JP3766900B2 - Titanium dioxide photocatalyst-containing coating composition - Google Patents
Titanium dioxide photocatalyst-containing coating composition Download PDFInfo
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Description
【０００１】
本発明の分野
本発明は、脱臭、大気浄化、セルフクリーニング、抗菌等の機能を有する、二酸化チタン光触媒含有塗料組成物に関する。
【０００２】
背景技術
近年微粒子二酸化チタンの光触媒活性を利用し、有害物質を光化学反応によって分解し、除去ないし無害化しようとする研究が盛んに行われている。光触媒となる二酸化チタンは一般に平均粒子径０．１μｍ以下の微粒子ないし超微粒子であるから、飛散や流出を避けるため何らかの形で支持体へ光触媒を固定化しなければならない。一つの固定化方法は光劣化を受けにくい無機バインダー、例えばシリカゾル中に分散して塗料化し、これを基材に塗布、乾燥して光触媒を含む塗膜を形成する方法である（特開平８−１６４３３４）。
【０００３】
無機バインダーを使用するとバインダー自身が光触媒によって劣化することは避けられるが、塗膜性能特に耐衝撃性において有機樹脂をバインダーとする塗料に及ばない。
【０００４】
有機樹脂バインダーを使用した塗膜の光触媒による劣化を抑制するため、二酸化チタン光触媒と無機系脱臭吸着剤の混合物をシリカゾルを使って多孔質マイクロカプセル化し、これを有機樹脂に分散する方法が特開平９−３１３３５に記載されている。ところが、一般に顔料を塗料に均一に分散するためには、凝集により二次粒子に成長した粒子を一定の粒度以下にするためミルを使用してバインダー中で機械的に粉砕しなければならない。この時の物理的応力により光触媒の多孔質無機被覆層の少なくとも一部が破壊され、バインダー樹脂と直接接触するようになると、樹脂の光劣化による塗膜のチョーキング化が促進される。表面を多孔質シリカでコーティングした光触媒を使用しても同じ問題に遭遇する。
【０００５】
本発明の開示
そこで本発明は、塗料化に際し避けられない分散工程によっても所望の触媒活性レベルを維持しつつ、バインダー樹脂が比較的長期間光触媒作用によって劣化しない、多孔質シリカ被覆二酸化チタン光触媒を含む塗料組成物を提供する。
【０００６】
本発明は、乾燥塗膜中、多孔質シリカ被覆二酸化チタン光触媒含有量が５〜７０重量％（好ましくは３０〜６０重量％）、顔料二酸化チタン含有量が５〜５０重量％（好ましくは５〜２０重量％）となるように、多孔質シリカ被覆二酸化チタン光触媒および顔料二酸化チタンを有機樹脂ビヒクル中に分散してなる二酸化チタン光触媒含有塗料組成物を提供する。
【０００７】
詳細な議論
光触媒として機能するためには大きい比表面積を持たなければならないので、数ｎｍないし数１０ｎｍ範囲の微粒子ないし超微粒子が使用される。これに対し顔料二酸化チタンは通常０．２〜０．３μｍ（２００〜３００ｎｍ）の粒径を持っている。このような粒子径の相違により、顔料二酸化チタンは隠蔽力の大きい白色顔料として広く用いられるが、微粒子二酸化チタンはそのような光学的性質を持たない。また顔料二酸化チタンは、表面をＺｎＯ，Ａｌ2 Ｏ3 ，ＳｉＯ2 ，ＴｉＯ2 ，ＺｒＯ2 等の含水酸化物によってコーティングすることによって光触媒活性を抑制してある。光触媒として使用する微粒子二酸化チタンもマトリック樹脂と直接接触しないようにシリカ等によるコーティングが施されている。しかしこの場合は外気と接触する表面を持たなければならないから、コーティング量も顔料二酸化チタンに比較して少なく、かつ被覆層は多孔質である。
【０００８】
このような多孔質被覆処理された二酸化チタン光触媒は、例えば石原産業（株）から光触媒酸化チタンＳＴＥシリーズとして市販されている。光触媒となる二酸化チタンの結晶形は通常アナターゼ型である。
【０００９】
顔料二酸化チタンは、用途により各種銘柄のものが各社から市販されている。塗料用には耐候性にすぐれたルチル型が一般に使用されており、本発明においてもこれが好ましい。
【００１０】
これまで論じたように、有機マトリックス樹脂で固定した二酸化チタン光触媒塗膜の触媒活性と耐チョーキング性は一般に両立しない。換言すれば高い触媒活性を有する塗膜は短期間でチョーキングを起こし易い。本発明者らは、二酸化チタン光触媒と顔料二酸化チタンを一定の割合で併用することにより、触媒活性を所望レベルに維持しつつ耐チョーキング寿命を有意義に延長できることを発見した。
【００１１】
その結果、乾燥塗膜中の光触媒の顔料重量濃度ＰＷＣは５〜７０％，好ましくは３０〜６０％，顔料二酸化チタンのＰＷＣは５〜５０％，好ましくは５〜２０％が適当であることがわかった。総ＰＷＣは少なくとも４０％，好ましくは４０〜７０％が適当である。
【００１２】
有機樹脂は、乾燥塗膜中で光触媒および顔料二酸化チタンのマトリックスを構成する。使用される有機樹脂は慣用のものでよいが、特に含フッ素およびアクリルシリコーン系有機樹脂が好ましい。これら成分は塗料の分野では周知であり、これ以上の詳しい説明は不要であろう。
【００１３】
塗料化は、光触媒、顔料二酸化チタンおよび必要により他の添加剤をバインダー樹脂のワニスへ添加し、先に述べたように各種塗料用ミルを用いて所望粒度に達するまで均一に分散する。ガラスビーズ等の分散媒体を使用するミルが好ましい。
【００１４】
塗装は、ハケ、ローラー、吹付け等の一般の塗装法を用いて実施することができる。基材は金属、ガラス、セラミックス、コンクリート、木材等であるが、密着性を向上させるためブラスト処理やプライマー塗布を行った後に塗装してもよい。
【００１５】
形成された塗膜は、二酸化チタン光触媒による光化学反応によって大気中の有害物質を分解することにより、脱臭、大気浄化、セルフクリーニング、抗菌等の機能を発揮し、かつ有機樹脂を使用するにも拘らず有効寿命が長い。
【００１６】
以下の実施例において「部」および「％」は重量基準による。
【００１７】
実施例１
表１に示す配合の分散液Ｎｏ．１〜Ｎｏ．８を調製した。
【００１８】
【表１】
原料混合物をビーカーに入れ、これに粒径１．２〜１．５ｍｍのガラスビーズ（東芝）３００重量部を投入し、ディゾルバーにて１２００ｒｐｍの速度で約２０分間分散し、分散終了後ガラスビーズを濾過して除去し、分散液を得た。
【００２０】
この分散液９０重量部と、住友バイエルウレタン（株）製ＨＤＩ系ポリイソシアネート硬化剤Ｎ−７５（６０％酢酸ブチル溶液）１０重量部と、酢酸ブチル４５部を混合し、塗料液とした。
【００２１】
この塗料液をガラス板及びフッ素エナメル塗料既塗装板へそれぞれスプレー塗装し、室温で１４日間乾燥し、塗板を得た。
【００２２】
フッ素エナメル塗料既塗装板へ塗布したものはＪＩＳ Ｋ５４００に規定するサンシャインウエザーメーターにて１０００時間の促進暴露試験を行い、その塗膜劣化度をＪＩＳ Ｋ５４００に規定される白亜化度にて評価した。
【００２３】
ガラス板に塗布した塗板は強度５ｍＷ／ｃｍ2 の照射量にてブラックライトを４８時間照射した後、以下の試験方法によりＮＯガス分解性能を評価した。
【００２４】
ＮＯガス分解性能試験方法
試験装置：
ガス入口および出口を有する頂面を石英ガラス板で覆ったアクリル樹脂製ボックスに５０×３００ｍｍの試験片を石英ガラス板との間隔５ｍｍを保って固定し、石英ガラスの上方に設置したブラックライトから照射エネルギー１．５ｍＶ／ｃｍ2 にて試験片に紫外線を照射する。
試験方法：
測定開始前、前記装置にＮＯガス濃度３ｐｐｍの空気を１．５Ｌ／ｍｉｎの流量で６０分間通過させ、平衡化させる。平衡に達した後、装置の入口および出口においてガス中のＮＯ濃度それぞれＮＯINおよびＮＯOUT を測定し、以下の式を用いてＮＯガス分解率（％）を求める。
分解率（％）＝（ＮＯIN−ＮＯOUT ）×１００／ＮＯIN
結果：
塗膜中の光触媒と顔料二酸化チタン含量の白亜化度およびＮＯ分解率に対する影響を表２に示す。
【００２５】
【表２】
実施例２
フッ素樹脂塗料（イソシアネート架橋形）
樹脂：ルミフロンＬＦ−１００ ４８．０部
光触媒：タイペークＳＴＥ−０１ ２７．８部
着色顔料：タイペークＣＲ−９７ ２．７部
溶剤：酢酸ブチル １８．５部
ルミフロンＬＦ−１００：旭硝子（株）製フッソ樹脂系ポリオール
上記の原料混合物をビーカーに入れ、これに粒径１．２〜１．５ｍｍのガラスビーズ２００重量部を投入し、ディゾルバーにて１２００ｒｐｍの速度で約２０分間分散し、分散終了後、ガラスビーズを濾過により除去し、分散液を得た。この分散液９０部と硬化剤（住友バイエルウレタン（株）製ポリイソシアネート硬化剤Ｎ−７５ ６０％酢酸ブチル溶液）１０重量部と酢酸ブチル４５部を混合し、塗料液とした。
【００２７】
実施例３
フッ素樹脂塗料（メラミン架橋形）
樹脂：ルミフロンＬＦ−１００ ４８．０部
光触媒：タイペークＳＴＥ−０１ ２５．０５部
着色顔料：タイペークＣＲ−９７ ５．４５部
溶剤：酢酸ブチル １８．５部
添加剤：ＤＩＳＰＥＲ ＢＹＫ１６３ ３．０部
上記の原料混合物をビーカーに入れ、これに粒径１．２〜１．５ｍｍのガラスビーズ２００重量部を投入し、ディゾルバーにて１２００ｒｐｍの速度で約２０分間分散し、分散終了後、ガラスビーズを濾過により除去し、分散液を得た。この分散液９０部と三井サイナミッド（株）製メラミン樹脂３２５ １０重量部と酢酸ブチル４５部を混合し、塗料液とした。
【００２８】
実施例４
【００２９】
実施例５
【００３０】
実施例６
アクリルポリオール樹脂塗料（イソシアネート架橋形）
樹脂：アクリディックＡ−８０１ ４８．０部
光触媒：タイペークＳＴＥ−０１ ２５．０５部
着色顔料：タイペークＣＲ−９７ ５．４５部
溶剤：酢酸ブチル １８．５部
添加剤：ＤＩＳＰＥＲ ＢＹＫ１６３ ３．０部
上記の原料混合物をビーカーに入れ、これに粒径１．２〜１．５ｍｍのガラスビーズ２００重量部を投入し、ディゾルバーにて１２００ｒｐｍの速度で約２０分間分散し、分散終了後、ガラスビーズを濾過により除去し、分散液を得た。この分散液９０部と硬化剤（住友バイエルウレタン（株）製ポリイソシアネート硬化剤Ｎ−７５ ６０％酢酸溶液）１０重量部と酢酸ブチル４５部を混合し、塗料液とした。
【００３１】
実施例７
【００３２】
実施例２〜７の塗料について、実施例１と同様に促進耐候性試験およびＮＯ分解試験を行った。
【００３３】
試験片の作成および試験方法：
実施例２〜７の塗料を塗装用スプレーガンにてガラス板、及びフッ素塗料エナメル既塗装板に塗布し、実施例２，４〜７は室温にて１４日乾燥させたものを試験片とした。実施例３は室温で１時間セッティング後、１８０℃×２０分焼付硬化したものを試験片とした。
作成試験片のうち、フッ素塗料エナメル既塗装板に塗布乾燥したものについては、ＪＩＳ Ｋ５４００に規定するサンシャインウエザーメーターにて１０００時間、及び２０００時間の促進暴露を実施し、その塗膜表面劣化度をＪＩＳ Ｋ５４００に規定する白亜化度にて評価した。また、ガラス板に塗布乾燥したものについては、実施例１と同じ方法でＮＯ分解率を測定した。
【００３４】
【表３】
上の結果から、二酸化チタン光触媒に顔料二酸化チタンを併用することにより、有機ビヒクル樹脂の光触媒による劣化を抑制し得ることが明らかである。[0001]
Field of the present invention The present invention relates to a titanium dioxide photocatalyst-containing coating composition having functions such as deodorization, air purification, self-cleaning, and antibacterial.
[0002]
Background Art In recent years, active research has been conducted to decompose or remove harmful substances by photochemical reaction using the photocatalytic activity of fine particle titanium dioxide. Since titanium dioxide as a photocatalyst is generally fine particles or ultrafine particles having an average particle diameter of 0.1 μm or less, the photocatalyst must be fixed to the support in some form in order to avoid scattering and outflow. One immobilization method is a method of forming a coating film containing a photocatalyst by dispersing it in an inorganic binder that is not easily subject to photodegradation, for example, silica sol, and coating it on a base material and drying it (Japanese Patent Laid-Open No. Hei 8- 164334).
[0003]
When an inorganic binder is used, it is avoided that the binder itself deteriorates due to the photocatalyst, but the coating performance, particularly impact resistance, is not as good as that of a paint using an organic resin as a binder.
[0004]
In order to suppress deterioration due to the photocatalyst of the coating film using the organic resin binder, there is disclosed a method in which a mixture of a titanium dioxide photocatalyst and an inorganic deodorizing adsorbent is made into a porous microcapsule using silica sol and dispersed in an organic resin. 9-31335. However, in general, in order to uniformly disperse the pigment in the coating material, it is necessary to mechanically grind in the binder using a mill in order to make the particles that have grown into secondary particles by aggregation have a certain particle size or less. When at least a part of the porous inorganic coating layer of the photocatalyst is destroyed due to physical stress at this time and comes into direct contact with the binder resin, the choking of the coating film due to photodegradation of the resin is promoted. The same problem is encountered when using a photocatalyst whose surface is coated with porous silica.
[0005]
DISCLOSURE OF THE INVENTION Accordingly, the present invention provides a porous silica coating in which the binder resin is not deteriorated by photocatalysis for a relatively long period of time while maintaining a desired catalytic activity level even by a dispersion process that is unavoidable during coating. A coating composition comprising a titanium dioxide photocatalyst is provided.
[0006]
In the dried coating film, the present invention has a porous silica-coated titanium dioxide photocatalyst content of 5 to 70% by weight (preferably 30 to 60% by weight), and a pigment titanium dioxide content of 5 to 50% by weight (preferably 5 to 5%). A titanium dioxide photocatalyst-containing coating composition obtained by dispersing a porous silica-coated titanium dioxide photocatalyst and pigment titanium dioxide in an organic resin vehicle so as to be 20% by weight).
[0007]
Detailed discussion Since it must have a large specific surface area in order to function as a photocatalyst, fine particles or ultrafine particles in the range of several nm to several tens of nm are used. In contrast, pigmented titanium dioxide usually has a particle size of 0.2 to 0.3 μm (200 to 300 nm). Due to the difference in particle diameter, pigment titanium dioxide is widely used as a white pigment having a large hiding power, but fine particle titanium dioxide does not have such optical properties. The pigment titanium dioxide has a photocatalytic activity suppressed by coating the surface with a hydrous oxide such as ZnO, Al 2 O 3 , SiO 2 , TiO 2 or ZrO 2 . Fine titanium dioxide used as a photocatalyst is also coated with silica or the like so as not to come into direct contact with the matrix resin. However, in this case, since the surface must be in contact with the outside air, the coating amount is smaller than that of the pigment titanium dioxide, and the coating layer is porous.
[0008]
Such a porous coating-treated titanium dioxide photocatalyst is commercially available from, for example, Ishihara Sangyo Co., Ltd. as a photocatalytic titanium oxide STE series. The crystal form of titanium dioxide serving as a photocatalyst is usually anatase type.
[0009]
Pigmented titanium dioxide is commercially available from various companies depending on the application. A rutile type having excellent weather resistance is generally used for coatings, and this is preferable in the present invention.
[0010]
As discussed so far, the catalytic activity and choking resistance of a titanium dioxide photocatalyst film fixed with an organic matrix resin are generally incompatible. In other words, a coating film having high catalytic activity is likely to cause choking in a short period of time. The present inventors have found that the combined use of a titanium dioxide photocatalyst and pigment titanium dioxide in a certain ratio can significantly extend the anti-choking life while maintaining the catalyst activity at a desired level.
[0011]
As a result, it is appropriate that the pigment weight concentration PWC of the photocatalyst in the dried coating film is 5 to 70%, preferably 30 to 60%, and the PWC of the pigment titanium dioxide is 5 to 50%, preferably 5 to 20%. all right. The total PWC is suitably at least 40%, preferably 40-70%.
[0012]
The organic resin constitutes a matrix of photocatalyst and pigment titanium dioxide in the dried coating. Although the organic resin used may be a conventional one, fluorine-containing and acrylic silicone organic resins are particularly preferable. These components are well known in the field of paints and need no further explanation.
[0013]
In the coating process, a photocatalyst, pigment titanium dioxide and, if necessary, other additives are added to the varnish of the binder resin, and uniformly dispersed until reaching the desired particle size using various coating mills as described above. A mill using a dispersion medium such as glass beads is preferred.
[0014]
The painting can be carried out using a general painting method such as brushing, roller, spraying or the like. The base material is metal, glass, ceramics, concrete, wood, etc., but may be applied after blasting or primer application to improve adhesion.
[0015]
The formed coating film exhibits functions such as deodorization, air purification, self-cleaning, and antibacterial by decomposing harmful substances in the atmosphere by photochemical reaction with titanium dioxide photocatalyst, and even though organic resin is used. Long useful life.
[0016]
In the following examples, “parts” and “%” are based on weight.
[0017]
Example 1
Dispersion No. 1 having the composition shown in Table 1. 1-No. 8 was prepared.
[0018]
[Table 1]
The raw material mixture is put into a beaker, and 300 parts by weight of glass beads (Toshiba) having a particle size of 1.2 to 1.5 mm are added thereto, and dispersed in a dissolver at a speed of 1200 rpm for about 20 minutes. Removal by filtration gave a dispersion.
[0020]
90 parts by weight of this dispersion, 10 parts by weight of HDI polyisocyanate curing agent N-75 (60% butyl acetate solution) manufactured by Sumitomo Bayer Urethane Co., Ltd., and 45 parts of butyl acetate were mixed to prepare a coating liquid.
[0021]
The coating liquid was spray-coated on a glass plate and a fluorine enamel coating plate, and dried at room temperature for 14 days to obtain a coated plate.
[0022]
The coating applied to the pre-painted fluorine enamel paint plate was subjected to an accelerated exposure test for 1000 hours with a sunshine weather meter specified in JIS K5400, and the degree of coating film deterioration was evaluated based on the chalking degree specified in JIS K5400.
[0023]
The coated plate coated on the glass plate was irradiated with black light for 48 hours at an intensity of 5 mW / cm 2 and evaluated for NO gas decomposition performance by the following test method.
[0024]
NO gas decomposition performance test method <br/> Test equipment:
From a black light placed above the quartz glass, a 50 × 300 mm test piece was fixed to an acrylic resin box whose top surface with a gas inlet and outlet was covered with a quartz glass plate with a spacing of 5 mm from the quartz glass plate. The test piece is irradiated with ultraviolet rays at an irradiation energy of 1.5 mV / cm 2 .
Test method:
Before starting the measurement, air with an NO gas concentration of 3 ppm is passed through the apparatus at a flow rate of 1.5 L / min for 60 minutes to equilibrate. After reaching equilibrium, the NO concentrations in the gas, NO IN and NO OUT, are measured at the inlet and outlet of the apparatus, respectively, and the NO gas decomposition rate (%) is determined using the following equation.
Decomposition rate (%) = (NO IN −NO OUT ) × 100 / NO IN
result:
Table 2 shows the effects of the photocatalyst and pigment titanium dioxide content in the coating film on the chalking degree and the NO decomposition rate.
[0025]
[Table 2]
Example 2
Fluorine resin paint (isocyanate cross-linked type)
Resin: Lumiflon LF-100 48.0 parts Photocatalyst: Typek STE-01 27.8 parts Color pigment: Typek CR-97 2.7 parts Solvent: Butyl acetate 18.5 parts Lumiflon LF-100: Fluoro manufactured by Asahi Glass Co., Ltd. Resin-based polyol The above raw material mixture is placed in a beaker, 200 parts by weight of glass beads having a particle size of 1.2 to 1.5 mm are added thereto, and dispersed in a dissolver at a speed of 1200 rpm for about 20 minutes. The glass beads were removed by filtration to obtain a dispersion. 90 parts of this dispersion, 10 parts by weight of a curing agent (polyisocyanate curing agent N-75 60% butyl acetate solution manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 45 parts of butyl acetate were mixed to obtain a coating liquid.
[0027]
Example 3
Fluorine resin paint (melamine cross-linked type)
Resin: Lumiflon LF-100 48.0 parts Photocatalyst: Typek STE-01 25.05 parts Color pigment: Typek CR-97 5.45 parts Solvent: Butyl acetate 18.5 parts Additive: DISPER BYK163 3.0 parts The raw material mixture is put into a beaker, 200 parts by weight of glass beads having a particle size of 1.2 to 1.5 mm are added thereto, and dispersed in a dissolver at a speed of 1200 rpm for about 20 minutes. After the dispersion is completed, the glass beads are filtered. Removal gave a dispersion. 90 parts of this dispersion, 10 parts by weight of melamine resin 325 manufactured by Mitsui Sinamid Co., Ltd., and 45 parts of butyl acetate were mixed to obtain a coating liquid.
[0028]
Example 4
[0029]
Example 5
[0030]
Example 6
Acrylic polyol resin paint (isocyanate cross-linked type)
Resin: Acridic A-801 48.0 parts Photocatalyst: Typek STE-01 25.05 parts Color pigment: Typek CR-97 5.45 parts Solvent: Butyl acetate 18.5 parts Additive: DISPER BYK163 3.0 parts Above Into a beaker, 200 parts by weight of glass beads having a particle size of 1.2 to 1.5 mm are added and dispersed in a dissolver at a speed of 1200 rpm for about 20 minutes. After the dispersion is completed, the glass beads are filtered. To obtain a dispersion. 90 parts of this dispersion, 10 parts by weight of a curing agent (polyisocyanate curing agent N-75 60% acetic acid solution manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 45 parts of butyl acetate were mixed to obtain a coating liquid.
[0031]
Example 7
[0032]
The paints of Examples 2 to 7 were subjected to an accelerated weather resistance test and an NO decomposition test in the same manner as in Example 1.
[0033]
Test piece preparation and test method:
The paints of Examples 2 to 7 were applied to a glass plate and a fluorine paint enameled pre-painted plate with a spray gun for painting, and Examples 2 and 4 to 7 were used as test pieces that were dried at room temperature for 14 days. . In Example 3, after setting for 1 hour at room temperature, a sample which was baked and cured at 180 ° C. for 20 minutes was used as a test piece.
Of the prepared test pieces, those that were applied and dried on a pre-coated board with fluorine paint enamel were subjected to 1000 hours and 2000 hours of accelerated exposure using a sunshine weather meter specified in JIS K5400, and the coating surface deterioration degree was determined. Evaluation was made according to the chalking degree defined in JIS K5400. Moreover, about what apply | coated and dried to the glass plate, the NO decomposition rate was measured by the same method as Example 1. FIG.
[0034]
[Table 3]
From the above results, it is clear that the deterioration of the organic vehicle resin due to the photocatalyst can be suppressed by using the titanium dioxide photocatalyst in combination with the pigment titanium dioxide.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05155698A JP3766900B2 (en) | 1998-02-16 | 1998-02-16 | Titanium dioxide photocatalyst-containing coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05155698A JP3766900B2 (en) | 1998-02-16 | 1998-02-16 | Titanium dioxide photocatalyst-containing coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11228873A JPH11228873A (en) | 1999-08-24 |
| JP3766900B2 true JP3766900B2 (en) | 2006-04-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP05155698A Expired - Fee Related JP3766900B2 (en) | 1998-02-16 | 1998-02-16 | Titanium dioxide photocatalyst-containing coating composition |
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| US9073009B2 (en) * | 2006-06-01 | 2015-07-07 | Carrier Corporation | Air purification system |
| JP5137352B2 (en) * | 2006-07-28 | 2013-02-06 | 旭化成イーマテリアルズ株式会社 | Aqueous pollution control composition and painted product |
| ES2357083T3 (en) | 2007-08-28 | 2011-04-18 | Basf Se | TIO2 PHOTOACTIVE IN COATING MATERIALS. |
| US8431220B2 (en) * | 2009-06-05 | 2013-04-30 | Xerox Corporation | Hydrophobic coatings and their processes |
| WO2014097309A1 (en) | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
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| JPH11228873A (en) | 1999-08-24 |
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