JP3509462B2 - Photocatalyst coating - Google Patents
Photocatalyst coatingInfo
- Publication number
- JP3509462B2 JP3509462B2 JP10821697A JP10821697A JP3509462B2 JP 3509462 B2 JP3509462 B2 JP 3509462B2 JP 10821697 A JP10821697 A JP 10821697A JP 10821697 A JP10821697 A JP 10821697A JP 3509462 B2 JP3509462 B2 JP 3509462B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- layer
- photocatalyst layer
- titanium oxide
- particles
- 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 110
- 239000011248 coating agent Substances 0.000 title claims description 20
- 238000000576 coating method Methods 0.000 title claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000007740 vapor deposition Methods 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 230000009471 action Effects 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000001877 deodorizing effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003405 preventing effect Effects 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 101150103171 DARS1 gene Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車、船舶、航
空機、建築物等の外壁、窓ガラス、透明プラスチック部
材等の汚染防止や防曇用、紫外線遮蔽用等に好適である
ととも、優れた耐候性を有する光触媒被覆体に関する。TECHNICAL FIELD The present invention is excellent in that it is suitable for the prevention of contamination of the outer walls of automobiles, ships, aircrafts, buildings, etc., window glass, transparent plastic members, etc., antifogging, and ultraviolet shielding. And a photocatalyst coating having excellent weather resistance.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】最近酸
化チタンの光活性が注目され、空気清浄化用、殺菌用、
脱臭用、防曇用、水浄化用、セルフクリーニング用等の
種々の用途への使用が提案されている。酸化チタンの結
晶構造には、正方晶系に属する高温型のルチル型及び低
温型のアナターゼ型、並びに斜方晶系のブルッカイト型
の３種類があるが、一般的に使用されているのは正方晶
系の２つの結晶型であり、なかでもルチル型の酸化チタ
ンが広く使用されているが、光触媒活性に関してはアナ
ターゼ型の方が高い。2. Description of the Related Art Recently, the photoactivity of titanium oxide has attracted attention, and it is used for air cleaning, sterilization,
It has been proposed to be used for various purposes such as deodorization, antifogging, water purification, and self-cleaning. There are three types of titanium oxide crystal structures, which are the high temperature type rutile type and low temperature type anatase type, which belong to the tetragonal system, and the orthorhombic brookite type, but the tetragonal system is generally used. Two types of crystal system, rutile type titanium oxide are widely used, but the anatase type has a higher photocatalytic activity.
【０００３】このような光活性を有する酸化チタンは、
400 nm以下の紫外線を吸収すると表面に強い酸化力を示
し、その表面に接触した化合物を分解する。そのため、
例えば酸化チタンを含む表面に汚染物質や匂い物質が付
着すると、それらの物質を酸化分解し、汚れ防止や消臭
の効果を発揮する。また紫外線等の光線を吸収すると表
面が超親水化して水滴が形成されなくなるため、防曇性
を発揮する。Titanium oxide having such photoactivity is
When it absorbs UV rays of 400 nm or less, it shows strong oxidizing power on the surface and decomposes the compounds in contact with the surface. for that reason,
For example, when contaminants or odorous substances adhere to the surface containing titanium oxide, these substances are oxidatively decomposed, and the effects of preventing stains and deodorizing are exhibited. Further, when light rays such as ultraviolet rays are absorbed, the surface becomes superhydrophilic and water droplets are not formed, so that antifogging property is exhibited.
【０００４】上記目的のために光触媒を外壁材や窓ガラ
ス等に付着させて使用する場合、外気に露出する表面
（外面）では過酷な気候条件に耐え得る十分な耐候性
や、雨等による汚れを除去し易い性質（セルフクリーニ
ング性）が要求されるし、室内に面する表面（内面）で
は空気清浄化作用、殺菌作用、脱臭作用、防曇作用等の
光活性が十分に発揮されなければならない。光触媒層の
耐候性や耐久性を向上させるためには酸化チタン粒子の
粒径を比較的大きくしたり、酸化チタン粒子を耐候性樹
脂で固定する必要があるが、そうすると光活性が低下す
る傾向がある。一方十分な光活性を得るためには酸化チ
タン粒子の粒径を比較的小さくしたり、酸化チタン粒子
の露出度を増大させたりする必要があるが、そうすると
耐候性や耐久性が低下し、汚染物質の吸着性が増大する
傾向がある。そのため、室内を外気から遮断するような
用途に使用する部材に光活性と耐候性を同時に満足する
光触媒層を形成し得る技術が望まれている。When the photocatalyst is used by adhering it to an outer wall material or a window glass for the above purpose, the surface (outer surface) exposed to the outside air has sufficient weather resistance to withstand harsh climatic conditions and stains due to rain or the like. Is required to be easily removed (self-cleaning property), and the surface facing the room (inner surface) must exhibit sufficient photoactivity such as air cleaning action, sterilizing action, deodorizing action, and antifogging action. I won't. In order to improve the weather resistance and durability of the photocatalyst layer, it is necessary to make the particle size of titanium oxide particles relatively large or fix the titanium oxide particles with a weather resistant resin, but this tends to decrease the photoactivity. is there. On the other hand, in order to obtain sufficient photoactivity, it is necessary to make the particle size of titanium oxide particles relatively small or to increase the degree of exposure of titanium oxide particles, but doing so lowers the weather resistance and durability and causes contamination. The adsorptivity of substances tends to increase. Therefore, there is a demand for a technique capable of forming a photocatalyst layer that simultaneously satisfies photoactivity and weather resistance on a member used for the purpose of shielding the room from the outside air.
【０００５】したがって本発明の目的は、室内を外気か
ら遮断するために使用される基材（窓ガラス等のガラス
板）の外面に光活性とともに十分な耐候性、耐久性及び
セルフクリーニング性を有する光触媒層を設け、内面に
高い光活性を有する光触媒層を設けてなる光触媒被覆体
を提供することである。Therefore, an object of the present invention is to provide a base material (a glass such as a window glass) used to shield a room from the outside air.
It is intended to provide a photocatalyst coated body in which a photocatalyst layer having photoactivity and sufficient weather resistance, durability and self-cleaning property is provided on the outer surface of a plate) and a photocatalyst layer having high photoactivity is provided on the inner surface.
【０００６】[0006]
【課題を解決するための手段】上記目的に鑑み鋭意検討
の結果、本発明者らは、基材の一方の面及び他方の面に
それぞれ異なる平均粒径の酸化チタン粒子を含有する光
触媒層を形成することにより、上記要求を満たす光触媒
被覆体を得ることができることを発見した。本発明者ら
はまた、外気に露出する面の光触媒層のバインダーとし
て十分な耐久性を有するフッ素系樹脂を使用することに
より、外面の光触媒層の耐候性、耐久性及びセルフクリ
ーニング性を向上させることができることを発見した。
本発明はかかる発見に基づき完成したものである。As a result of intensive studies in view of the above objects, the present inventors have found that a photocatalyst layer containing titanium oxide particles having different average particle diameters on one surface and the other surface of a substrate, respectively. It has been discovered that a photocatalyst coating satisfying the above requirements can be obtained by forming the photocatalyst. The present inventors also improve the weather resistance, durability and self-cleaning property of the outer photocatalyst layer by using a fluororesin having sufficient durability as a binder of the photocatalyst layer on the surface exposed to the outside air. I have found that I can.
The present invention has been completed based on these findings.
【０００７】すなわち、本発明の光触媒被覆体は、ガラ
ス板の両面に光触媒層を有し、前記ガラス板は一方の面
が外気に露出し、他方の面が室内に面しており、前記外
気に露出する側の面に形成された第一の光触媒層は、平
均粒径30〜100 nmの光触媒粒子がバインダーに分散して
なり、かつ厚さが 0.5 〜 50 μｍであり、前記室内に面す
る側の面に形成された第二の光触媒層は、平均粒径５〜
25 nmの光触媒粒子がバインダーに分散してなり、かつ
厚さが 0.5 〜 3.0 μｍであることを特徴とする。Namely, the photocatalyst-coated body of the present invention, Gala
The glass plate has photocatalytic layers on both sides, and the glass plate is on one side.
Is exposed to the outside air, and the other surface faces the room.
The first photocatalyst layer formed on the surface exposed to the air has photocatalyst particles with an average particle size of 30 to 100 nm dispersed in a binder.
And has a thickness of 0.5 to 50 μm and faces the room.
The second photocatalyst layer formed on the side surface of the
25 nm photocatalyst particles are dispersed in the binder, and
It is characterized in that the thickness is 0.5 to 3.0 μm .
【０００８】第一の光触媒層中の光触媒粒子をフッ素系
樹脂からなるバインダーに分散させることにより、優れ
た耐久性、耐候性及びセルフクリーニング性を発揮させ
ることができる。また第二の光触媒層中の光触媒粒子は
セラミックスゾルからなるバインダーに分散しており、
高光活性を示す。第一の光触媒層の光触媒粒子とバイン
ダーの重量比は１：９〜９：１であるのが好ましい。第
二の光触媒層は、酸化物系セラミックスの蒸着層を介し
てガラス板上に形成されているのが好ましい。また光触
媒粒子は酸化チタンからなるのが好ましい。By dispersing the photocatalyst particles in the first photocatalyst layer in a binder made of a fluororesin, excellent durability, weather resistance and self-cleaning property can be exhibited. The photocatalyst particles in the second photocatalyst layer are dispersed in a binder made of ceramics sol,
It exhibits high photoactivity. Photocatalyst particles and vine in the first photocatalyst layer
The weight ratio of the dars is preferably 1: 9 to 9: 1. First
The second photocatalyst layer is through the oxide ceramics vapor deposition layer.
And is preferably formed on a glass plate. See again
The medium particles are preferably made of titanium oxide .
【０００９】[0009]
【発明の実施の形態】以下、本発明を詳細に説明する。
[1] 光触媒被覆体の構成
[A] 第一の実施例
本発明の第一の実施例による光触媒被覆体は、図１に示
すように、基材１の一方の面に平均粒径30〜100 nmの光
触媒粒子を含有する第一の光触媒層２が形成されてお
り、他方の面に平均粒径５〜25nmの光触媒粒子を含有す
る第二の光触媒層３が形成されている。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [1] Configuration of Photocatalyst Coated Body [A] First Example As shown in FIG. 1, the photocatalyst coated body according to the first example of the present invention has an average particle diameter of 30 to 30 A first photocatalyst layer 2 containing photocatalyst particles of 100 nm is formed, and a second photocatalyst layer 3 containing photocatalyst particles having an average particle diameter of 5 to 25 nm is formed on the other surface.
【００１０】(1) 基材
基材１としては、ガラス板を用いることができる。基材
の大きさ、及び形状は特に制限されない。特に透明なガ
ラス板の場合、汚染防止作用、セルフクリーニング作
用、防曇性、消臭作用、殺菌作用等の他に紫外線吸収作
用を利用することができる。(1) Substrate As the substrate 1, a glass plate can be used. The size and shape of the base material are not particularly limited. In particular, in the case of a transparent glass plate, it is possible to utilize an ultraviolet absorbing function in addition to a pollution preventing function, a self-cleaning function, an antifogging property, a deodorizing function, a sterilizing function and the like.
【００１１】(2) 第一の光触媒層
(a) 光触媒粒子
第一の光触媒層２は外気に露出する層で、その中の酸化
チタン粒子の平均粒径は30〜100 nmである。酸化チタン
粒子の平均粒径が30nm未満であると、第一の光触媒層２
の耐候性が不十分であり、また100 nmを超えると光活性
が低下する。(2) First Photocatalyst Layer (a) Photocatalyst Particles The first photocatalyst layer 2 is a layer exposed to the outside air, and the titanium oxide particles therein have an average particle size of 30 to 100 nm. When the average particle size of titanium oxide particles is less than 30 nm, the first photocatalyst layer 2
Has insufficient weather resistance, and if it exceeds 100 nm, the photoactivity decreases.
【００１２】(b) バインダー
酸化チタン粒子を基材表面に固定するために、酸化チタ
ン粒子をバインダー中に均一に分散させる。バインダー
としては、耐候性及び耐久性に優れているとともに酸化
チタン粒子に対して不活性なフッ素系樹脂を用いる。使
用可能なフッ素系樹脂としては、ポリテトラフルオロエ
チレン、ポリフッ化ビニリデン樹脂、ビニルエーテル−
フルオロオレフィン共重合体、ビニルエステル−フルオ
ロオレフィン共重合体等が挙げられる。バインダー中に
は、架橋剤や分散剤等を配合しても良い。(B) Binder In order to fix the titanium oxide particles on the surface of the substrate, the titanium oxide particles are uniformly dispersed in the binder. As the binder, a fluorine-based resin having excellent weather resistance and durability and inert to titanium oxide particles is used. Fluorine-based resins that can be used include polytetrafluoroethylene, polyvinylidene fluoride resin, vinyl ether-
Examples thereof include fluoroolefin copolymers and vinyl ester-fluoroolefin copolymers. A crosslinking agent, a dispersant, or the like may be added to the binder.
【００１３】(c) 配合比
酸化チタン粒子とバインダー樹脂との配合比（重量比）
は、１：９〜９：１とするのが好ましく、２：８〜８：
２とするのがより好ましい。酸化チタン粒子／バインダ
ー樹脂の重量比が１：９未満であると光活性が不十分で
あり、また９：１を超えると第一の光触媒層２の耐候性
及び耐久性が低下する。(C) Compounding ratio Compounding ratio of titanium oxide particles and binder resin (weight ratio)
Is preferably 1: 9 to 9: 1 and 2: 8 to 8 :.
2 is more preferable. If the weight ratio of titanium oxide particles / binder resin is less than 1: 9, photoactivity is insufficient, and if it exceeds 9: 1, the weather resistance and durability of the first photocatalyst layer 2 are deteriorated.
【００１４】(d) 厚さ
第一の光触媒層２の厚さは0.5 〜50μｍ程度が好まし
い。第一の光触媒層２の厚さが0.5 μｍ未満であると光
活性が不十分であり、また50μｍを超えると過剰品質と
なる。より好ましい厚さは1.0 〜20μｍである。一般
に、窓ガラス等の透過光の歪み防止や透光率維持の観点
から、第一の光触媒層２の厚さを出来るだけ薄くするの
が好ましい。(D) Thickness The thickness of the first photocatalyst layer 2 is preferably about 0.5 to 50 μm. If the thickness of the first photocatalyst layer 2 is less than 0.5 μm, the photoactivity is insufficient, and if it exceeds 50 μm, the quality is excessive. A more preferable thickness is 1.0 to 20 μm. In general, it is preferable to make the thickness of the first photocatalyst layer 2 as thin as possible from the viewpoint of preventing distortion of transmitted light such as a window glass and maintaining the light transmittance.
【００１５】(3) 第二の光触媒層
(a) 光触媒粒子
第二の光触媒層３は室内に面する層で、その中の酸化チ
タン粒子の平均粒径は５〜25nmである。酸化チタン粒子
の平均粒径が５nm未満であると、光活性が不十分であ
り、また25nmを超えると第二の光触媒層３の耐候性が不
十分となる。(3) Second photocatalyst layer (a) Photocatalyst particles The second photocatalyst layer 3 is a layer facing the room, and the average particle diameter of titanium oxide particles therein is 5 to 25 nm. If the average particle size of the titanium oxide particles is less than 5 nm, the photoactivity is insufficient, and if it exceeds 25 nm, the weather resistance of the second photocatalyst layer 3 is insufficient.
【００１６】(b) バインダー
第二の光触媒層３は酸化チタン微粒子を均一に分散させ
るバインダーを含有するのが好ましい。酸化チタンの活
性の維持、下地密着性及び光触媒層の強度の向上等のた
めに、バインダーをセラミックスゾルから形成するのが
好ましい。バインダー用セラミックスゾルとしては、一
般式：Ｍ（ＯＲ）n （ただしＭはチタン以外の金属元素
であり、Ｒはアルキル基であり、ｎは金属元素の酸化数
である。）により表される金属アルコキシドからゾル−
ゲル法により得られたものが好ましい。バインダー用の
金属アルコキシドとしては珪素アルコキシドが好まし
く、例えばＳｉ（ＯＣＨ3 ) 4 、Ｓｉ（ＯＣ2 Ｈ5 )
4 、Ｓｉ（ｉ−ＯＣ3 Ｈ7 ) 4、Ｓｉ（ｔ−ＯＣ
4 Ｈ9 ) 4 等が挙げられる。またアルミニウムのアルコ
キシド（例えばＡｌ（ＯＣＨ3 ）3 、Ａｌ（ＯＣ
2 Ｈ5 )3、Ａｌ（ｉ−ＯＣ3 Ｈ7 ) 3、Ａｌ（ｔ−ＯＣ
4 Ｈ9 ) 3 等を使用しても良い。(B) Binder The second photocatalyst layer 3 preferably contains a binder for uniformly dispersing the titanium oxide fine particles. The binder is preferably formed of a ceramic sol in order to maintain the activity of titanium oxide, improve the adhesion to the base, and improve the strength of the photocatalyst layer. As a ceramic sol for a binder, a metal represented by the general formula: M (OR) n (where M is a metal element other than titanium, R is an alkyl group, and n is the oxidation number of the metal element). Alkoxide to sol-
Those obtained by the gel method are preferable. The metal alkoxide for the binder is preferably a silicon alkoxide, for example, Si (OCH 3 ) 4 or Si (OC 2 H 5 ).
4 , Si (i-OC 3 H 7 ) 4 , Si (t-OC
4 H 9 ) 4 and the like. Also, aluminum alkoxides (eg, Al (OCH 3 ) 3 , Al (OC
2 H 5) 3, Al ( i-OC 3 H 7) 3, Al (t-OC
4 H 9 ) 3 etc. may be used.
【００１７】(c) 配合比
第二の光触媒層３内において、酸化チタン微粒子とバイ
ンダーとの配合比（重量比）は、50／50〜80／20程度が
好ましい。酸化チタン微粒子の割合が50重量％未満であ
ると、光触媒活性が不十分であり、また80重量％を超え
ると第二の光触媒層３の強度が不十分になる。(C) Mixing ratio In the second photocatalyst layer 3, the mixing ratio (weight ratio) of the titanium oxide fine particles and the binder is preferably about 50/50 to 80/20. If the proportion of the titanium oxide fine particles is less than 50% by weight, the photocatalytic activity is insufficient, and if it exceeds 80% by weight, the strength of the second photocatalytic layer 3 is insufficient.
【００１８】(d) 厚さ
第二の光触媒層３の厚さは0.5 〜3.0 μｍであるのが好
ましい。0.5 μm 未満では光触媒活性が無く、また3.0
μm を超えてもさらなる光活性の向上はほとんどない。(D) Thickness The thickness of the second photocatalyst layer 3 is preferably 0.5 to 3.0 μm. Below 0.5 μm, there is no photocatalytic activity,
There is almost no further improvement in photoactivity beyond μm.
【００１９】[B] 第二の実施例
窓ガラスのようにナトリウム等の酸化チタンに対して反
応性を有する成分を含有する基材１の場合、直接酸化チ
タンからなる光触媒層を形成すると、酸化チタンとナト
リウムとが反応して光活性が劣化するおそれがあるの
で、図２に示すように予め基材１上にバリアー層４を蒸
着法により形成しておくのが好ましい。なお図２では第
二の光触媒層３の下にのみバリアー層４が示されている
が、第一の光触媒層２の下に形成しても良い。[B] Second Example In the case of the substrate 1 containing a component having reactivity with titanium oxide such as sodium as in a window glass, when a photocatalyst layer made of titanium oxide is directly formed, it is oxidized. Since titanium and sodium may react with each other to deteriorate the photoactivity, it is preferable to previously form the barrier layer 4 on the substrate 1 by vapor deposition as shown in FIG. Although the barrier layer 4 is shown only under the second photocatalyst layer 3 in FIG. 2, it may be formed under the first photocatalyst layer 2.
【００２０】基材１の少なくとも一方の面に蒸着するバ
リアー層４は一般的に酸化物系セラミックスからなる。
特に上に形成する光触媒層中の成分との親和性を考慮し
て、酸化珪素（SiO2）又は酸化チタン（TiO2）が好まし
い。The barrier layer 4 deposited on at least one surface of the substrate 1 is generally made of oxide ceramics.
Particularly, silicon oxide (SiO 2 ) or titanium oxide (TiO 2 ) is preferable in consideration of the affinity with the components in the photocatalyst layer formed above.
【００２１】バリアー層４の蒸着方法としては、例えば
スパッタリング法、真空蒸着法、ＣＶＤ法、イオンプレ
ーティング法等を挙げることができる。酸化珪素等の酸
化物系セラミックスはプラスチックに対して特に親和性
を有さないので、基材１がプラスチックの場合、バリア
ー層４の緻密性及び基材１への密着性を向上させるため
には、蒸着法を利用する必要がある。また酸化物系セラ
ミックスの蒸着層は非常に薄くできるので、バリアー層
４の形成後に基材１に変形応力をかけることはなく、基
材１の変形が防止できる。Examples of the vapor deposition method of the barrier layer 4 include a sputtering method, a vacuum vapor deposition method, a CVD method, an ion plating method and the like. Oxide ceramics such as silicon oxide has no particular affinity for plastics. Therefore, in the case where the substrate 1 is plastic, in order to improve the denseness of the barrier layer 4 and the adhesion to the substrate 1, , It is necessary to use the vapor deposition method. In addition, since the vapor deposition layer of oxide-based ceramics can be made very thin, deformation stress of the base material 1 can be prevented without applying deformation stress to the base material 1 after the barrier layer 4 is formed.
【００２２】バリアー層４の厚さは30〜300 nmであるの
が好ましい。バリアー層４の厚さが30nm未満であると、
基材１と第二の光触媒層３の分離が不十分であり、第二
の光触媒層３に微細なクラックが発生する。またバリア
ー層４の厚さを300 nm超としても基材保護効果のさらな
る向上が得られない。バリアー層４のより好ましい厚さ
は50〜100 nmである。The thickness of the barrier layer 4 is preferably 30 to 300 nm. When the thickness of the barrier layer 4 is less than 30 nm,
Separation of the base material 1 and the second photocatalyst layer 3 is insufficient, and fine cracks occur in the second photocatalyst layer 3. Further, even if the thickness of the barrier layer 4 exceeds 300 nm, the base material protecting effect cannot be further improved. The more preferable thickness of the barrier layer 4 is 50 to 100 nm.
【００２３】[2] 光触媒被覆体の製造方法
[A] 第一の光触媒層の形成
第一の光触媒層２を形成するための塗布液としては、酸
化チタン微粒子又はゾルとフッ素系樹脂とを適当な溶剤
に溶解・分散させたものが好ましい。酸化チタンゾルは
チタンアルコキシドのゾル−ゲル法による加水分解中間
生成物である。ゾル−ゲル法では、チタンアルコキシド
を出発物質とし、溶液中での化合物の加水分解・重合に
より金属酸化物又は水酸化物のゾル微粒子とする。チタ
ンアルコキシドの好ましい例としては、Ｔｉ（ＯＣ
Ｈ3 ) 4 、Ｔｉ( ＯＣ2 Ｈ5 ) 4 、Ｔｉ( ｉ−ＯＣ3 Ｈ
7 ) 4 、Ｔｉ（ｔ−ＯＣ4 Ｈ9 ) 4 等が挙げられる。ま
た酸化チタン微粒子は酸化チタンゾルのゲル化したもの
でよい。[2] Method for Producing Photocatalyst Coated Body [A] Formation of First Photocatalyst Layer As a coating liquid for forming the first photocatalyst layer 2, titanium oxide fine particles or sol and a fluororesin are suitable. Those dissolved and dispersed in another solvent are preferable. Titanium oxide sol is an intermediate product of hydrolysis of titanium alkoxide by the sol-gel method. In the sol-gel method, a titanium alkoxide is used as a starting material, and a compound in a solution is hydrolyzed and polymerized to form metal oxide or hydroxide sol fine particles. A preferred example of titanium alkoxide is Ti (OC
H 3) 4, Ti (OC 2 H 5) 4, Ti (i-OC 3 H
7 ) 4 , Ti (t-OC 4 H 9 ) 4 and the like. Further, the titanium oxide fine particles may be a gel of titanium oxide sol.
【００２４】酸化チタンを含む塗布液を基材１上又はバ
リアー層４上に均一に塗布するために、スピンコーティ
ング法、ドクターブレードコーティング法、スプレー法
等を利用する。塗布・乾燥後、必要に応じて室温〜350
℃で焼き付ける。In order to uniformly apply the coating solution containing titanium oxide on the substrate 1 or the barrier layer 4, a spin coating method, a doctor blade coating method, a spray method or the like is used. After coating and drying, if necessary, room temperature to 350
Bake at ℃.
【００２５】[B] 第二の光触媒層の形成
第二の光触媒層３を形成するための塗布液としては、酸
化チタンゾルと酸化チタン以外のセラミックスのゾルと
の混合物を主成分とするものが好ましい。第一の光触媒
層２と同じ方法で塗布・乾燥した後、大気中に放置する
か室温〜200 ℃に加熱処理することにより酸化チタンゾ
ル及びそれ以外のセラミックスゾルをゲル化（固化）さ
せる。[B] Formation of Second Photocatalyst Layer The coating liquid for forming the second photocatalyst layer 3 preferably contains a mixture of titanium oxide sol and a sol of ceramics other than titanium oxide as a main component. . After coating and drying in the same manner as the first photocatalyst layer 2, the titanium oxide sol and the other ceramic sol are gelled (solidified) by leaving them in the air or by heating them at room temperature to 200 ° C.
【００２６】[3] 各光触媒層の作用
以上の方法により形成された第一及び第二の光触媒層
２、３は、下記の作用を有する。
(イ) いずれの光触媒層の表面に付着した汚染物質、臭気
物質、菌類等でも分解するので、汚染防止作用、自浄作
用（セルフクリーニング作用）、消臭作用、殺菌作用等
がある。
(ロ) 第二の光触媒層３は、表面に付着した水分子（水酸
基）による超親水化作用（防曇作用）を有する。
(ハ) 基材１が透明である場合、酸化チタンの紫外線吸収
により紫外線の透過量を低減する作用を利用できる。
(ニ) 特に第一の光触媒層２はフッ素系樹脂をバインダー
としているため、優れた撥水性、耐候性及び耐久性を有
する。[3] Action of each photocatalyst layer The first and second photocatalyst layers 2 and 3 formed by the above method have the following actions. (A) Since any pollutant, odorous substance, fungus, etc. attached to the surface of any photocatalyst layer is decomposed, it has a pollution preventing action, a self-cleaning action (self-cleaning action), a deodorizing action, a bactericidal action and the like. (B) The second photocatalyst layer 3 has a superhydrophilic action (anti-fog action) by water molecules (hydroxyl groups) attached to the surface. (C) When the base material 1 is transparent, the effect of reducing the amount of transmitted ultraviolet light by absorbing the ultraviolet light of titanium oxide can be utilized. (D) Especially, the first photocatalyst layer 2 has excellent water repellency, weather resistance and durability because it uses a fluorine resin as a binder.
【００２７】[0027]
【実施例】本発明を以下の具体的実施例によりさらに詳
細に説明するが、本発明はそれらの実施例に限定される
ものではない。EXAMPLES The present invention will be described in more detail with reference to the following specific examples, but the present invention is not limited to these examples.
【００２８】実施例１
フッ素系樹脂系コーティング液（商品名：超ガラコ、Ｓ
ＯＦＴ９９コーポレーション（株）製）100 重量部に対
して50重量部（固形分基準）の酸化チタン微粒子（平均
粒径：55nm）を混合し、均一に分散させることにより、
第一の光触媒層用塗布液を作製した。また酸化チタン微
粒子（平均粒径：6.8 nm）と酸化珪素ゾルとの混合液
（重量比：50／50）を第二の光触媒層用塗布液とした。 Example 1 Fluorine-based resin coating liquid (trade name: Super Garako, S
By mixing 50 parts by weight (based on solid content) of fine particles of titanium oxide (average particle size: 55 nm) with 100 parts by weight of OFT99 Corporation, and uniformly dispersing them,
A coating liquid for the first photocatalyst layer was prepared. A mixed solution (weight ratio: 50/50) of titanium oxide fine particles (average particle size: 6.8 nm) and silicon oxide sol was used as a second photocatalyst layer coating solution.
【００２９】厚さ1.0mm の透明板ガラスの片面に厚さ80
nmの酸化珪素の薄膜を真空蒸着法により形成した後で、
薄膜のない面に第一の光触媒層用塗布液をスプレー法に
より塗布した。乾燥後80℃で焼き付けることにより、第
一の光触媒層を形成した。次いで、酸化珪素薄膜の表面
に第二の光触媒層用塗布液をスプレー法により塗布し、
乾燥後24時間放置することにより固化させた。[0029] A thickness of 80 mm on one side of a transparent plate glass with a thickness of 1.0 mm.
After forming a thin film of silicon oxide of nm by the vacuum deposition method,
The first photocatalyst layer coating liquid was applied to the surface without the thin film by a spray method. After drying, the first photocatalyst layer was formed by baking at 80 ° C. Then, the second photocatalyst layer coating liquid is applied to the surface of the silicon oxide thin film by a spray method,
After drying, it was left to stand for 24 hours to solidify.
【００３０】得られた光触媒被覆体（試験片Ａ）、及び
いずれの面にも光触媒層を形成していないガラス板（試
験片Ｂ）に対して、以下の実験をした。
(1) 防曇性
試験片Ａ及びＢの各表面に呼気を当てて曇りが発生する
か否かを調べ、次に90℃の温水の蒸気を１時間接触させ
た。その結果、試験片Ａでは第二の光触媒層側には曇り
が発生しなかったが、試験片Ｂでは両面とも曇りが発生
した。The following experiment was carried out on the obtained photocatalyst coated body (test piece A) and the glass plate (test piece B) on which no photocatalyst layer was formed. (1) Exhalation was applied to each surface of the antifogging test pieces A and B to examine whether or not fogging occurred, and then steam of warm water at 90 ° C. was contacted for 1 hour. As a result, the test piece A did not fog on the second photocatalyst layer side, but the test piece B did fog on both sides.
【００３１】(2) 汚染防止性
試験片Ａ（第一の光触媒層を上に向けた）及びＢをそれ
ぞれ屋外に１か月間放置し、表面の汚れを肉眼で観察し
た。その結果、試験片Ａの第一の光触媒層の方が試験片
Ｂの表面より著しく汚れが少なかった。またそれぞれの
試験片にホースで水を噴射したところ、試験片Ａの汚れ
は簡単に除去できた。(2) Contamination prevention test pieces A (first photocatalyst layer facing up) and B were left outdoors for one month, respectively, and surface stains were visually observed. As a result, the first photocatalyst layer of the test piece A was significantly less dirty than the surface of the test piece B. When water was sprayed on each test piece with a hose, the stains on the test piece A could be easily removed.
【００３２】(3) 消臭性
微量のアンモニアガスを含む室内に、試験片Ａを紫外線
を照射しながら１週間放置した後で臭気を調べたとこ
ろ、室内のアンモニア臭は非常に低減していた。(3) Deodorant In a room containing a small amount of ammonia gas, the test piece A was left for one week while being irradiated with ultraviolet rays, and then the odor was examined. As a result, the ammonia odor in the room was significantly reduced. .
【００３３】(4) 殺菌性
試験片Ａの第二の光触媒層の表面及び試験片Ｂの表面に
黴を散布し、高湿気の条件に１カ月間放置した。その結
果、試験片Ｂの表面には黴のコロニーが認められたが、
試験片Ａの第二の光触媒層の表面には実質的に黴はなか
った。(4) A mold was sprayed on the surface of the second photocatalyst layer of the sterilizing test piece A and the surface of the test piece B, and the test piece was allowed to stand in a high humidity condition for one month. As a result, a mold colony was observed on the surface of the test piece B,
The surface of the second photocatalyst layer of test piece A was substantially free of mold.
【００３４】(5) 紫外線遮蔽性
試験片Ａ及び試験片Ｂに紫外線を照射して透過率を測定
したところ、試験片Ａの透過率は試験片Ｂの透過率の５
％であった。(5) Ultraviolet-shielding property The test piece A and the test piece B were irradiated with ultraviolet rays to measure the transmittance. The transmittance of the test piece A was 5 times that of the test piece B.
%Met.
【００３５】以上の結果から、本発明の光触媒被覆体は
優れた防曇作用、汚染防止作用、消臭作用、殺菌作用及
び紫外線遮蔽作用を有することが分かる。From the above results, it can be seen that the photocatalyst coated body of the present invention has excellent antifogging action, antifouling action, deodorizing action, bactericidal action and ultraviolet ray shielding action.
【００３６】[0036]
【発明の効果】以上詳述したように、本発明の光触媒被
覆体は基材の両面に異なる平均粒径の酸化チタンを含有
する光触媒層を有し、一方（第一の光触媒層）は光活性
の他に耐候性及び耐久性を有し、他方（第二の光触媒
層）は高光活性を有する。そこで第一の光触媒層を外気
に露出する側とし、第二の光触媒層を室内に面する側と
することにより、優れた耐候性、耐久性及びセルフクリ
ーニング性とともに、著しい汚染防止作用、セルフクリ
ーニング作用、防曇性、消臭作用、殺菌作用、紫外線吸
収作用等を発揮することができる。このような特徴を有
する本発明の光触媒被覆体は、透明な基材（ガラス板）
であれば、自動車、船舶、航空機等の窓ガラス、建築物
の外装材、内装材、水回り材、窓ガラス等に好適であ
る。As described in detail above, the photocatalyst coating of the present invention has a photocatalyst layer containing titanium oxide having different average particle diameters on both sides of the substrate, while one (the first photocatalyst layer) is a photocatalyst. Besides activity, it has weather resistance and durability, while the other (second photocatalyst layer) has high photoactivity. Therefore, by setting the first photocatalyst layer to the side exposed to the outside air and the second photocatalyst layer to the side facing the room, excellent weather resistance, durability and self-cleaning property as well as a remarkable anti-pollution function and self-cleaning function are provided. It can exhibit the action, antifogging property, deodorizing action, bactericidal action, ultraviolet absorbing action and the like. The photocatalyst coated body of the present invention having such characteristics is a transparent substrate (glass plate).
Thus, it is suitable for window glass of automobiles, ships, aircrafts, exterior materials for buildings, interior materials, water supply materials, window glass, and the like.
【図１】 本発明の第一の実施例による光触媒被覆体の
層構造を示す部分断面図である。FIG. 1 is a partial cross-sectional view showing a layer structure of a photocatalyst coating according to a first embodiment of the present invention.
【図２】 本発明の第二の実施例による光触媒被覆体の
層構造を示す部分断面図である。FIG. 2 is a partial cross-sectional view showing a layer structure of a photocatalyst coating according to a second embodiment of the present invention.
１・・・基材 ２・・・第一の光触媒層 ３・・・第二の光触媒層 ４・・・バリアー層 1 ... Base material 2 ... First photocatalyst layer 3 ... Second photocatalyst layer 4 ... Barrier layer
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 B01D 53/00 - 53/96 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) B01J 21/00-38/74 B01D 53/00-53/96
Claims (6)
媒被覆体において、前記ガラス板は一方の面が外気に露
出し、他方の面が室内に面しており、前記外気に露出す
る側の面に形成された第一の光触媒層は、平均粒径30〜
100 nmの光触媒粒子がバインダーに分散してなり、かつ
厚さが 0.5 〜 50 μｍであり、前記室内に面する側の面に
形成された第二の光触媒層は、平均粒径５〜25 nmの光
触媒粒子がバインダーに分散してなり、かつ厚さが 0.5
〜 3.0 μｍであることを特徴とする光触媒被覆体。1. A photocatalyst coating having a photocatalytic layer on both surfaces of the glass plate, the glass plate is exposed one face to the outside air
Exposed, and the other side faces the room and is exposed to the outside air.
The first photocatalyst layer formed on the surface of the
100 nm photocatalyst particles are dispersed in the binder, and
The thickness is 0.5 to 50 μm, and the surface facing the room is
The formed second photocatalyst layer is composed of photocatalyst particles having an average particle size of 5 to 25 nm dispersed in a binder and has a thickness of 0.5.
A photocatalyst coated body having a thickness of up to 3.0 μm .
て、前記第一の光触媒層は、前記光触媒粒子がフッ素系
樹脂からなるバインダーに分散してなることを特徴とす
る光触媒被覆体。2. The photocatalyst coated body according to claim 1, wherein the first photocatalyst layer comprises the photocatalyst particles dispersed in a binder made of a fluororesin.
おいて、前記第二の光触媒層は、前記光触媒粒子がセラ
ミックスゾルからなるバインダーに分散してなることを
特徴とする光触媒被覆体。3. The photocatalyst coating according to claim 1 or 2, wherein the second photocatalyst layer is formed by dispersing the photocatalyst particles in a binder made of ceramic sol.
被覆体において、前記第一の光触媒層の前記光触媒粒子
と前記バインダーの重量比が１：９〜９：１であること
を特徴とする光触媒被覆体。 4. The photocatalyst coated body according to claim 1, wherein the photocatalyst particles in the first photocatalyst layer.
And the weight ratio of the binder is 1: 9 to 9: 1.
A photocatalyst-coated body characterized by:
被覆体において、前記第二の光触媒層は、酸化物系セラ
ミックスの蒸着層を介して前記ガラス板上に形成されて
いることを特徴とする光触媒被覆体。 5. The photocatalyst coating body according to claim 1, wherein the second photocatalyst layer is formed on the glass plate via a vapor deposition layer of oxide-based ceramics. A characteristic photocatalyst coating.
被覆体において、前記光触媒粒子が酸化チタンからなる
ことを特徴とする光触媒被覆体。6. The photocatalyst coated body according to any one of claims 1 to 5, wherein the photocatalyst particles are made of titanium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10821697A JP3509462B2 (en) | 1997-04-10 | 1997-04-10 | Photocatalyst coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10821697A JP3509462B2 (en) | 1997-04-10 | 1997-04-10 | Photocatalyst coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10277402A JPH10277402A (en) | 1998-10-20 |
| JP3509462B2 true JP3509462B2 (en) | 2004-03-22 |
Family
ID=14478983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10821697A Expired - Fee Related JP3509462B2 (en) | 1997-04-10 | 1997-04-10 | Photocatalyst coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3509462B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6884399B2 (en) | 2001-07-30 | 2005-04-26 | Carrier Corporation | Modular photocatalytic air purifier |
| AT503936B1 (en) * | 2006-09-07 | 2008-02-15 | Univ Graz Tech | CLEANING DEVICE WITH POROUS, PHOTOCATALYTICALLY ACTIVE BULK |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2667331B2 (en) * | 1992-03-13 | 1997-10-27 | 東陶機器株式会社 | Member having photocatalytic function and method for manufacturing the same |
| AU676299B2 (en) * | 1993-06-28 | 1997-03-06 | Akira Fujishima | Photocatalyst composite and process for producing the same |
| ES2155941T5 (en) * | 1995-09-15 | 2012-04-30 | Rhodia Chimie | Substrate with photocatalytic coating based on titanium dioxide and organic dispersions based on titanium dioxide |
| JP3759651B2 (en) * | 1996-05-28 | 2006-03-29 | 日本パーカライジング株式会社 | Resin or resin coating material having photocatalytic surface and method for producing the same |
-
1997
- 1997-04-10 JP JP10821697A patent/JP3509462B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10277402A (en) | 1998-10-20 |
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