3の
１種又は２種以上が使用される。なかでも、化学的安定
性に優れ安価で活性度の高い微粒子（粒径：５〜２００
ｎｍ）が得られることから、アナターゼ型のＴｉＯ2が
好ましい。光触媒粒子４は、粒径が小さいほど活性度が
高くなるが、あまり細かな粒径では塗料への分散が困難
になる。The photocatalyst coating film 3 is formed by applying a coating material in which the photocatalyst particles 4 coated with the zeolite film 5 are dispersed by electrostatic spraying, roll coating, or the like, and baking it. When an inorganic binder such as silica or alumina is used, it can be baked at 400 ° C. or lower, and when an organic binder is used, low temperature baking at 200 ° C. or lower is also possible. Examples of the organic binder include polyester resin, acrylic resin, epoxy resin, urethane resin, vinylidene fluoride resin, and silicone resin. As the photocatalyst particles 4,
One or more of TiO 2 , ZnO, WO 3 , FeTiO 3 , and SrTiO 3 are used. Among them, fine particles with excellent chemical stability, low cost and high activity (particle size: 5 to 200
nm), anatase type TiO 2 is preferable. The smaller the particle size of the photocatalyst particle 4, the higher the activity, but if the particle size is too small, it becomes difficult to disperse it in the paint.
【００１４】アルミニウムアルコキシド，アルコキシシ
ラン、アルカリ金属及び／又はアルカリ土類金属アルコ
キシド，アミン類及び水を有機溶媒に溶解して調製した
溶液に光触媒粒子を分散させた後、粉末を濾過して１０
０〜４００℃で乾燥すると、溶液に含まれているアルコ
キシドが加水分解した状態で光触媒粒子４の表面に付着
し、加熱工程で脱水及び縮重合反応してゼオライト膜５
が形成される。このとき、アミン類が存在していると加
水分解後の白濁化が防止され、均質なゼオライト膜５が
生成すると共にゲル化が防止される。その結果、光触媒
粒子４の表面が均一なゼオライト膜５で覆われる。The photocatalyst particles are dispersed in a solution prepared by dissolving aluminum alkoxide, alkoxysilane, alkali metal and / or alkaline earth metal alkoxide, amines and water in an organic solvent, and the powder is filtered to obtain 10
When dried at 0 to 400 ° C., the alkoxide contained in the solution adheres to the surface of the photocatalyst particles 4 in a hydrolyzed state, and undergoes dehydration and polycondensation reaction in the heating step to cause the zeolite membrane 5
Is formed. At this time, the presence of amines prevents turbidity after hydrolysis, forms a homogeneous zeolite membrane 5 and prevents gelation. As a result, the surface of the photocatalyst particles 4 is covered with the uniform zeolite film 5.
【００１５】ゼオライト膜５で被覆された光触媒粒子４
は、５〜８０質量％の割合で光触媒塗膜３に分散され
る。光触媒粒子４の分散量が５質量％未満では光触媒反
応による有機物，ＳＯｘ，ＮＯｘ等の分解効率が十分で
なく、逆に８０質量％を超える配合量では光触媒塗膜３
の形成が困難になる。ゼオライト膜５は、５ｎｍ〜５μ
ｍの膜厚で光触媒粒子４の表面に形成することが好まし
い。５ｎｍ未満の膜厚では、ガスに対する吸着能が不足
すると共に、バインダとして有機樹脂を用いた場合に光
触媒粒子４と有機樹脂との接触を完全には防止できなく
なる。逆に、５μｍを超える膜厚では、ゼオライト膜５
にクラックが発生しやすくなる。なお、ゼオライト膜５
の膜厚は、溶液の濃度，粘度及び光触媒粒子４との接触
時間等によって調整される。Photocatalyst particles 4 coated with a zeolite film 5
Is dispersed in the photocatalyst coating film 3 at a ratio of 5 to 80 mass%. If the dispersed amount of the photocatalyst particles 4 is less than 5% by mass, the decomposition efficiency of organic substances, SOx, NOx, etc. due to the photocatalytic reaction is not sufficient, and conversely, if the compounded amount exceeds 80% by mass, the photocatalyst coating film 3
Formation becomes difficult. Zeolite membrane 5 is 5nm-5μ
It is preferable to form it on the surface of the photocatalyst particles 4 with a film thickness of m. When the film thickness is less than 5 nm, the gas adsorption ability becomes insufficient, and when the organic resin is used as the binder, the contact between the photocatalyst particles 4 and the organic resin cannot be completely prevented. Conversely, if the film thickness exceeds 5 μm, the zeolite film 5
Cracks are likely to occur. In addition, the zeolite membrane 5
The film thickness of is adjusted by the concentration and viscosity of the solution, the contact time with the photocatalyst particles 4, and the like.
【００１６】有機樹脂をバインダに使用する場合、光触
媒塗膜３形成時の焼付け温度は、使用する樹脂の種類に
応じた最適温度に定められる。一般の樹脂では１５０〜
３００℃の焼付け温度で十分であるが、耐熱樹脂を使用
する場合には４５０℃まで焼付け温度を拡げることがで
きる。１５０℃未満の焼付け温度では、高分子間の架橋
が十分に進行せず、密着不良や塗膜剥離を生じやすい。
逆に高すぎる焼付け温度では、樹脂の分解による塗膜剥
離が生じ、加工性が低下する。焼付け温度を適正に設定
することにより、プライマ層２と光触媒塗膜３との間に
強固な結合が得られ、プライマ層２に対する光触媒塗膜
３の密着性が向上する。なお、フッ化ビニリデン樹脂及
びアクリル樹脂の混合物をベースにした塗料では、焼付
け後に塗膜の結晶化を抑制するため制御冷却することが
好ましい。When an organic resin is used as the binder, the baking temperature for forming the photocatalytic coating film 3 is set to the optimum temperature according to the type of resin used. For general resins, 150-
Although a baking temperature of 300 ° C is sufficient, the baking temperature can be extended to 450 ° C when a heat-resistant resin is used. At a baking temperature of less than 150 ° C., crosslinking between the polymers does not proceed sufficiently, resulting in poor adhesion and peeling of the coating film.
On the other hand, if the baking temperature is too high, the coating film peels due to the decomposition of the resin, and the workability deteriorates. By setting the baking temperature appropriately, a strong bond is obtained between the primer layer 2 and the photocatalyst coating film 3, and the adhesion of the photocatalyst coating film 3 to the primer layer 2 is improved. In the case of a coating material based on a mixture of vinylidene fluoride resin and acrylic resin, it is preferable to perform controlled cooling in order to suppress crystallization of the coating film after baking.
【００１７】[0017]
【実施例１】アルミニウムイソプロポキシド１．０モ
ル，テトラエトキシシラン２．５モル，ナトリウムメト
キシド１．０モル，モノイソプロパノールアミン５．０
モル，水７．０モルをブチルセロソルブ１５．０モルに
溶解することにより、ゼオライトのゾル−ゲル基本浴を
調製した。ゾルゲル浴にブチルセロソルブを加えて粘度
を低下させたもの，及びヒドロキシプロピルセルロース
を０．２〜２．０％添加して粘度を増大させた浴を準備
した。Example 1 Aluminum isopropoxide 1.0 mol, tetraethoxysilane 2.5 mol, sodium methoxide 1.0 mol, monoisopropanolamine 5.0
A sol-gel basic bath of zeolite was prepared by dissolving 1 mol of water and 7.0 mol of water in 15.0 mol of butyl cellosolve. A sol-gel bath was prepared by adding butyl cellosolve to reduce the viscosity, and a bath in which hydroxypropyl cellulose was added in an amount of 0.2 to 2.0% to increase the viscosity was prepared.
【００１８】各ゾルゲル浴１リットルに粒径２０ｎｍの
アナターゼ型ＴｉＯ2粒子をそれぞれ１ｋｇ添加し、攪
拌して十分に分散させた後、フィルタで濾過し、３００
℃の乾燥炉で１０分間加熱した。ＴｉＯ2粒子４の表面
に形成されたゼオライト膜５は、５．０ｎｍ〜５．０μ
ｍの膜厚をもっていた。基材１にコンクリート板及び板
厚０．５ｍｍのアルミニウムめっき鋼板を使用し、防錆
顔料及び体質顔料を分散させたエポキシ樹脂塗料を塗布
し、２００℃×２０分で焼き付けてプライマ層２を形成
した。1 kg of anatase-type TiO 2 particles having a particle size of 20 nm was added to 1 liter of each sol-gel bath, stirred and sufficiently dispersed, and then filtered with a filter to obtain 300
It was heated in a drying oven at 0 ° C for 10 minutes. The zeolite film 5 formed on the surface of the TiO 2 particles 4 has a thickness of 5.0 nm to 5.0 μm.
It had a film thickness of m. A concrete plate and an aluminum-plated steel plate having a plate thickness of 0.5 mm are used as the base material 1, an epoxy resin paint in which a rust preventive pigment and an extender pigment are dispersed is applied, and baked at 200 ° C. for 20 minutes to form a primer layer 2. did.
【００１９】コンクリート板に対しては、ゼオライト膜
５で被覆した粒径２０ｎｍのアナターゼ型ＴｉＯ2粒子
５を分散させた光触媒塗料をプライマ層２に塗布し、２
００℃×２０分の焼付けで光触媒塗膜３を形成した。ア
ルミニウムめっき鋼板に対しては、ゼオライト膜５で被
覆した粒径７ｎｍのアナターゼ型ＴｉＯ2粒子４を分散
させた光触媒塗料を用いて同様に光触媒塗膜３を形成し
た。For the concrete plate, a photocatalyst paint in which the anatase type TiO 2 particles 5 having a particle diameter of 20 nm coated with the zeolite film 5 are dispersed is applied to the primer layer 2 and
The photocatalyst coating film 3 was formed by baking at 00 ° C. for 20 minutes. On the aluminum-plated steel sheet, the photocatalyst coating film 3 was similarly formed by using the photocatalyst coating material in which the anatase type TiO 2 particles 4 having a particle diameter of 7 nm and coated with the zeolite film 5 were dispersed.
【００２０】比較のため、ゼオライト膜５で被覆してい
ない粒径２０ｎｍのアナターゼ型ＴｉＯ2粒子を含む光
触媒塗膜３を形成したコンクリート板，粒径２０ｎｍの
アナターゼ型ＴｉＯ2粒子４及び粒径２μｍのゼオライ
ト粉末を含む光触媒塗膜３を形成したコンクリート板，
ゼオライト膜５で被覆していない粒径７ｎｍのアナター
ゼ型ＴｉＯ2粒子４を含む光触媒塗膜３を形成したアル
ミニウムめっき鋼板，粒径７ｎｍのアナターゼ型ＴｉＯ
2粒子４及び粒径２μｍのゼオライト粉末を含む光触媒
塗膜３を形成したアルミニウムめっき鋼板を用意した。For comparison, a concrete plate formed with a photocatalytic coating film 3 containing anatase-type TiO 2 particles having a particle size of 20 nm which is not covered with a zeolite film 5, anatase-type TiO 2 particles 4 having a particle size of 20 nm and a particle size of 2 μm. Concrete plate having a photocatalytic coating 3 containing the zeolite powder of
Aluminum-plated steel sheet having a photocatalytic coating film 3 containing anatase-type TiO 2 particles 4 having a particle size of 7 nm which is not coated with zeolite film 5, anatase-type TiO having a particle size of 7 nm
An aluminum-plated steel sheet on which a photocatalytic coating film 3 containing 2 particles 4 and a zeolite powder having a particle diameter of 2 μm was formed was prepared.
【００２１】光触媒塗膜３が形成された各複合部材をＮ
Ｏｘ分解能試験及び耐光性試験に供した。ＮＯｘ分解能
試験では、光触媒被覆複合部材をサイズ２１０ｍｍ×３
００ｍｍの試験片に切り出し、ガラス容器に入れた。蛍
光灯で照射しながら、濃度１ｐｐｍのＮＯガスを含む高
純度空気を流量０.５リットル／分で連続的にガラス容
器に送り込み、ガラス容器のガス出側でＮＯ濃度及びＮ
Ｏ2濃度をＮＯｘメータで測定した。測定値から次式に
従ってＮＯｘ除去率を算出し、得られたＮＯｘ除去率か
ら各試験片のＮＯｘ分解能を評価した。
Each composite member having the photocatalyst coating film 3 formed thereon is
It was subjected to an Ox resolution test and a light resistance test. In the NOx resolution test, the photocatalyst-coated composite member had a size of 210 mm × 3
A 00 mm test piece was cut out and placed in a glass container. While irradiating with a fluorescent lamp, high-purity air containing NO gas with a concentration of 1 ppm was continuously fed into the glass container at a flow rate of 0.5 liter / min, and NO concentration and N 2 were discharged at the gas outlet side of the glass container.
The O 2 concentration was measured with a NOx meter. The NOx removal rate was calculated from the measured value according to the following formula, and the NOx resolution of each test piece was evaluated from the obtained NOx removal rate.
【００２２】耐光性試験では、光触媒被覆複合部材をサ
イズ１００ｍｍ×１００ｍｍの試験片に切り出し、１０
センチ離れた位置に配置した２０Ｗのブラックライト
（ＵＶ強度： ５．０ｍＷ／ｃｍ2）で照射した。照射を
２４時間継続した後、試験片の表面を指でこすり、塗膜
が指に付着したものを×，指に付着することはないが光
沢保持率が８０％未満のものを△，指に付着せず光沢保
持率が８０％以上を○として耐光性を評価した。In the light resistance test, the photocatalyst-coated composite member was cut into a test piece having a size of 100 mm × 100 mm, and 10
Irradiation was performed with a 20 W black light (UV intensity: 5.0 mW / cm 2 ) arranged at a position separated by a centimeter. After irradiating for 24 hours, rub the surface of the test piece with a finger, x if the coating film adheres to the finger, x if it does not adhere to the finger but gloss retention rate is less than 80%, △, to the finger When the gloss retention rate was 80% or more without sticking, the light resistance was evaluated.
【００２３】表１及び表２の調査結果にみられるよう
に、ゼオライト膜５で被覆したＴｉＯ 2粒子４を分散さ
せた光触媒塗膜３は、ＴｉＯ2粒子４を単独で分散させ
た光触媒塗膜３やＴｉＯ2粒子及びゼオライト粉末を分
散させた光触媒塗膜３に比較して高いＮＯｘ分解能を示
した。また、紫外線照射によっても塗膜の有機成分が分
解されることなく、耐光性も良好であった。As seen in the survey results in Tables 1 and 2.
TiO coated with zeolite membrane 5 2Dispersed particles 4
The photocatalyst coating 3 formed is TiO 2.2Disperse particles 4 alone
Photocatalytic coating 3 and TiO2Separates particles and zeolite powder
Higher NOx resolution than the scattered photocatalytic coating 3
did. Also, the organic components of the coating film can be separated by UV irradiation.
The light resistance was also good without being understood.
【００２４】 [0024]
【００２５】 [0025]
【００２６】[0026]
【実施例２】基材１に板厚０.５ｍｍの亜鉛めっき鋼板
及びアルミニウムめっき鋼板を使用し、アルカリ脱脂，
リン酸塩処理を施した後、水洗，乾燥した。次いで、防
錆顔料及び体質顔料を分散させたポリエステル樹脂塗料
を塗布し、２１５℃×４０秒で焼き付けてプライマ層２
を形成した。亜鉛めっき鋼板に対してはゼオライト膜で
被覆した粒径２０ｎｍのアナターゼ型ＴｉＯ2を各種有
機樹脂に分散させた光触媒塗料をプライマ層２に塗布
し、アルミニウムめっき鋼板に対してはゼオライト膜５
で被覆した粒径７ｎｍのアナターゼ型ＴｉＯ2を各種有
機樹脂に分散させた光触媒塗料を用いて同様に光触媒塗
膜３を形成した。ゼオライト膜５で被覆した光触媒粒子
４としては、実施例１と同様に調製したものを使用し
た。ポリエステル樹脂をベースとする光触媒塗膜３では
２００〜２５０℃×１分間、フッ化ビニリデン−アクリ
ル混合樹脂をベースとする光触媒塗膜３では２５０℃×
１分間で焼き付けた。Example 2 Using a zinc-plated steel sheet and an aluminum-plated steel sheet having a plate thickness of 0.5 mm as the base material 1, alkali degreasing,
After the phosphate treatment, it was washed with water and dried. Then, a polyester resin coating material in which a rust preventive pigment and an extender pigment are dispersed is applied and baked at 215 ° C. for 40 seconds to form a primer layer 2
Was formed. A photocatalytic coating in which anatase-type TiO 2 having a particle diameter of 20 nm coated with a zeolite film is dispersed in various organic resins is applied to the primer layer 2 for a galvanized steel sheet, and a zeolite film 5 is applied for an aluminum-plated steel sheet.
Photocatalyst coating film 3 was similarly formed by using a photocatalyst paint in which anatase-type TiO 2 having a particle diameter of 7 nm coated with was dispersed in various organic resins. As the photocatalyst particles 4 coated with the zeolite film 5, those prepared in the same manner as in Example 1 were used. The photocatalytic coating film 3 based on polyester resin has a temperature of 200 to 250 ° C. × 1 minute, and the photocatalytic coating film 3 based on vinylidene fluoride-acrylic mixed resin has a temperature of 250 ° C. ×
It was baked in 1 minute.
【００２７】比較のため、ゼオライト膜５で被覆してい
ない粒径２０ｎｍのアナターゼ型ＴｉＯ2粒子４を含む
光触媒塗膜３を形成した亜鉛めっき鋼板，粒径２０ｎｍ
のアナターゼ型ＴｉＯ2粒子４及び粒径２μｍのゼオラ
イト粉末を含む光触媒塗膜３を形成した亜鉛めっき鋼
板，ゼオライト膜５で被覆していない粒径７ｎｍのアナ
ターゼ型ＴｉＯ2粒子４を含む光触媒塗膜３を形成した
アルミニウムめっき鋼板，粒径７ｎｍのアナターゼ型Ｔ
ｉＯ2粒子４及び粒径２μｍのゼオライト粉末を含む光
触媒塗膜３を形成したアルミニウムめっき鋼板を用意し
た。For comparison, a galvanized steel sheet having a photocatalytic coating film 3 containing anatase-type TiO 2 particles 4 having a particle size of 20 nm which is not coated with a zeolite film 5, a particle size of 20 nm
Galvanized steel sheet on which the photocatalytic coating film 3 containing the anatase-type TiO 2 particles 4 and the zeolite powder having a particle size of 2 μm is formed, and the photocatalytic coating film containing the anatase-type TiO 2 particles 4 having a particle size of 7 nm which is not covered with the zeolite film 5 3 plated aluminum plated steel sheet, anatase type T with a grain size of 7 nm
An aluminum-plated steel sheet on which a photocatalytic coating film 3 containing iO 2 particles 4 and zeolite powder having a particle diameter of 2 μm was formed was prepared.
【００２８】光触媒塗膜３が形成された各複合部材につ
いて、実施例１と同様な試験でＮＯｘ分解能及び耐光性
を調査すると共に、加工性も評価した。加工性試験で
は、２５ｍｍ×５０ｍｍの試験片を２ｔ曲げし、曲げ部
に粘着テープを貼り付けて瞬時に引き剥がした後、曲げ
部の塗膜剥離状況を目視観察し、塗膜剥離が検出された
ものを×，塗膜剥離が生じなかったものを○として加工
性を評価した。表３及び表４の調査結果にみられるよう
に、ゼオライト膜５で被覆したＴｉＯ 2粒子４を分散さ
せた光触媒塗膜３は、高いＮＯｘ分解能を示すと共に、
耐光性及び加工性も良好であった。これに対し、ＴｉＯ
2粒子４を単独で分散させた光触媒塗膜３やＴｉＯ2粒子
４及びゼオライト粉末を分散させた光触媒塗膜３は，紫
外線照射で塗膜の有機成分が分解しチョーキングが発生
した。For each composite member having the photocatalyst coating film 3 formed thereon,
Then, in the same test as in Example 1, NOx resolution and light resistance were obtained.
And the workability was also evaluated. In workability test
Bends a 25 mm x 50 mm test piece for 2t and bends
Attach the adhesive tape to the tape, peel it off instantly, and then bend it.
The film peeling situation of the part was visually observed, and the film peeling was detected.
Processed as x, and those where peeling of the coating did not occur were processed as o
The sex was evaluated. As seen in the survey results in Tables 3 and 4.
TiO coated with zeolite membrane 5 2Dispersed particles 4
The photocatalyst coating film 3 provided has a high NOx resolution and
The light resistance and workability were also good. On the other hand, TiO
2Photocatalyst coating 3 or TiO in which particles 4 are dispersed alone2particle
4 and the photocatalyst coating 3 in which the zeolite powder is dispersed are purple.
Choking occurs due to decomposition of organic components in the coating film by external irradiation
did.
【００２９】 [0029]
【００３０】 [0030]
【００３１】[0031]
【発明の効果】以上に説明したように、本発明の光触媒
被覆複合部材は，ゼオライト膜で被覆された光触媒粒子
を分散させた光触媒塗膜を形成しているので、雰囲気中
のホルムアルデヒド，ＳＯｘ，ＮＯｘ等の有害成分がゼ
オライト膜で吸着され，光触媒粒子の至近距離に維持さ
れる。そのため、光触媒反応が有害成分の分解に効率よ
く利用され、高い分解能が示される。また、光触媒粒子
を被覆するゼオライト膜は、塗膜を構成する有機成分と
光触媒粒子との直接接触を防止するため、光照射で励起
された光触媒粒子が発生するラジカルによって塗膜の有
機成分が分解されることがない。したがって、耐光性に
優れた光触媒塗膜となる。更に、基材に金属製基板を使
用するとき、加工性にも優れた塗装金属板が得られるの
で、光触媒活性を利用した各種内装建材，家電機器外板
等として広範な分野で使用される。As described above, since the photocatalyst-coated composite member of the present invention forms the photocatalyst coating film in which the photocatalyst particles coated with the zeolite film are dispersed, formaldehyde, SOx, Noxious components such as NOx are adsorbed by the zeolite membrane and maintained at a close distance to the photocatalyst particles. Therefore, the photocatalytic reaction is efficiently used for decomposing harmful components, and high resolution is exhibited. In addition, the zeolite membrane coating the photocatalyst particles prevents the organic components constituting the coating film from directly contacting the photocatalyst particles, so that the organic components of the coating film are decomposed by radicals generated by the photocatalyst particles excited by light irradiation. Never be done. Therefore, the photocatalytic coating film has excellent light resistance. Furthermore, when a metal substrate is used as the base material, a coated metal plate having excellent workability can be obtained, and thus it is used in a wide range of fields as various interior building materials utilizing photocatalytic activity, outer panels of home appliances, and the like.
【図１】 プライマ層を介して光触媒塗膜を形成した光
触媒被覆複合部材の表面層を示す断面図FIG. 1 is a cross-sectional view showing a surface layer of a photocatalyst-coated composite member in which a photocatalyst coating film is formed via a primer layer.
【図２】 基材に光触媒塗膜を直接形成した光触媒被覆
複合部材の表面層を示す断面図FIG. 2 is a cross-sectional view showing a surface layer of a photocatalyst-coated composite member in which a photocatalyst coating film is directly formed on a substrate.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ３２Ｂ 27/18 Ｂ３２Ｂ 27/18 Ｚ (72)発明者 坂戸 健二 千葉県市川市高谷新町７番１号 日新製 鋼株式会社技術研究所内 (72)発明者 安藤 彰啓 千葉県市川市高谷新町７番１号 日新製 鋼株式会社技術研究所内 (56)参考文献 特開2001−152362（ＪＰ，Ａ) 特開 平９−276706（ＪＰ，Ａ) 特開 平９−225321（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 1/00 - 35/00 C09D 1/00 - 201/10 B01J 21/00 - 35/02 Continuation of front page (51) Int.Cl. 7 Identification code FI B32B 27/18 B32B 27/18 Z (72) Inventor Kenji Sakado 7-1 Takatani Shinmachi, Ichikawa City, Chiba Nisshin Steel Co., Ltd. (72) Akihiro Ando 7-1 Takatani Shinmachi, Ichikawa City, Chiba Nisshin Steel Co., Ltd. Technical Research Laboratory (56) Reference JP 2001-152362 (JP, A) JP 9-276706 (JP, A) JP-A-9-225321 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B32B 1/00-35/00 C09D 1/00-201/10 B01J 21/00- 35/02
Claims (4)
散した光触媒塗膜が基材表面に形成されていることを特
徴とする光触媒活性及び耐光性に優れた光触媒被覆複合
部材。1. A photocatalyst-coated composite member having excellent photocatalytic activity and light resistance, wherein a photocatalyst coating film in which photocatalyst particles coated with zeolite are dispersed is formed on the surface of a substrate.
〜８０質量％の割合で光触媒塗膜に分散している請求項
１記載の光触媒被覆複合部材。2. Photocatalyst particles coated with zeolite are 5
The photocatalyst-coated composite member according to claim 1, which is dispersed in the photocatalyst coating film at a ratio of -80% by mass.
覆われた光触媒粒子が光触媒塗膜に分散している請求項
１記載の光触媒被覆複合部材。3. The photocatalyst-coated composite member according to claim 1, wherein the photocatalyst particles covered with a zeolite film having a film thickness of 5 nm to 5 μm are dispersed in the photocatalyst coating film.
む有機樹脂塗料をプライマ塗膜の上に塗布し、熱処理に
よりゼオライトで被覆された光触媒粒子が分散した光触
媒塗膜を形成することを特徴とする光触媒活性及び耐光
性に優れた光触媒被覆複合部材の製造方法。4. An organic resin paint containing photocatalyst particles coated with zeolite is applied on the primer coating film, and a photocatalytic coating film in which the zeolite-coated photocatalyst particles are dispersed is formed by heat treatment. A method for producing a photocatalyst-coated composite member having excellent photocatalytic activity and light resistance.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2000083903A JP3371104B2 (en) | 2000-03-24 | 2000-03-24 | Photocatalyst-coated composite member excellent in photocatalytic activity and light resistance and method for producing the same |
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| EP1990378A1 (en) * | 2007-05-10 | 2008-11-12 | SigmaKalon B.V. | A primer composition |
| WO2011115237A1 (en) * | 2010-03-15 | 2011-09-22 | 株式会社キャタラー | Photocatalyst filter, and deodorizing device equipped with same |
| JP7382687B2 (en) | 2021-03-08 | 2023-11-17 | 株式会社クリエイティブコーティングス | Zeolite membrane manufacturing method |
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