JPH11228873A - Titanium dioxide photocatalyst-containing coating material composition - Google Patents
Titanium dioxide photocatalyst-containing coating material compositionInfo
- Publication number
- JPH11228873A JPH11228873A JP10051556A JP5155698A JPH11228873A JP H11228873 A JPH11228873 A JP H11228873A JP 10051556 A JP10051556 A JP 10051556A JP 5155698 A JP5155698 A JP 5155698A JP H11228873 A JPH11228873 A JP H11228873A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- photocatalyst
- parts
- weight
- resin
- 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.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title abstract description 10
- 239000000463 material Substances 0.000 title abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000000049 pigment Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000008199 coating composition Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 230000001877 deodorizing effect Effects 0.000 abstract description 2
- 230000000845 anti-microbial effect Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 19
- 239000011521 glass Substances 0.000 description 18
- 239000003973 paint Substances 0.000 description 14
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 13
- 239000011324 bead Substances 0.000 description 13
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- -1 Acrylic polyol Chemical class 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
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。[0001] The present invention relates to a coating composition containing a titanium dioxide photocatalyst, which has functions such as deodorization, air purification, self-cleaning, and antibacterial activity.
【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）。2. Description of the Related Art In recent years, intensive studies have been made to utilize a photocatalytic activity of fine particle titanium dioxide to decompose harmful substances by a photochemical reaction to remove or render them harmless. Since titanium dioxide serving 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 immobilized on the support in some form to avoid scattering and outflow.
One immobilization method is a method of dispersing in an inorganic binder that is not easily deteriorated by light, for example, silica sol to form a coating, applying the coating to a substrate, and drying to form a coating film containing a photocatalyst (Japanese Patent Application Laid-Open No. Hei 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。When an inorganic binder is used, the binder itself can be prevented from being deteriorated by a photocatalyst, but the performance of the coating film, particularly the impact resistance, is inferior to that of a coating using an organic resin as a binder.
【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。In order to suppress the deterioration of a coating film using an organic resin binder due to a photocatalyst, a method of dispersing the mixture of titanium dioxide photocatalyst and an inorganic deodorizing adsorbent in an organic resin by using a silica sol to form a porous microcapsule. Is described in JP-A-9-31335. However, generally, in order to uniformly disperse the pigment in the paint, it is necessary to mechanically pulverize the particles grown into secondary particles by agglomeration in a binder using a mill in order to reduce the particles to a certain particle size or less. At least a part of the porous inorganic coating layer of the photocatalyst is destroyed by the physical stress at this time, and if it comes into direct contact with the binder resin, choking of the coating film due to photodeterioration of the resin is promoted. The same problem is encountered using a photocatalyst whose surface is coated with porous silica.
【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。[0005] disclosure The present invention of the present invention, while maintaining a desired catalytic activity levels by dispersing step inevitable upon paint, not degraded by relatively long photocatalysis binder resin,
A coating composition comprising a porous silica-coated titanium dioxide photocatalyst is provided.
【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。According to the present invention, the content of the porous silica-coated titanium dioxide photocatalyst in the dried coating film is 5 to 70% by weight (preferably 30 to 60% by weight) and the content of the pigment titanium dioxide is 5 to 70% by weight.
Provided is a titanium dioxide photocatalyst-containing coating composition in which a porous silica-coated titanium dioxide photocatalyst and a pigmented titanium dioxide are dispersed in an organic resin vehicle so as to be 50% by weight (preferably 5 to 20% by weight).
【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（２００〜３００ｎ
ｍ）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。 Detailed Discussion Since fine particles must have a large specific surface area to function as a photocatalyst, fine particles or ultrafine particles in the range of several nm to several tens of nm are used. On the other hand, the pigment titanium dioxide is usually 0.2 to 0.3 μm (200 to 300 n
m). Due to such a difference in particle diameter, the pigment titanium dioxide is widely used as a white pigment having a large hiding power, but the fine particle titanium dioxide does not have such optical properties. The surface of the pigment titanium dioxide is coated with a hydrated oxide such as ZnO, Al 2 O 3 , SiO 2 , TiO 2 , and ZrO 2 to suppress the photocatalytic activity. The particulate 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】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。[0008] Such a titanium dioxide photocatalyst treated with a porous coating is commercially available, for example, as a photocatalytic titanium oxide STE series from Ishihara Sangyo Co., Ltd. The crystal form of titanium dioxide serving as a photocatalyst is usually an anatase type.
【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。Various brands of pigment titanium dioxide are commercially available from various companies depending on the application. A rutile type having excellent weather resistance is generally used for paints, and is also preferred in the present invention.
【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。As discussed above, the catalytic activity and choking resistance of a titanium dioxide photocatalytic coating film fixed with an organic matrix resin are generally incompatible. In other words, a coating having high catalytic activity is liable to cause chalking in a short period of time. The present inventors have found that the combined use of a titanium dioxide photocatalyst and a pigmented titanium dioxide at a certain ratio can significantly extend the choking life while maintaining the desired level of catalytic activity.
【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。As a result, 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 50%.
20% has been found to be suitable. Suitably the total PWC is at least 40%, preferably 40-70%.
【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。The organic resin constitutes the matrix of the photocatalyst and the pigmented titanium dioxide in the dried coating. The organic resin used may be a conventional one, but a fluorine-containing and acrylic silicone-based organic resin is particularly preferred. These components are well known in the coatings art and will not require further elaboration.
【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。In the preparation of a paint, a photocatalyst, a pigment titanium dioxide and, if necessary, other additives are added to a varnish of a binder resin and, as described above, are uniformly dispersed by using various paint mills until a desired particle size is reached. . Mills using a dispersion medium such as glass beads are preferred.
【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。The coating can be performed by using a general coating method such as brushing, roller, spraying and the like. The base material is metal,
The material may be glass, ceramics, concrete, wood, etc., but may be applied after blasting or primer application to improve adhesion.
【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。The formed coating film exhibits functions such as deodorization, air purification, self-cleaning, and antibacterial by decomposing harmful substances in the atmosphere by a photochemical reaction with a titanium dioxide photocatalyst, and uses an organic resin. Nevertheless, the service life is long.
【００１６】以下の実施例において「部」および「％」
は重量基準による。In the following examples, "part" and "%"
Is based on weight.
【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。Example 1 A dispersion No. having the composition shown in Table 1 was prepared. 1 to No. 8 was prepared.
【００１８】[0018]
【表１】 [Table 1]
【００１９】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。The raw material mixture is placed in a beaker, and 300 parts by weight of glass beads (Toshiba) having a particle size of 1.2 to 1.5 mm are put into the beaker and dispersed with a dissolver at a speed of 1200 rpm for about 20 minutes. The glass beads were removed by filtration to obtain a dispersion.
【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。90 parts by weight of this dispersion and an HDI-based polyisocyanate curing agent N-manufactured by Sumitomo Bayer Urethane Co., Ltd.
10 parts by weight of 75 (60% butyl acetate solution) and 45 parts of butyl acetate were mixed to prepare a coating liquid.
【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。The coating liquid was spray-coated on a glass plate and a plate already coated with a fluorine-containing enamel, and dried at room temperature for 14 days to obtain a coated plate.
【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。The coating applied to the plate already coated with the fluorine enamel paint is subjected to an accelerated exposure test for 1000 hours using a sunshine weather meter specified in JIS K5400, and the degree of deterioration of the coating film is determined by the degree of chalking specified in JIS K5400. evaluated.
【００２３】ガラス板に塗布した塗板は強度５ｍＷ／ｃ
ｍ2 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。The coated plate applied to the glass plate has a strength of 5 mW / c.
After irradiation with black light for 48 hours at an irradiation amount of m 2, the NO gas decomposition performance was evaluated by the following test method.
【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５０×３００ｍ
ｍ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３ｐｐ
ｍ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Ｎ
ＯOUT 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。 NO gas decomposition performance test method Test apparatus: 50 × 300 m in an acrylic resin box whose top surface having a gas inlet and an outlet is covered with a quartz glass plate
The test piece of m is fixed with a distance of 5 mm from the quartz glass plate, and the test piece is irradiated with ultraviolet light from a black light placed above the quartz glass at an irradiation energy of 1.5 mV / cm 2 . Test method: NO gas concentration 3 pp before the start of measurement
m of air at a flow rate of 1.5 L / min for 60 minutes to equilibrate. After reaching equilibrium, the NO concentration in the gas at the inlet and outlet of the device, NO IN and N, respectively.
O OUT is measured, and the NO gas decomposition rate (%) is obtained using the following equation. Decomposition rate (%) = (NO IN -NO OUT ) × 100 / NO IN Result: Table 2 shows the effect of the photocatalyst and pigment titanium dioxide content in the coating film on the degree of chalking and the NO decomposition rate.
【００２５】[0025]
【表２】 [Table 2]
【００２６】 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。Example 2 Fluororesin paint (isocyanate cross-linked type) Resin: Lumiflon LF-100 48.0 parts Photocatalyst: Taipaque STE-01 27.8 parts Color pigment: Taipaque CR-97 2.7 parts Solvent: butyl acetate 18 .5 parts Lumiflon LF-100: Fluoro resin-based polyol manufactured by Asahi Glass Co., Ltd.
200 parts by weight of glass beads having a size of ~ 1.5 mm were charged and dispersed by a dissolver at a speed of 1200 rpm for about 20 minutes. After the dispersion was completed, the glass beads were removed by filtration to obtain a dispersion. 90 parts of this dispersion and a curing agent (a polyisocyanate curing agent N-75 manufactured by Sumitomo Bayer Urethane Co., Ltd.)
A coating liquid was prepared by mixing 10 parts by weight of a 60% butyl acetate solution) and 45 parts of butyl acetate.
【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。Example 3 Fluororesin paint (melamine crosslinked type) Resin: Lumiflon LF-100 48.0 parts Photocatalyst: Taipaque STE-01 25.05 parts Color pigment: Taipaque CR-97 5.45 parts Solvent: butyl acetate 18 .5 parts Additive: DISPER BYK163 3.0 parts The above raw material mixture is placed in a beaker, and the particle size is 1.2.
200 parts by weight of glass beads having a size of ~ 1.5 mm were charged and dispersed by a dissolver at a speed of 1200 rpm for about 20 minutes. After the dispersion was completed, the glass beads were removed by filtration to obtain a dispersion. 90 parts of this dispersion was mixed with 10 parts by weight of melamine resin 325 manufactured by Mitsui Cynamid Co., Ltd. and 45 parts of butyl acetate to prepare a coating liquid.
【００２８】 実施例４ アクリルシリコーン樹脂塗料 樹脂：ゼムラックＡＭ１５３２ 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 ゼムラックＡＭ１５３２：鐘淵化学工業（株）製 アクリルシリコーン樹脂 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１００部とジブチル錫ジラウレ
ートのキシレン溶液（ジブチル錫ジラウレート：キシレ
ン＝１：９）１部と酢酸ブチル４５部を混合し、塗料液
とした。Example 4 Acrylic silicone resin paint Resin: Zemurac AM1532 48.0 parts Photocatalyst: Taipaque STE-01 25.05 parts Color pigment: Taipaque CR-97 5.45 parts Solvent: butyl acetate 18.5 parts Zemurac AM1532: Acrylic silicone resin manufactured by Kanegabuchi Chemical Industry Co., Ltd.
200 parts by weight of glass beads having a size of ~ 1.5 mm were charged and dispersed by a dissolver at a speed of 1200 rpm for about 20 minutes. After the dispersion was completed, the glass beads were removed by filtration to obtain a dispersion. 100 parts of this dispersion, 1 part of a xylene solution of dibutyltin dilaurate (dibutyltin dilaurate: xylene = 1: 9) and 45 parts of butyl acetate were mixed to prepare a coating liquid.
【００２９】 実施例５ フッ素エマルション樹脂塗料 ゼッフルＳＥ−３１０ 1) ４８．０部 テキサノール 2) ４．８部 タイペークＳＴＥ−０１ ２５．０５部 デイスパティックＳＭＡ 3) １．０部 プライマルＲＭ−８（２５％プロピレングリコール溶液） 4) ０．３部 脱イオン水 ９．９５部 ノプコ８０３４ 5) １．０部 リオファーストＨ−２０１ 6) ９．９部 １）ダイキン工業（株）製 ２）イーストマンケミカル社製 ３）日華化学（株）製 ４）ロームアンドハース社製 ５）サンノプコ（株）製 ６）東洋インキ製造（株）製ルチル型二酸化チタン顔料
分散水性ペースト 上記原料混合物をビーカーに入れ、デイゾルバーにて１
２００ｒｐｍの速度で約２０分間分散し、この分散液１
００部と脱イオン水２０部を混合し、塗料液とした。Example 5 Fluorine Emulsion Resin Paint Zeffle SE-310 1) 48.0 parts Texanol 2) 4.8 parts Taipaque STE-01 25.05 parts DISPATIC SMA 3) 1.0 part Primal RM-8 (25) 4) 0.3 part Deionized water 9.95 parts Nopco 8034 5) 1.0 part Rio First H-201 6) 9.9 parts 1) Daikin Industries, Ltd. 2) Eastman Chemical 3) Nichika Chemical Co., Ltd. 4) Rohm and Haas Co., Ltd. 5) Sannopco Co., Ltd. 6) Toyo Ink Mfg. Co., Ltd. rutile-type titanium dioxide pigment-dispersed aqueous paste The above raw material mixture is placed in a beaker, 1 at dissolver
The dispersion was dispersed at a speed of 200 rpm for about 20 minutes.
00 parts and 20 parts of deionized water were mixed to obtain a coating liquid.
【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。Example 6 Acrylic polyol resin paint (isocyanate crosslinked type) Resin: Acridic A-801 48.0 parts Photocatalyst: Taipaque STE-01 25.05 parts Color pigment: Taipaque CR-97 5.45 parts Solvent: acetic acid Butyl 18.5 parts Additive: DISPER BYK163 3.0 parts The above raw material mixture was placed in a beaker, and the particle size was 1.2.
200 parts by weight of glass beads having a size of ~ 1.5 mm were charged and dispersed by a dissolver at a speed of 1200 rpm for about 20 minutes. After the dispersion was completed, the glass beads were removed by filtration to obtain a dispersion. 90 parts of this dispersion and a curing agent (a polyisocyanate curing agent N-75 manufactured by Sumitomo Bayer Urethane Co., Ltd.)
10 parts by weight (60% acetic acid solution) and 45 parts of butyl acetate were mixed to prepare a coating liquid.
【００３１】 実施例７ アクリル樹脂塗料 樹脂：アクリディックＡ−１９８ＸＢ 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 ５０．０部 添加剤：ＤＩＳＲＥＲ ＢＹＫ１６３ ３．０部 アクリディックＡ−１９８ＸＢ：大日本インキ化学工業（株）製 アクリル樹脂 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部と酢酸ブチル４５部を混
合し、塗料液とした。Example 7 Acrylic resin paint Resin: Acridic A-198XB 48.0 parts Photocatalyst: Taipaque STE-01 25.05 parts Color pigment: Taipaque CR-97 5.45 parts Solvent: 50.0 parts of butyl acetate Agent: DISRER BYK163 3.0 parts Acrydic A-198XB: Acrylic resin manufactured by Dainippon Ink & Chemicals, Inc. The above-mentioned raw material mixture is placed in a beaker, and the particle size is 1.2.
200 parts by weight of glass beads having a size of ~ 1.5 mm were charged and dispersed by a dissolver at a speed of 1200 rpm for about 20 minutes. After the dispersion was completed, the glass beads were removed by filtration to obtain a dispersion. 90 parts of this dispersion and 45 parts of butyl acetate were mixed to prepare a coating liquid.
【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。The accelerated weathering test and the NO decomposition test were performed on the coating materials of Examples 2 to 7 in the same manner as in Example 1.
【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 Ｋ５４０
０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Ｎ
Ｏ分解率を測定した。Preparation of test piece and test method: Examples 2 to
The paint of No. 7 was applied to a glass plate and a prepainted plate of a fluorine paint enamel using a spray gun for coating, and the test pieces of Examples 2, 4 to 7 were dried at room temperature for 14 days. In Example 3, test pieces were set at room temperature for 1 hour, and baked and cured at 180 ° C. for 20 minutes. Of the prepared test pieces, those coated and dried on a pre-coated plate of fluorine paint enamel were subjected to accelerated exposure for 1000 hours and 2000 hours with a sunshine weather meter specified in JIS K5400, and the degree of deterioration of the coating film surface was measured. JIS K540
The evaluation was based on the degree of chalking defined as 0. In the case of coating and drying on a glass plate, N was applied in the same manner as in Example 1.
The O decomposition rate was measured.
【００３４】[0034]
【表３】 [Table 3]
【００３５】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。From the above results, it is clear that the degradation of the organic vehicle resin by the photocatalyst can be suppressed by using the titanium dioxide photocatalyst in combination with the pigment titanium dioxide.
Claims (3)
量％および５〜５０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
樹脂塗料ビヒクルに分散してなる二酸化チタン光触媒含
有塗料組成物。A porous silica-coated titanium dioxide photocatalyst and a pigmented titanium dioxide are dispersed in an organic resin coating vehicle so that the contents in a dry coating film are 5 to 70% by weight and 5 to 50% by weight, respectively. A titanium dioxide photocatalyst-containing coating composition comprising:
チタンの含有量がそれぞれ３０〜６０重量％および５〜
２０重量％である請求項１の塗料組成物。2. The content of the titanium dioxide photocatalyst and the content of the pigment titanium dioxide are 30 to 60% by weight and 5 to 5, respectively.
The coating composition according to claim 1, which is 20% by weight.
り、顔料二酸化チタンはルチル型である請求項１または
２の塗料組成物。3. The coating composition according to claim 1, wherein the titanium dioxide photocatalyst is an anatase type and the pigment titanium dioxide is a rutile type.
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 true JPH11228873A (en) | 1999-08-24 |
| JP3766900B2 JP3766900B2 (en) | 2006-04-19 |
Family
ID=12890278
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05155698A Expired - Fee Related JP3766900B2 (en) | 1998-02-16 | 1998-02-16 | Titanium dioxide photocatalyst-containing coating composition |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031297A (en) * | 2006-07-28 | 2008-02-14 | Asahi Kasei Chemicals Corp | Aqueous pollution control composition and painted product |
| WO2009027432A1 (en) | 2007-08-28 | 2009-03-05 | Basf Se | Photoactive tio2 in coating materials |
| JP2010280887A (en) * | 2009-06-05 | 2010-12-16 | Xerox Corp | Hydrophobic coating and process thereof |
| WO2014097309A1 (en) | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
| US9073009B2 (en) * | 2006-06-01 | 2015-07-07 | Carrier Corporation | Air purification system |
-
1998
- 1998-02-16 JP JP05155698A patent/JP3766900B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9073009B2 (en) * | 2006-06-01 | 2015-07-07 | Carrier Corporation | Air purification system |
| JP2008031297A (en) * | 2006-07-28 | 2008-02-14 | Asahi Kasei Chemicals Corp | Aqueous pollution control composition and painted product |
| WO2009027432A1 (en) | 2007-08-28 | 2009-03-05 | Basf Se | Photoactive tio2 in coating materials |
| US8283277B2 (en) | 2007-08-28 | 2012-10-09 | Basf Se | Photoactive TiO2 in coating materials |
| JP2010280887A (en) * | 2009-06-05 | 2010-12-16 | Xerox Corp | Hydrophobic coating and process thereof |
| WO2014097309A1 (en) | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
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| Publication number | Publication date |
|---|---|
| JP3766900B2 (en) | 2006-04-19 |
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