JP2003231204A - Functional material and functional coating composition - Google Patents
Functional material and functional coating compositionInfo
- Publication number
- JP2003231204A JP2003231204A JP2002357195A JP2002357195A JP2003231204A JP 2003231204 A JP2003231204 A JP 2003231204A JP 2002357195 A JP2002357195 A JP 2002357195A JP 2002357195 A JP2002357195 A JP 2002357195A JP 2003231204 A JP2003231204 A JP 2003231204A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- contact angle
- water
- contamination
- oil
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000008199 coating composition Substances 0.000 title claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003746 surface roughness Effects 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 17
- 230000001699 photocatalysis Effects 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 239000002344 surface layer Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 238000009499 grossing Methods 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 7
- 239000004615 ingredient Substances 0.000 abstract 3
- 229910052573 porcelain Inorganic materials 0.000 abstract 1
- 230000004304 visual acuity Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 230000001443 photoexcitation Effects 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- -1 titanium alkoxides Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は屋内、屋外の油性成
分を含んだ汚染物質が付着しやすい部材において、付着
した油性成分を含んだ汚染物質を降雨、シャワー洗浄な
どで除去しやすくすることができる機能材に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention makes it easy to remove pollutants containing oily components attached indoors and outdoors by rainfall, shower washing or the like. It relates to functional materials that can be used.
【０００２】[0002]
【従来の技術】従来のガラス、陶磁器の釉薬の表層部に
おいて、光触媒を表層部に固定化し、その有機分解能力
で汚れを自然分解することや、表面を平滑にして物理的
に堆積しにくくすることで、汚れを付着しにくくする方
法がとられていた。2. Description of the Related Art In the surface layer of glazes of conventional glass and ceramics, a photocatalyst is fixed to the surface layer, and its organic decomposing ability allows natural decomposition of stains and smoothing of the surface to prevent physical accumulation. Therefore, a method has been taken to make it difficult for dirt to adhere.
【０００３】しかし、十分な紫外線が得られない場合や
汚れの負荷量が非常に多い場合において、油性成分を含
んだ汚染物質を降雨、シャワー洗浄などの方法で除去で
きない場合があった。However, when sufficient ultraviolet rays cannot be obtained or when the load of dirt is very large, there are cases where pollutants containing oily components cannot be removed by methods such as rainfall and shower washing.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、屋
内、屋外の油性成分を含んだ汚染物質が付着しやすい部
材において、水との接触角より油との接触角が大きくな
るようにすることで、付着した油性成分による汚染物質
を除去しやすくすることができる機能材を提供すること
にある。DISCLOSURE OF THE INVENTION An object of the present invention is to make a contact angle with oil larger than a contact angle with water in a member to which pollutants containing oily components indoors and outdoors easily adhere. Therefore, it is to provide a functional material capable of easily removing contaminants due to the attached oily component.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記課題を解
決するためになされたもので、酸化物からなる微細な凹
凸膜を表面に有し、前記表面が水との接触角より油との
接触角の方が大きく、前記酸化物はＣｕ、Ａｇ、Ｚｎ、
Ｖ、Ｗ、Ｐｔ、Ｎｂ、Ｓｂから選ばれる少なくとも一種
の金属が担持された光触媒機能を有する酸化物を含み、
前記凹凸膜の表面粗さＲａは基材の表面粗さより６ｎｍ
以上４０ｎｍ以下の範囲で大きく、前記酸化物の原料の
１次粒径が１５ｎｍ以下である機能材を提供する。The present invention has been made to solve the above-mentioned problems, and has a fine uneven film made of an oxide on the surface thereof, and the surface is formed of oil from a contact angle with water. Has a larger contact angle, and the oxide is Cu, Ag, Zn,
At least one metal selected from V, W, Pt, Nb, and Sb is included, and includes an oxide having a photocatalytic function,
The surface roughness Ra of the uneven film is 6 nm from the surface roughness of the base material.
Provided is a functional material which is large in the range of 40 nm or less and has a primary particle size of the oxide raw material of 15 nm or less.
【０００６】また、酸化物の微細な凹凸膜を形成するこ
とにより、水の接触角を２５度以下、帯電半減期を１０
秒以下のいずれかまたはその両方の機能を有することが
できる。さらに、光触媒機能を有する酸化物を用いるこ
とで、光励起により、この機能を向上させ維持すること
ができる。Further, by forming a fine uneven film of oxide, the contact angle of water is 25 degrees or less and the charging half-life is 10 degrees.
It may have either or both sub-second capabilities. Furthermore, by using an oxide having a photocatalytic function, this function can be improved and maintained by photoexcitation.
【０００７】微細な凹凸膜の形成方法は、酸化物の組成
または液濃度、塗布条件および焼成温度、焼成時間など
の固定化方法を変えることにより、適当な凹凸間隔およ
び凹凸高さ（表面粗さ）を持った微細な凹凸膜を形成す
る。例えば、ＳｉＯ2、Ａｌ2Ｏ3、Ｋ2Ｏ、Ｎａ2Ｏ、Ｌ
ｉ2Ｏ、ＴｉＯ2などの酸化物を１つまたは２つ以上含む
塗布液を１種類または２種類以上作製し、これを温度コ
ントロールされた基材上に１回または多数回、スプレー
などの方法で塗布し、十分な膜強度が得られる温度まで
加熱することにより、膜を形成させる。The method of forming a fine uneven film is carried out by changing the fixing method such as the composition or liquid concentration of the oxide, the coating conditions and the baking temperature, and the baking time to obtain an appropriate uneven interval and uneven height (surface roughness). ) Has a fine uneven film. For example, SiO 2 , Al 2 O 3 , K 2 O, Na 2 O, L
A method of preparing one or two or more kinds of coating solutions containing one or two or more oxides such as i 2 O and TiO 2 and spraying them once or multiple times on a temperature-controlled substrate. To form a film by heating to a temperature at which sufficient film strength is obtained.
【０００８】[0008]
【作用】適当な表面粗さを持った微細な凹凸膜を形成す
ることで、部材表面での油の拡散抵抗を増加させ、油の
接触角を低下させず、一方、部材表面の凹凸膜での水の
浸透力を増加させ、水の接触角を低下させる。このた
め、油性成分を含んだ汚染物質が表面に付着したあと、
降雨、シャワー、高圧スプレー、水を含ませたスポンジ
拭きなどで洗浄する場合、水の接触角より油の接触角が
大きくなるため、油と部材表面の間に水が入り込みやす
くなり、除去性が良くなる。微細な凹凸膜の凹凸間隔お
よび表面粗さが大きすぎると、油が凹凸にしみ込むこと
から拭き取りや洗浄で除去しにくくなることから、微細
な凹凸膜の表面粗さが基材表面の表面粗さに比べて、６
ｎｍ以上４０ｎｍ以下の範囲で大きいことが、好まし
い。[Function] By forming a fine uneven film having an appropriate surface roughness, the diffusion resistance of oil on the surface of the member is increased and the contact angle of the oil is not reduced. Increases water penetration and reduces water contact angle. Therefore, after contaminants containing oily components adhere to the surface,
When cleaning with rain, shower, high-pressure spray, or wiping with a sponge containing water, the contact angle of oil is larger than the contact angle of water, so water easily enters between the oil and the surface of the member, and the removability is improved. Get better. If the unevenness interval and the surface roughness of the fine uneven film are too large, the oil will soak into the unevenness, making it difficult to remove by wiping or washing.Therefore, the surface roughness of the fine uneven film is the surface roughness of the substrate surface. 6 compared to
It is preferable that it is large in the range of not less than 40 nm and not more than 40 nm.
【０００９】水との接触角を油との接触角より小さく
し、水の接触角を２５度以下とすることで、表面を水で
濡れやすくなるため、洗浄する場合に、油と部材表面の
間に水が入り込みやすくなり、除去性が良くなる。さら
に、光触媒機能を有する酸化物を用いることで、光励起
により、水の接触角をさらに低下させることができ、除
去性がさらに良くなる。When the contact angle with water is made smaller than the contact angle with oil and the contact angle with water is 25 degrees or less, the surface is easily wetted with water. Water can easily get in between and the removability is improved. Furthermore, by using an oxide having a photocatalytic function, the contact angle of water can be further reduced by photoexcitation, and the removability can be further improved.
【００１０】また、帯電半減期を１０秒以下にすること
で空気中の帯電した埃が静電気的に付着することも防止
できる。さらに、光触媒機能を有する酸化物を用いるこ
とで、光励起により、帯電半減期をさらに低下させるこ
とができ、付着防止効果が大きくなる。以上に加えて、
光触媒による有機物分解作用により、ねめり、カビ、藻
の発生を防ぐことができ新たな汚れを発生させず、汚れ
を付着させる油性成分を分解することができる。By setting the charging half-life to 10 seconds or less, it is possible to prevent electrostatically adhering charged dust in the air. Furthermore, by using an oxide having a photocatalytic function, the charging half-life can be further reduced by photoexcitation, and the anti-adhesion effect is enhanced. In addition to the above,
The action of photocatalysts to decompose organic substances can prevent the generation of entrainment, mold, and algae, can generate new stains, and can decompose the oily components to which the stains are attached.
【００１１】[0011]
【発明の実施の形態】次に、本発明の実施の形態を図面
に基づき説明する。図１、図２、図３は、本発明の実施
形態に係る機能材の概略を示す断面図である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1, FIG. 2 and FIG. 3 are cross-sectional views schematically showing a functional material according to an embodiment of the present invention.
【００１２】本発明の機能材の表面は図１に示すとお
り、基材表面１を酸化物２が覆い、微細な凹凸膜を形成
している。図２は基材表面１を酸化物２と光触媒機能を
有する酸化物３が微視的に分散された微細な凹凸膜を形
成している。図３は基材表面１を酸化物２が覆い、その
表面に光触媒機能を有する酸化物３が微視的に分散さ
れ、微細な凹凸膜を形成している。As shown in FIG. 1, the surface of the functional material of the present invention covers the substrate surface 1 with the oxide 2 to form a fine uneven film. In FIG. 2, a fine uneven film in which an oxide 2 and an oxide 3 having a photocatalytic function are microscopically dispersed is formed on a substrate surface 1. In FIG. 3, the base material surface 1 is covered with the oxide 2, and the oxide 3 having a photocatalytic function is microscopically dispersed on the surface to form a fine uneven film.
【００１３】タイル、ガラス、セラミクス、ホーローパ
ネルなどの基材表面１に対して、ＳｉＯ2、Ａｌ2Ｏ2、
Ｋ2Ｏ、Ｎａ2Ｏ、Ｌｉ2Ｏ、ＴｉＯ2などを必要に応じた
配合された酸化物、金属アルコシドまたはチタンアルコ
キシド、有機チタネートまたはその誘導体などを均一層
または多層に塗布後焼成することで酸化物２を固定化す
る。For a substrate surface 1 such as tile, glass, ceramics, enamel panel, etc., SiO 2 , Al 2 O 2 ,
By coating K 2 O, Na 2 O, Li 2 O, TiO 2 and the like, if necessary compounded oxides, metal alcosides or titanium alkoxides, organic titanates or their derivatives, etc. in a uniform layer or multiple layers and baking. The oxide 2 is fixed.
【００１４】この場合、酸化物の各粒子間の空隙や微細
気孔による表面粗さを、液組成、液濃度、基材温度、塗
布圧力、塗布量、塗布回数、加熱温度、加熱時間、昇温
速度などを適宜調整することにより、最適化する。例え
ば、液組成および液濃度について、酸化物ゾルであれば
１％以下が望ましく、金属アルコキシドでは５％以下が
望ましい。また、基材温度は８０度以上が望ましく、塗
布圧力、塗布量、塗布回数についてはできるだけ微細な
均一な霧化状態となるように適宜調整する。さらに、昇
温速度は基材の熱衝撃性を考慮しながら、基材表面温度
をできるだけ迅速に、かつ、均一になるように加熱装置
の選定を行い、適宜調整することが必要である。In this case, the surface roughness due to the voids and fine pores between the particles of the oxide is determined by the liquid composition, the liquid concentration, the substrate temperature, the coating pressure, the coating amount, the coating frequency, the heating temperature, the heating time, and the temperature rise. It optimizes by adjusting speed etc. appropriately. For example, the liquid composition and the liquid concentration are preferably 1% or less for oxide sol and 5% or less for metal alkoxide. The substrate temperature is preferably 80 ° C. or higher, and the coating pressure, coating amount, and number of coatings are appropriately adjusted so that the atomized state is as fine and uniform as possible. Furthermore, it is necessary to select the heating device and adjust the heating rate appropriately so that the surface temperature of the base material is as rapid and uniform as possible while taking into consideration the thermal shock resistance of the base material.
【００１５】微細な凹凸膜の凹凸間隔および表面粗さが
大きすぎると、油が凹凸にしみ込むことから拭き取りや
洗浄で除去しにくくなることから、５００ｎｍ以下であ
ることが望ましく、４００ｎｍ以下であることが好まし
い。さらに、微細な凹凸膜の表面粗さが基材表面の表面
粗さに比べて、６ｎｍ以上４０ｎｍ以下の範囲で大きい
ことが、より好ましい。なお、表面粗さＲａはＪＩＳＢ
０６０１に準拠して下記の測定条件で測定した。（触針
速度０．０３ｍｍ／ｓ、カットオフ０．０２５ｍｍ、測
定長さ０．３ｍｍ）。If the unevenness interval and the surface roughness of the fine uneven film are too large, the oil penetrates the unevenness and is difficult to remove by wiping or washing. Therefore, the thickness is preferably 500 nm or less, and 400 nm or less. Is preferred. Furthermore, it is more preferable that the surface roughness of the fine concavo-convex film is larger than the surface roughness of the substrate surface in the range of 6 nm or more and 40 nm or less. The surface roughness Ra is JISB.
According to 0601, it measured on the following measurement conditions. (Stylus speed 0.03 mm / s, cutoff 0.025 mm, measurement length 0.3 mm).
【００１６】表面粗さが大きくなりすぎないためには、
特に、酸化物の原料として１次粒径は１５ｎｍ以下が好
ましく、１０ｎｍ以下であれば望ましい。金属アルコキ
シドを使用する場合はチタンアルコキシド、アルコキシ
シランなどが挙げられ、チタンテトライソプロポキシド
が望ましい。有機チタネート誘導体ではチタンキレート
などが挙げられ、ジ−ｉ−プロポキシ−ビス（アセチル
アセトナト）チタンが望ましい。In order to prevent the surface roughness from becoming too large,
In particular, the primary particle size of the oxide raw material is preferably 15 nm or less, and more preferably 10 nm or less. When a metal alkoxide is used, titanium alkoxide, alkoxysilane, etc. are mentioned, and titanium tetraisopropoxide is preferable. Examples of the organic titanate derivative include titanium chelate, and di-i-propoxy-bis (acetylacetonato) titanium is preferable.
【００１７】酸化物は、例えば、ＳｉＯ2、Ａｌ2Ｏ3、
Ｋ2Ｏ、Ｎａ2Ｏ、Ｌｉ2Ｏ、ＴｉＯ2などを含む混合ゾル
をガラスまたは釉薬層の表面に塗布し、この上に、下層
に用いた混合ゾルよりアルカリ金属を減少させ、ＴｉＯ
2を加えた混合ゾルを塗布するなど基材表面層に対して
傾斜組成し多層構造にすることにより、光触媒機能や膜
強度を向上させることができる。The oxide is, for example, SiO 2 , Al 2 O 3 ,
A mixed sol containing K 2 O, Na 2 O, Li 2 O, TiO 2 or the like is applied to the surface of the glass or glaze layer, and alkali metal is reduced on the mixed sol used in the lower layer to form TiO 2.
The photocatalytic function and the film strength can be improved by forming a multi-layered structure by gradient composition with respect to the surface layer of the base material such as coating a mixed sol containing 2 added.
【００１８】一般に、例えば、施釉タイル表層部の水の
接触角は３０度、油の接触角は２０度と、水の接触角が
大きいため、油性成分が多い空気中の汚れ物質が付着し
た場合、水で洗浄しても、油と基材表面の隙間に水が入
り込みにくいため、除去しにくいことになる。また、こ
の表層部の帯電半減期は３０〜６０秒であり、空気中の
帯電した埃が静電気的に付着することを十分に防止でき
ていない。一方、本発明の機能材では、酸化物の微細な
凹凸膜を形成することにより油との接触角より水との接
触角の方が小さくなり、水の接触角は１５度、油の接触
角は２２度、帯電半減期は１．１秒であった。この場
合、水の接触角の方が小さいため、油性成分が多い空気
中の汚れ物質が付着した表面を水で洗浄する場合、油と
基材表面の隙間に水が入り込みやすいため、除去しやす
いことになり、さらに、空気中の帯電した埃が静電気的
に付着することを十分に防止できることで、長期に渡
り、付着した油性成分による汚れを除去しやすくするこ
とができる。なお、帯電半減期はＪＩＳＬ１０９４（Ａ
法）に準拠して測定した。Generally, for example, when the contact angle of water on the surface of the glazed tile is 30 degrees and the contact angle of oil is 20 degrees, the contact angle of water is large. Even if it is washed with water, it is difficult to remove it because it is difficult for water to enter the gap between the oil and the surface of the base material. In addition, the charging half-life of the surface layer portion is 30 to 60 seconds, and electrostatic charge of charged dust in the air cannot be sufficiently prevented. On the other hand, in the functional material of the present invention, the contact angle with water becomes smaller than the contact angle with oil by forming the fine uneven film of oxide, the contact angle of water is 15 degrees, and the contact angle of oil is Was 22 degrees and the charging half-life was 1.1 seconds. In this case, since the contact angle of water is smaller, it is easy to remove when cleaning the surface with dirt substances in the air, which is rich in oily components, with water, because water easily enters the gap between the oil and the base material surface. In addition, since it is possible to sufficiently prevent electrostatically attached charged dust in the air, it is possible to easily remove stains due to the attached oily component for a long period of time. The charging half-life is JISL1094 (A
Method).
【００１９】光触媒機能を有する酸化物は、光励起によ
って、洗浄の際、油性の汚れ物質をさらに流れ落ちやす
くすることができる。水の接触角は望ましくは２５度以
下に、好ましくは１０度以下に、また、帯電半減期は望
ましくは１０秒以下に、好ましくは５秒以下するため
に、液組成、液濃度、塗布量、塗布回数を適宜調整す
る。また、光触媒機能を有する酸化物には酸化チタン、
酸化亜鉛、酸化錫の少なくとも１つ以上を含んでいるこ
とが好ましい。The oxide having a photocatalytic function can further facilitate the flow of oily contaminants during cleaning by photoexcitation. Since the contact angle of water is desirably 25 degrees or less, preferably 10 degrees or less, and the charging half-life is desirably 10 seconds or less, preferably 5 seconds or less, the liquid composition, the liquid concentration, the coating amount, The number of applications is adjusted appropriately. Further, the oxide having a photocatalytic function is titanium oxide,
It preferably contains at least one of zinc oxide and tin oxide.
【００２０】光触媒機能を有する酸化物に担持される金
属は、光触媒機能が向上するものであれば良い。例え
ば、Ｃｕ、Ａｇ、Ｚｎ、Ｖ、Ｗ、Ｐｔ、Ｎｂ、Ｓｂなど
が挙げられる。特に、光触媒へ金属を担持する方法とし
て、ドーピングおよび光還元のどちらか一方またはその
組み合わせを用いることで、機能の持続性が得られる。The metal supported on the oxide having a photocatalytic function may be any one as long as the photocatalytic function is improved. For example, Cu, Ag, Zn, V, W, Pt, Nb, Sb, etc. may be mentioned. In particular, as a method of supporting a metal on the photocatalyst, by using either one of doping and photoreduction or a combination thereof, the sustainability of the function can be obtained.
【００２１】光触媒機能を有する酸化物は光励起により
親水化する部位または有機物を分解する部位として微視
的に配列されことが必要であり、配列間隔が４００ｎｍ
以下であることが好ましく、２００ｎｍ以下であること
が望ましい。The oxide having a photocatalytic function is required to be microscopically arranged as a site that becomes hydrophilic by photoexcitation or a site that decomposes an organic substance, and the array interval is 400 nm.
It is preferably not more than 200 nm, and more preferably not more than 200 nm.
【００２２】上記の製造方法を用いることにより、陶磁
器、ガラス、タイル、ホーローパネル、セラミックの表
面に直接形成することができる。By using the above manufacturing method, it can be directly formed on the surface of ceramics, glass, tiles, enamel panels and ceramics.
【００２３】（参考例１）あらかじめ表面温度を１２０
℃に加熱されたガラスの表面に、シリカゾル、アルミナ
ゾルを固形分比で１：１の総固形分０．３％の混合液を
２５ｇ／ｍ2の塗布量を２回に分けてスプレー噴霧した
あと、シリカゾル、カリウムゾルを固形分比で３：１の
総固形分０．２％の混合液を２５ｇ／ｍ2の塗布量を２
回に分けてスプレー噴霧し８５０℃で加熱処理を行い、
ガラス上に酸化物の微細な凹凸膜を形成した。この表面
の水の接触角は１５度、油の接触角は２５度、表面粗さ
Ｒａは２０ｎｍであった。このガラスの表面にカーボン
ブラックと油を混合したものを線上に垂らし、この線の
両側から水を垂らしたところ、この液が水の表面に浮い
たため、簡単にガラスの表面から落とすことができた。Reference Example 1 A surface temperature of 120
After spraying a mixed solution of silica sol and alumina sol having a solid content ratio of 1: 1 and a total solid content of 0.3% at a coating amount of 25 g / m 2 in two portions on the surface of the glass heated to ℃. , silica sol, potassium sol solid content ratio 3: 1 of the total solids of 0.2% of the mixture coating amount of 25 g / m 2 2
Spray spray and heat treatment at 850 ℃,
A fine uneven film of oxide was formed on the glass. The contact angle of water on this surface was 15 degrees, the contact angle of oil was 25 degrees, and the surface roughness Ra was 20 nm. When a mixture of carbon black and oil was dripped on the surface of this glass and water was dripped from both sides of this wire, this liquid floated on the surface of the water, so it could be easily dropped from the surface of the glass. .
【００２４】（参考例２）実施例１のスプレー噴霧しな
い以外は同様の処置を行った。この表面の水の接触角は
３１度、油の接触角は２２度、表面粗さＲａは８ｎｍで
あったが、カーボンブラックと油を混合したものを簡単
にガラスの表面から落とすことができなかった。Reference Example 2 The same treatment as in Example 1 was carried out except that the spray was not applied. The contact angle of water on this surface was 31 degrees, the contact angle of oil was 22 degrees, and the surface roughness Ra was 8 nm. However, a mixture of carbon black and oil could not be easily dropped from the glass surface. It was
【００２５】（実施例１）あらかじめ表面温度を８０℃
に加熱された施釉マットタイルの表面に、ＣｕとＡｇを
表面に担持した酸化チタンゾル、シリカゾル、カリウム
ゾルを固形分比で１：７：２の総固形分０．５％の混合
液を２５ｇ／ｍ2の塗布量で１回スプレー噴霧したあ
と、連続してＩＰＡで希釈されたチタンテトライソプロ
ポキシド５％液を２５ｇ／ｍ2の塗布量で１回スプレー
噴霧したあと７００℃で加熱処理を行い、施釉タイル上
に酸化物の微細な凹凸膜を形成した。この表面の水の接
触角は２２度、油の接触角は２６度、表面粗さＲａは４
００ｎｍ、帯電半減期は１．６秒であった。この施釉タ
イルの表面にカーボンブラックと油を混合したものを線
上に垂らし、この線の両側から水を垂らしたところ、こ
の液が水の表面に浮いたため、簡単に施釉タイルの表面
から落とすことができた。(Example 1) The surface temperature was previously set to 80 ° C.
On the surface of the glazed mat tile heated to 1, 25 g / titanium oxide sol carrying Cu and Ag, silica sol, and potassium sol in a solid content ratio of 1: 7: 2 with a total solid content of 0.5% were added. after once sprayed in a coating amount of m 2, a heat treatment in a continuous after 700 titanium tetraisopropoxide 5% solution diluted in IPA and once sprayed in a coating amount of 25 g / m 2 by ℃ Then, a fine uneven film of oxide was formed on the glazed tile. The contact angle of water on this surface is 22 degrees, the contact angle of oil is 26 degrees, and the surface roughness Ra is 4
00 nm, the charging half-life was 1.6 seconds. When a mixture of carbon black and oil was dripped on the surface of this glazed tile and water was dripped from both sides of this line, this liquid floated on the surface of the water, so it could be easily dropped from the surface of the glazed tile. did it.
【００２６】さらに、この施釉タイルを屋外に１週間曝
露しておいた。この表面の水の接触角は１５度、油の接
触角は２２度、帯電半減期は０．６秒であった。この施
釉タイルの表面にカーボンブラックと油を混合したもの
を線上に垂らし、この線の両側から水を垂らしたとこ
ろ、この液が水の表面に浮いたため、簡単に施釉タイル
の表面から落とすことができた。Further, the glazed tile was exposed outdoors for one week. The contact angle of water on this surface was 15 degrees, the contact angle of oil was 22 degrees, and the charging half-life was 0.6 seconds. When a mixture of carbon black and oil was dripped on the surface of this glazed tile and water was dripped from both sides of this line, this liquid floated on the surface of the water, so it could be easily dropped from the surface of the glazed tile. did it.
【００２７】（比較例１）実施例２で使用した酸化チタ
ンゾル、シリカゾル、アルミナゾルの固形分１．５％の
混合液を、１００ｇ／ｍ2の塗布量で１回スプレー噴霧
した以外は実施例２と同様の処置を行った。この表面の
水の接触角は１８度、油の接触角は２５度、表面粗さＲ
ａは５２０ｎｍ、帯電半減期は１．１秒であった。この
施釉タイルの表面にカーボンブラックと油を混合したも
のを線上に垂らし、この線の両側から水を垂らしたとこ
ろ、表面にこの液がしみ込んでいるため、水の表面に浮
くことがなく簡単に落とすことができなかった。[0027] (Comparative Example 1) Example 2 oxide using sol, silica sol, a mixture of solids 1.5% alumina sol, except were once sprayed in a coating weight of 100 g / m 2 Example 2 The same treatment was performed. The contact angle of water on this surface is 18 degrees, the contact angle of oil is 25 degrees, and the surface roughness R
a was 520 nm, and the charging half-life was 1.1 seconds. A mixture of carbon black and oil was draped on the surface of this glazed tile, and water was dripped from both sides of this line.Since this liquid soaked into the surface, it did not float on the surface of the water and could be easily I couldn't drop it.
【００２８】さらに、この施釉タイルを屋外に１週間曝
露しておいた。この表面の水の接触角は１４度、油の接
触角は２０度、帯電半減期は０．６秒であった。この施
釉タイルの表面にカーボンブラックと油を混合したもの
を線上に垂らし、この線の両側から水を垂らしたとこ
ろ、表面にこの液がしみ込んでいるため、水の表面に浮
くことがなく簡単に落とすことができなかった。Further, the glazed tile was exposed outdoors for one week. The contact angle of water on this surface was 14 degrees, the contact angle of oil was 20 degrees, and the charging half-life was 0.6 seconds. A mixture of carbon black and oil was draped on the surface of this glazed tile, and water was dripped from both sides of this line.Since this liquid soaked into the surface, it did not float on the surface of the water and could be easily I couldn't drop it.
【００２９】[0029]
【発明の効果】以上、説明したように、本発明によれ
ば、屋内、屋外の油性成分を含んだ汚染物質が付着しや
すい部材において、水との接触角より油との接触角のほ
うが大きくなる酸化物の微細な凹凸膜を形成すること
で、付着した油性成分を含んだ汚染物質を除去しやすく
することができる機能材を提供することが可能である。
また、本発明によれば、洗浄の際に使用する洗剤を低減
でき、水質汚染・浄化にかかるエネルギーと同時に二酸
化炭素の排出も抑制できる。As described above, according to the present invention, the contact angle with oil is larger than the contact angle with water in a member to which pollutants containing oily components indoors and outdoors easily adhere. It is possible to provide a functional material capable of easily removing adhered pollutants containing an oily component by forming a fine uneven film of the oxide.
Further, according to the present invention, the amount of detergent used for cleaning can be reduced, and the emission of carbon dioxide as well as the energy required for water pollution / purification can be suppressed.
【図１】本発明の一実施形態に係る機能材の概略を示す
断面図である。FIG. 1 is a cross-sectional view schematically showing a functional material according to an embodiment of the present invention.
【図２】本発明の一実施形態に係る機能材の概略を示す
断面図である。FIG. 2 is a sectional view schematically showing a functional material according to an embodiment of the present invention.
【図３】本発明の一実施形態に係る機能材の概略を示す
断面図である。FIG. 3 is a cross-sectional view schematically showing a functional material according to an embodiment of the present invention.
１…基材表層、 ２…酸化物、 ３…光触媒機能を有す
る酸化物。1 ... Substrate surface layer, 2 ... Oxide, 3 ... Oxide having photocatalytic function.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 3/00 Ｃ０９Ｋ 3/00 Ｒ (72)発明者 真弓 禎隆 福岡県北九州市小倉北区中島２丁目１番１ 号 東陶機器株式会社内 Ｆターム(参考） 4F100 AA17B AA18B AA19B AA20B AT00A BA02 DD07B DE01B GB90 JA20B JG10B JL06 JL08 4G069 AA03 BA04B BA48A BB04A BB04B BC26A BC31A BC31B BC32A BC32B BC35A BC54A BC55A BC60A BC75A CD10 DA06 EB18X FA03 FB23 4J038 HA171 HA211 HA441 JA16 JC38 NA05 PC03 PC04 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09K 3/00 C09K 3/00 R (72) Inventor Mayumi Sadataka 2nd Nakajima, Kitakyushu Kitakyushu City, Fukuoka Prefecture No. 1 No. 1 F-term inside Totoki Equipment Co., Ltd. 4J038 HA171 HA211 HA441 JA16 JC38 NA05 PC03 PC04
Claims (6)
し、前記表面が水との接触角より油との接触角の方が大
きく、前記酸化物はＣｕ、Ａｇ、Ｚｎ、Ｖ、Ｗ、Ｐｔ、
Ｎｂ、Ｓｂから選ばれる少なくとも一種の金属が担持さ
れた光触媒機能を有する酸化物を含み、前記凹凸膜の表
面粗さＲａは基材の表面粗さより６ｎｍ以上４０ｎｍ以
下の範囲で大きく、前記酸化物の原料の１次粒径が１５
ｎｍ以下であることを特徴とする機能材。1. A fine concavo-convex film made of an oxide is formed on the surface, the surface has a larger contact angle with oil than the contact angle with water, and the oxide has Cu, Ag, Zn, V, W, Pt,
At least one metal selected from Nb and Sb is included in the oxide having a photocatalytic function, and the surface roughness Ra of the concavo-convex film is larger than the surface roughness of the base material in the range of 6 nm or more and 40 nm or less. The raw material has a primary particle size of 15
A functional material having a thickness of nm or less.
あることを特徴とする請求項１に記載の機能材。2. The functional material according to claim 1, wherein a contact angle of the surface with water is 25 degrees or less.
徴とする請求項１または２に記載の機能材。3. The functional material according to claim 1, which has a charging half-life of 10 seconds or less.
2Ｏ、Ｎａ2Ｏ、Ｌｉ2Ｏから選ばれる少なくとも一種を
含むことを特徴とする請求項１乃至３のいずれか１項に
記載の機能材。4. The oxide is SiO 2 , Al 2 O 3 or K.
The functional material according to any one of claims 1 to 3, comprising at least one selected from 2 O, Na 2 O, and Li 2 O.
含むコーティング剤であって、前記酸化物はＣｕ、Ａ
ｇ、Ｚｎ、Ｖ、Ｗ、Ｐｔ、Ｎｂ、Ｓｂから選ばれる少な
くとも一種の金属が担持された光触媒機能を有する酸化
物を含み、該コーティング剤を塗布された表面は酸化物
からなる微細な凹凸膜を表面に有し、前記表面が水との
接触角より油との接触角の方が大きく、前記凹凸膜の表
面粗さＲａは基材の表面粗さより６ｎｍ以上４０ｎｍ以
下の範囲で大きいことを特徴とする機能性コーティング
組成物。5. A coating agent containing an oxide having a primary particle size of 15 nm or less, wherein the oxide is Cu or A.
A fine concavo-convex film containing an oxide having a photocatalytic function, in which at least one metal selected from g, Zn, V, W, Pt, Nb, and Sb is supported, and the surface coated with the coating agent is an oxide. On the surface, the surface has a larger contact angle with oil than the contact angle with water, and the surface roughness Ra of the concavo-convex film is larger than the surface roughness of the substrate in the range of 6 nm to 40 nm. A characteristic functional coating composition.
2Ｏ、Ｎａ2Ｏ、Ｌｉ2Ｏから選ばれる少なくとも一種を
含むことを特徴とする請求項５に記載の機能性コーティ
ング組成物。6. The oxide is SiO 2 , Al 2 O 3 or K.
The functional coating composition according to claim 5, comprising at least one selected from 2 O, Na 2 O, and Li 2 O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002357195A JP2003231204A (en) | 2002-12-09 | 2002-12-09 | Functional material and functional coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002357195A JP2003231204A (en) | 2002-12-09 | 2002-12-09 | Functional material and functional coating composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10265737A Division JP2000071359A (en) | 1998-09-02 | 1998-09-02 | Functional material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003231204A true JP2003231204A (en) | 2003-08-19 |
Family
ID=27785633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002357195A Pending JP2003231204A (en) | 2002-12-09 | 2002-12-09 | Functional material and functional coating composition |
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| Country | Link |
|---|---|
| JP (1) | JP2003231204A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325257C (en) * | 2004-01-08 | 2007-07-11 | 寿原株式会社 | Ink fountain |
Citations (7)
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|---|---|---|---|---|
| JPS63100042A (en) * | 1986-10-14 | 1988-05-02 | Nippon Sheet Glass Co Ltd | Glass article difficult-to be dirtied |
| JPH05302173A (en) * | 1992-04-28 | 1993-11-16 | Central Glass Co Ltd | Hydrophilic coating film and method for forming the same |
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH09228072A (en) * | 1995-06-14 | 1997-09-02 | Toto Ltd | Outdoor member |
| JPH09227156A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Material expressing hydrophilic properties depending on optical excitation of optical semiconductor |
| JPH10101374A (en) * | 1996-09-27 | 1998-04-21 | Central Glass Co Ltd | Anticlouding coating film and its production |
| JPH10231146A (en) * | 1996-12-18 | 1998-09-02 | Nippon Ita Glass Techno Res Kk | Antifogging and antifouling glass article |
-
2002
- 2002-12-09 JP JP2002357195A patent/JP2003231204A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63100042A (en) * | 1986-10-14 | 1988-05-02 | Nippon Sheet Glass Co Ltd | Glass article difficult-to be dirtied |
| JPH05302173A (en) * | 1992-04-28 | 1993-11-16 | Central Glass Co Ltd | Hydrophilic coating film and method for forming the same |
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH09228072A (en) * | 1995-06-14 | 1997-09-02 | Toto Ltd | Outdoor member |
| JPH09227156A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Material expressing hydrophilic properties depending on optical excitation of optical semiconductor |
| JPH10101374A (en) * | 1996-09-27 | 1998-04-21 | Central Glass Co Ltd | Anticlouding coating film and its production |
| JPH10231146A (en) * | 1996-12-18 | 1998-09-02 | Nippon Ita Glass Techno Res Kk | Antifogging and antifouling glass article |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325257C (en) * | 2004-01-08 | 2007-07-11 | 寿原株式会社 | Ink fountain |
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