JP3371096B2 - Embossed stainless steel plate with excellent photocatalytic activity and no color unevenness - Google Patents
Embossed stainless steel plate with excellent photocatalytic activity and no color unevennessInfo
- Publication number
- JP3371096B2 JP3371096B2 JP19305699A JP19305699A JP3371096B2 JP 3371096 B2 JP3371096 B2 JP 3371096B2 JP 19305699 A JP19305699 A JP 19305699A JP 19305699 A JP19305699 A JP 19305699A JP 3371096 B2 JP3371096 B2 JP 3371096B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- steel plate
- photocatalyst layer
- layer
- photocatalyst
- 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
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 57
- 239000010935 stainless steel Substances 0.000 title claims description 57
- 230000001699 photocatalysis Effects 0.000 title claims description 15
- 239000011941 photocatalyst Substances 0.000 claims description 82
- 239000000463 material Substances 0.000 claims description 31
- 238000004049 embossing Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、触媒活性が高められた
光触媒層を表面にもち、干渉色等の色ムラが観察されな
いエンボス加工ステンレス鋼板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an embossed stainless steel sheet having a photocatalyst layer having an enhanced catalytic activity on its surface and in which color unevenness such as interference color is not observed.
【０００２】[0002]
【従来の技術】内装材，外装材等の建材には、耐食性及
び意匠性に優れたステンレス鋼板が多用されている。ス
テンレス鋼板は美麗な表面をもつことが特徴であり、そ
の外観を活用したＢＡ材，２Ｂ材，ダル仕上げ材，＃４
研磨仕上げ材，ヘアライン仕上げ材，エンボス仕上げ材
等として出荷されている。ところで、都市周辺では煤
煙，排ガス等による大気汚染がひどくなる最近の傾向に
伴って、外装材の汚れが目立つようになってきている。
特に、雨水が集まって流れる窓枠の下等の部分では、雨
水に浮遊している汚れが外装材の表面に付着し、スジ状
の汚れを発生させ易い。外装材の汚れは洗浄除去できる
ものの、度重なる洗浄は煩雑であるばかりでなく、ビル
等の大型建造物にあっては危険を伴う困難な作業が強い
られる。スジ状汚れは、雨水によるものばかりでなく、
ステンレス鋼製パネルの目地に充填されたコーキング剤
から溶出する樹脂分に由来するものもある。この種の汚
れは、通常の水を用いた洗浄では容易に除去できない。
また、エレベータ扉等の内装材では、指紋付着によって
外観が劣化する。この場合にも、付着した指紋を洗浄除
去する必要がある。2. Description of the Related Art Stainless steel sheets having excellent corrosion resistance and design are often used for building materials such as interior materials and exterior materials. Stainless steel sheet has a beautiful surface, and its appearance is used for BA material, 2B material, dull finish material, # 4
It is shipped as polishing finish, hairline finish, emboss finish, etc. By the way, in recent years, air pollution due to soot, exhaust gas, and the like has become serious around the city, and the dirt on the exterior material has become conspicuous.
In particular, in a portion under the window frame or the like where rainwater gathers and flows, dirt floating in the rainwater adheres to the surface of the exterior material, and streaky dirt is easily generated. Although dirt on the exterior material can be removed by washing, repeated washing is not only complicated, but also a large-scale building such as a building requires dangerous and difficult work. Streaky stains are not only caused by rainwater,
Some are derived from the resin content eluted from the caulking agent filled in the joints of stainless steel panels. This type of dirt cannot be easily removed by washing with normal water.
In addition, the appearance of interior materials such as elevator doors deteriorates due to fingerprints. Also in this case, it is necessary to wash and remove the attached fingerprint.
【０００３】外装材や内装材に使用されるステンレス鋼
板の防汚処理としては、アクリルクリア塗装，フッ素ク
リア塗装等が知られている。クリア塗装を施すことによ
り、ステンレス鋼板表面に付着した汚れは確かに拭き取
り易くなる。しかし、汚れの付着そのものを抑制できな
いため、依然として定期的な拭取り作業が必要になる。
そこで、光触媒反応を生起させる光触媒のコーティング
により金属，ガラス等の表面に油質分解能及び親水性を
付与し、付着した汚れを分解し流し去る方法が検討され
ている（ＷＯ９６／２９３７５）。Acrylic clear coating, fluorine clear coating and the like are known as antifouling treatments for stainless steel plates used for exterior materials and interior materials. By applying a clear coating, stains on the surface of the stainless steel plate can be easily wiped off. However, since the adhesion of dirt itself cannot be suppressed, regular wiping work is still required.
Therefore, a method has been studied in which a photocatalytic coating that causes a photocatalytic reaction is applied to the surface of a metal, glass, or the like to impart oily resolution and hydrophilicity, and the attached dirt is decomposed and washed away (WO96 / 29375).
【０００４】[0004]
【発明が解決しようとする課題】ステンレス鋼板の優れ
た意匠性を活かしたまま、光触媒による汚れ防止効果を
鋼板表面に付与するためには、クリアな光触媒層を形成
させる必要がある。しかし、クリアで且つ光照射時にク
ラックの発生がない膜を従来法で得ようとすると光触媒
層を薄膜化せざるを得ない。薄い光触媒層では、鋼板表
面に付与された親水性により汚れを洗い流す効果は期待
されるものの、付着した汚れを分解するほどの特性が得
られない。しかも、表面での反射光が強いステンレス鋼
板を基材として薄くクリアな光触媒層を形成すると、干
渉色が際立ちステンレス鋼板の外観を劣化させる。In order to impart the stain-preventing effect of the photocatalyst to the surface of the steel sheet while maintaining the excellent design of the stainless steel sheet, it is necessary to form a clear photocatalyst layer. However, in order to obtain a film that is clear and does not cause cracks when irradiated with light by the conventional method, the photocatalyst layer must be thinned. Although a thin photocatalyst layer is expected to have an effect of washing off stains due to the hydrophilicity imparted to the surface of the steel sheet, it does not have properties sufficient to decompose attached stains. Moreover, when a thin and clear photocatalyst layer is formed by using a stainless steel plate having a strong reflected light on the surface as a base material, an interference color is conspicuous and the appearance of the stainless steel plate is deteriorated.
【０００５】[0005]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、エンボス加工で
凹凸を付けたステンレス鋼板の表面に光触媒層を形成す
ることにより、汚れ分解能を向上させると共に干渉色に
よる外観不良を防止したステンレス鋼板を得ることを目
的とする。本発明のエンボス加工ステンレス鋼板は、そ
の目的を達成するため、エンボス深さ５〜５０μｍ，凸
部平坦部長さ０.２〜２.０ｍｍ及び凸部エッジ部長さ３
０〜２００μｍのエンボス模様を形成したステンレス鋼
板を基材とし、エンボス模様形成面に光触媒層が設けら
れていることを特徴とする。エンボス模様形成面と光触
媒層との間に、必要に応じてクリアな中間層を設けるこ
ともできる。光触媒層は、単独の膜厚で或いは中間層と
の合計膜厚で０.１〜６μｍの範囲に設定することが好
ましい。中間層としては、干渉色の発現を抑えるため低
い屈折率の材質で作ることが好ましい。DISCLOSURE OF THE INVENTION The present invention has been devised in order to solve such a problem, and stains are formed by forming a photocatalyst layer on the surface of a stainless steel plate having irregularities formed by embossing. It is an object of the present invention to obtain a stainless steel plate that improves resolution and prevents appearance defects due to interference colors. In order to achieve the object, the embossed stainless steel plate of the present invention has an emboss depth of 5 to 50 μm, a convex flat portion length of 0.2 to 2.0 mm and a convex edge portion length of 3.
A stainless steel plate having an embossed pattern of 0 to 200 μm is used as a base material, and a photocatalyst layer is provided on the embossed pattern formation surface. If necessary, a clear intermediate layer may be provided between the embossed pattern forming surface and the photocatalyst layer. The photocatalyst layer is preferably set to a thickness of 0.1 to 6 μm as a single film thickness or a total film thickness with the intermediate layer. The intermediate layer is preferably made of a material having a low refractive index in order to suppress the development of interference color.
【０００６】[0006]
【作用】ＢＡ仕上げ材，２Ｂ仕上げ材、ダル仕上げ材，
＃４仕上げ材，ヘアライン仕上げ材等のステンレス鋼板
に光触媒層をコーティングすると、光触媒コーティング
液のレベリング性が良好であるため、ステンレス鋼板の
表面粗さよりも光触媒コーティング後の表面粗さが小さ
くなる。この場合、形成された光触媒層の実効表面積
は、見掛けの表面積とほとんど変わらず、界面反応であ
る光触媒反応に必要な表面積が不足しがちになる。しか
も、光触媒層は、半導体特性をもち屈折率が高いことか
ら、比較的厚膜になっても光の干渉作用を生起させ易
い。たとえば、一般的な透明コーティングでは２μｍ以
上の膜厚で干渉色が観察されなくなるが、光触媒層では
ダル仕上げ材を除き５μｍの膜厚でも干渉色が観察され
る。[Function] BA finishing material, 2B finishing material, dull finishing material,
When a photocatalyst layer is coated on a stainless steel plate such as # 4 finishing material or hairline finishing material, the leveling property of the photocatalyst coating liquid is good, and therefore the surface roughness after the photocatalytic coating is smaller than the surface roughness of the stainless steel plate. In this case, the effective surface area of the formed photocatalyst layer is almost the same as the apparent surface area, and the surface area required for the photocatalytic reaction, which is an interfacial reaction, tends to be insufficient. Moreover, since the photocatalyst layer has semiconductor characteristics and a high refractive index, even if the photocatalyst layer has a relatively thick film, it is easy to cause a light interference action. For example, in a general transparent coating, the interference color is not observed at a film thickness of 2 μm or more, but in the photocatalyst layer, the interference color is observed even at a film thickness of 5 μm except for the dull finish material.
【０００７】ステンレス鋼板の意匠性を損うことなく、
必要とする触媒活性を鋼板表面に付与するためには、十
分な実効表面積の光触媒層を薄く、しかも干渉色が発現
しないように形成することが要求される。本発明では、
この要求を満足させるため、エンボス加工で凹凸を付け
たステンレス鋼板を基材として使用している。エンボス
加工されたステンレス鋼板１は、複数の凹部２及び凸部
３のある表面をもっている（図１）。この表面を光触媒
層４でコーティングすると（図２）、凹部２及び凸部３
の形状を倣った凹凸のある光触媒層４が形成される。そ
のため、光触媒層４の実効表面積は、フラットなステン
レス鋼表面に形成される光触媒層に比較して格段に大き
くなる。また、凹部２及び凸部３で光の乱反射が促進さ
れるため、干渉作用が抑制される。したがって、薄い光
触媒層４を形成しても、大きな実効表面積をもつため十
分な光触媒活性が得られると共に、干渉に起因した色ム
ラも抑制される。更には、凹部２，凸部３と光触媒層４
との機械的な噛合いが増すため、光触媒層４の密着性も
向上する。Without detracting from the design of the stainless steel plate,
In order to impart the required catalytic activity to the surface of the steel sheet, it is necessary to form a photocatalyst layer having a sufficient effective surface area so as to be thin and not to develop an interference color. In the present invention,
In order to satisfy this requirement, a stainless steel plate with unevenness made by embossing is used as a base material. The embossed stainless steel plate 1 has a surface having a plurality of concave portions 2 and convex portions 3 (FIG. 1). When this surface is coated with the photocatalyst layer 4 (FIG. 2), the concave portions 2 and the convex portions 3 are formed.
The photocatalyst layer 4 having irregularities is formed to follow the shape of the above. Therefore, the effective surface area of the photocatalyst layer 4 is significantly larger than that of the photocatalyst layer formed on the flat stainless steel surface. Further, since the irregular reflection of light is promoted by the concave portion 2 and the convex portion 3, the interference action is suppressed. Therefore, even if the thin photocatalyst layer 4 is formed, since it has a large effective surface area, sufficient photocatalytic activity can be obtained, and color unevenness due to interference is suppressed. Further, the concave portion 2, the convex portion 3 and the photocatalyst layer 4
Since the mechanical meshing with the is increased, the adhesion of the photocatalyst layer 4 is also improved.
【０００８】エンボス加工でステンレス鋼板１の表面に
付けられる凹凸形状は、浅いエンボス深さでは凹部２が
光触媒層４で埋められ、光触媒層４の実効表面積を大き
くできない。また、光触媒層４が厚膜化するほど凹部２
及び凸部３の段差（エンボス深さ）が減少し、光触媒層
４の実効表面積を小さくする。したがって、光触媒層４
の大きな実効表面積を確保するためには、エンボス深さ
及び光触媒層４の膜厚を適正に管理することが好まし
い。更に本発明者等による調査・研究の結果から判明し
たことであるが、凸部３を短くするとき、光触媒層４が
薄膜でも干渉色の発現が防止される。凸部３の長さが干
渉色発現に及ぼす影響は、次のように考えられる。すな
わち、ステンレス鋼板１の表面に島状に分布する凸部３
の長さを平坦部長さａ及びエッジ部長さｂで規定する
と、短い凸部３ほど平坦部長さａ及びエッジ部長さｂが
繰り返され、光触媒層４の膜厚が不均一化する。不均一
な膜厚は、ステンレス鋼板１の表面で反射した反射光の
光路差を連続的にずらし、光の干渉作用を抑制する。干
渉抑制効果は、屈折率が低い中間層５をステンレス鋼板
１（基材）と光触媒層４との間に介在させることによっ
ても大きくなる。中間層５は、ステンレス鋼板１に対す
る光触媒層４の密着性を改善する上でも有効である。As for the uneven shape formed on the surface of the stainless steel plate 1 by embossing, the recess 2 is filled with the photocatalyst layer 4 at a shallow embossing depth, and the effective surface area of the photocatalyst layer 4 cannot be increased. Further, as the photocatalyst layer 4 becomes thicker, the concave portion 2
Also, the step (emboss depth) of the convex portion 3 is reduced, and the effective surface area of the photocatalyst layer 4 is reduced. Therefore, the photocatalyst layer 4
In order to secure a large effective surface area, it is preferable to properly manage the emboss depth and the film thickness of the photocatalyst layer 4. Further, as is clear from the results of investigations and studies by the present inventors, when the convex portion 3 is shortened, the appearance of interference color is prevented even if the photocatalytic layer 4 is a thin film. The influence of the length of the convex portion 3 on the appearance of the interference color is considered as follows. That is, the convex portions 3 distributed in an island shape on the surface of the stainless steel plate 1.
Is defined by the flat portion length a and the edge portion length b, the shorter the convex portion 3, the flat portion length a and the edge portion length b are repeated, and the film thickness of the photocatalyst layer 4 becomes nonuniform. The non-uniform film thickness continuously shifts the optical path difference of the reflected light reflected on the surface of the stainless steel plate 1 to suppress the light interference effect. The interference suppressing effect is also increased by interposing the intermediate layer 5 having a low refractive index between the stainless steel plate 1 (base material) and the photocatalyst layer 4. The intermediate layer 5 is also effective in improving the adhesion of the photocatalyst layer 4 to the stainless steel plate 1.
【０００９】[0009]
【実施の形態】基材のステンレス鋼板としてはフェライ
ト系，オーステナイト系，マルテンサイト系等があり、
一般にはＳＵＳ３０４，ＳＵＳ４３０が使用される。エ
ンボス加工には、所定模様を付けた型板を使用するエン
ボス加工も可能であるが、生産性の高いロールエンボス
が好ましい。ロールエンボスでは、凹凸模様を付けたエ
ンボスロールを用いてステンレス鋼板を圧延し、鋼板表
面に凹凸模様を転写する。図１では片面エンボスを示し
ているが、両面エンボス加工したステンレス鋼板１を基
材として使用できることは勿論である。凹凸模様は、そ
の上に形成される光触媒層４の実効表面積を大きくする
ためエンボス深さを５〜５０μｍ，平坦部長さａを０．
２〜２ｍｍ，エッジ部長さｂを３０〜２００μｍにする
ことが好ましい。このような凹凸模様の上に好ましくは
膜厚０．１〜５μｍの光触媒層４又は合計膜厚０．１〜
６μｍの光触媒層４及び中間層５を形成するとき、光触
媒層４の実効表面積が大きくなり高い光触媒活性が付与
されると共に、干渉色に起因する外観不良も防止され
る。[Embodiment] As a stainless steel plate as a base material, there are ferrite type, austenite type, martensite type, etc.
Generally, SUS304 and SUS430 are used. The embossing can be embossing using a template having a predetermined pattern, but roll embossing with high productivity is preferable. In roll embossing, an embossing roll having an uneven pattern is used to roll a stainless steel plate to transfer the uneven pattern to the steel plate surface. Although FIG. 1 shows single-sided embossing, it goes without saying that the double-sided embossed stainless steel plate 1 can be used as a substrate. The concavo-convex pattern has an emboss depth of 5 to 50 μm and a flat part length a of 0. 0 to increase the effective surface area of the photocatalyst layer 4 formed thereon.
It is preferable that the edge length b is 2 to 2 mm and the edge length b is 30 to 200 μm. The photocatalyst layer 4 having a film thickness of 0.1 to 5 μm or the total film thickness of 0.1 to 0.1 is preferably formed on the uneven pattern.
When the photocatalyst layer 4 and the intermediate layer 5 having a thickness of 6 μm are formed, the effective surface area of the photocatalyst layer 4 is increased and a high photocatalytic activity is imparted, and the appearance defect due to the interference color is prevented.
【００１０】エンボス深さが５μｍ未満では、凹部２が
光触媒層４で埋められ易く、光触媒層４の実効表面積を
大きくすることが困難になる。逆に５０μｍを超えるエ
ンボス深さでは、薄い光触媒層４を均一に形成すること
が困難になる。また、深すぎるエンボス模様では、斜め
方向からの入射光が凸部３で遮られ、陰になる凹部２が
生じるため、光触媒反応に寄与しない光触媒層４の割合
が多くなり易い。平坦部長さａが０．２ｍｍに達しない
凸部３では、光触媒コーティング液をステンレス鋼板１
の表面に塗布したとき、凸部３で保持される液量が少な
く、大半が凹部２に流れ込み易くなる。その結果、光触
媒層４の実効表面積を大きくできなくなる。逆に２．０
ｍｍを超える平坦部長さａでは、光触媒層４が形成され
た凸部３に干渉色が発現し易い。エッジ部長さｂは、光
触媒層４の実効表面積を大きくする上から２００μｍ以
下にすることが好ましい。しかし、エッジ部長さｂを３
０μｍ以下にすることは、エンボス加工を困難にする。When the emboss depth is less than 5 μm, the recess 2 is easily filled with the photocatalyst layer 4, and it becomes difficult to increase the effective surface area of the photocatalyst layer 4. On the contrary, if the emboss depth exceeds 50 μm, it becomes difficult to uniformly form the thin photocatalyst layer 4. Further, if the embossed pattern is too deep, incident light from an oblique direction is blocked by the convex portion 3 and a concave portion 2 which is a shadow is generated, so that the proportion of the photocatalytic layer 4 that does not contribute to the photocatalytic reaction tends to increase. In the convex portion 3 where the flat portion length a does not reach 0.2 mm, the photocatalyst coating liquid is applied to the stainless steel plate 1
When applied to the surface of, the amount of liquid retained by the convex portions 3 is small, and most of the liquid easily flows into the concave portions 2. As a result, the effective surface area of the photocatalyst layer 4 cannot be increased. On the contrary, 2.0
When the flat portion length a exceeds mm, the interference color is likely to appear on the convex portion 3 on which the photocatalyst layer 4 is formed. The edge length b is preferably 200 μm or less in order to increase the effective surface area of the photocatalyst layer 4. However, the edge length b is 3
When the thickness is 0 μm or less, embossing becomes difficult.
【００１１】エンボス加工で凹部２及び凸部３を形成し
たステンレス鋼板１に、塗膜密着性を改善するために脱
脂，リン酸塩処理，クロメート処理等の前処理が施され
る。前処理としては、脱脂後に表面調整及び／又はクロ
メート処理する方法，フッ酸処理法等が採用される。前
処理されたステンレス鋼板１に光触媒コーティング液を
塗布し、熱処理すると、光触媒作用を呈する光触媒層４
が形成される。光触媒コーティング液は、シリカ系塗
料，アルミナ系塗料，シリカ・アルミナ系塗料，ゼオラ
イト系塗料等に酸化チタン，酸化亜鉛，チタン酸ストロ
ンチウム，酸化タングステン，酸化スズ，酸化ジルコニ
ウム等の光触媒を分散させることにより調製される。シ
リカ系塗料としては、たとえば水系のコロイダルシリカ
やＲ1 Ｓｉ（ＯＲ2 ）3 （ただし、Ｒ1 ，Ｒ2 はアルキ
ル基を示す）の構造をもつオルガノシリケートを有機溶
媒や水に溶解分散させたシリカゾルが使用される。The stainless steel plate 1 having the concave portions 2 and the convex portions 3 formed by embossing is subjected to pretreatments such as degreasing, phosphate treatment and chromate treatment in order to improve the adhesion of the coating film. As the pretreatment, a method of surface conditioning and / or chromate treatment after degreasing, a hydrofluoric acid treatment method and the like are adopted. A photocatalyst layer 4 exhibiting a photocatalytic action when a photocatalyst coating liquid is applied to the pretreated stainless steel plate 1 and heat-treated.
Is formed. The photocatalyst coating liquid is obtained by dispersing a photocatalyst such as titanium oxide, zinc oxide, strontium titanate, tungsten oxide, tin oxide, zirconium oxide in silica paint, alumina paint, silica-alumina paint, zeolite paint, etc. Is prepared. As the silica-based paint, for example, an aqueous colloidal silica or an organosilicate having a structure of R 1 Si (OR 2 ) 3 (wherein R 1 and R 2 represent an alkyl group) is dissolved and dispersed in an organic solvent or water. Silica sol is used.
【００１２】塗料に対する光触媒の配合量は、形成され
る光触媒層４の光触媒含有量が２０〜８０重量％となる
ように設定することが好ましい。光触媒含有量が２０重
量％未満では汚れ分解能や親水化が不充分であり、逆に
８０重量％を超える光触媒含有量では塗膜密着性が劣化
し易い。光触媒コーティング液は、光触媒以外にシリ
カ，アルミナ，シリカ・アルミナ，ゼオライト等の透明
膜形成成分を含む。The blending amount of the photocatalyst with respect to the paint is preferably set so that the photocatalyst content of the photocatalyst layer 4 formed is 20 to 80% by weight. If the photocatalyst content is less than 20% by weight, stain resolving power and hydrophilization are insufficient, and conversely, if the photocatalyst content exceeds 80% by weight, the coating film adhesion tends to deteriorate. The photocatalyst coating liquid contains a transparent film forming component such as silica, alumina, silica-alumina, or zeolite in addition to the photocatalyst.
【００１３】光触媒コーティング液の塗布に先立って、
必要に応じてクリアな中間層５をステンレス鋼板１上に
形成することもできる。中間層５の材質としては屈折率
の低いセラミックス，金属酸化物等があり、具体的には
シリカ，アルミナ，ゼオライト，酸化スズ等の酸化物が
使用される。屈折率の低い中間層５の介在により干渉色
が抑制されるメカニズムは次のように考えられる。すな
わち、光触媒層４を透過した光は、中間層５で屈折され
るが、光触媒層４より中間層５の屈折率が小さいため、
ステンレス鋼板１の表面における反射角が大きくなり、
干渉色が抑制される。なかでも、屈折率が２以下の中間
層５は、干渉色抑制効果が大きくなる。Prior to applying the photocatalyst coating liquid,
If necessary, a clear intermediate layer 5 can be formed on the stainless steel plate 1. Materials for the intermediate layer 5 include ceramics having a low refractive index, metal oxides, and the like, and specifically, oxides such as silica, alumina, zeolite, and tin oxide are used. The mechanism by which the interference color is suppressed by the intermediate layer 5 having a low refractive index is considered as follows. That is, the light transmitted through the photocatalyst layer 4 is refracted by the intermediate layer 5, but since the intermediate layer 5 has a smaller refractive index than the photocatalyst layer 4,
The reflection angle on the surface of the stainless steel plate 1 becomes large,
The interference color is suppressed. Above all, the intermediate layer 5 having a refractive index of 2 or less has a large effect of suppressing the interference color.
【００１４】中間層５は、ステンレス鋼板１と光触媒層
４との間の化学結合性を改善し、光触媒層４の密着性を
向上させる上でも有効である。すなわち、前処理された
ステンレス鋼板１の表面に水酸基が存在するが、この水
酸基が中間層５の形成に使用されるゾル中の金属水酸化
物の水酸基と脱水縮合反応し、強固な化学結合性を発現
する。また、中間層５の表面にある酸化物は、光触媒層
４の形成時にバインダとなるゾルと強固に結合する。そ
の結果、光触媒層４は、中間層５を介してステンレス鋼
板１に強固に結合する。中間層５は、後述する実施例に
もみられるように、油質分解能，ガス分解能，吸湿能等
の触媒性能を向上させる上でも有効である。The intermediate layer 5 is effective in improving the chemical bond between the stainless steel plate 1 and the photocatalyst layer 4 and improving the adhesion of the photocatalyst layer 4. That is, although a hydroxyl group is present on the surface of the pretreated stainless steel sheet 1, this hydroxyl group undergoes a dehydration condensation reaction with the hydroxyl group of the metal hydroxide in the sol used for forming the intermediate layer 5, resulting in a strong chemical bondability. Express. In addition, the oxide on the surface of the intermediate layer 5 is firmly bonded to the sol that serves as a binder when the photocatalyst layer 4 is formed. As a result, the photocatalyst layer 4 is firmly bonded to the stainless steel plate 1 via the intermediate layer 5. The intermediate layer 5 is also effective in improving catalytic performance such as oil-degrading ability, gas-degrading ability, and moisture absorption ability, as will be seen in Examples described later.
【００１５】このようにして形成された光触媒層４は、
ステンレス鋼表面に油質分解能及び親水性を付与する。
この光触媒層４が光照射されると光触媒反応を生起し、
付着している油質が分解して付着力が弱まり、親水性表
面と相俟って容易に除去される。光触媒層４を励起させ
る光源としては、太陽光，室内照明，蛍光燈，白熱電
球，メタルハライドランプ，水銀ランプ，キセノンラン
プ等がある。光触媒層４で油質分解能及び親水性が付与
されたステンレス鋼板１は、外装材，内装材は勿論、家
電機器，厨房機器，家具調度品等の表装材としても使用
される。The photocatalyst layer 4 thus formed is
It imparts oily resolution and hydrophilicity to the surface of stainless steel.
When this photocatalyst layer 4 is irradiated with light, a photocatalytic reaction occurs,
The adhering oil is decomposed to weaken the adhering force, and is easily removed together with the hydrophilic surface. Light sources for exciting the photocatalyst layer 4 include sunlight, indoor lighting, fluorescent lamps, incandescent lamps, metal halide lamps, mercury lamps, xenon lamps, and the like. The stainless steel plate 1 to which the photocatalytic layer 4 imparts oily resolution and hydrophilicity is used not only as an exterior material and an interior material, but also as a surface material for home appliances, kitchen equipment, furniture furniture and the like.
【００１６】[0016]
【実施例】（光触媒層４の直接形成）板厚０．８ｍｍの
ＳＵＳ３０４ステンレス鋼板をエンボス加工し、表１に
示すエンボス深さ，平坦部長さ及びエッジ部長さで凹凸
を付けた。次いで、ステンレス鋼板にアルカリ脱脂及び
クロメート処理を施した後、水洗・乾燥した。乾燥後の
ステンレス鋼板表面にＴｉＯ2 粒子分散シリカゾルをス
プレー塗装し、２００℃×２０分で焼成した。ＴｉＯ2
粒子分散シリカゾルとしては、光触媒層４の組成が５０
重量％ＴｉＯ2 −５０重量％ＳｉＯ2 となる割合で粒径
２０ｎｍのアナターゼ型ＴｉＯ2 粒子をシリカゾルに分
散配合したものを使用した。Example (Direct formation of photocatalyst layer 4) A 0.8 mm-thick SUS304 stainless steel plate was embossed and made uneven with the embossing depth, flat portion length and edge portion length shown in Table 1. Next, the stainless steel plate was subjected to alkali degreasing and chromate treatment, then washed with water and dried. The dried TiO 2 particle-dispersed silica sol was spray-coated on the surface of the dried stainless steel plate and baked at 200 ° C. for 20 minutes. TiO 2
As the particle-dispersed silica sol, the composition of the photocatalyst layer 4 is 50
Anatase-type TiO 2 particles having a particle diameter of 20 nm were dispersed and compounded in silica sol at a ratio of 50% by weight TiO 2 -50% by weight SiO 2 .
【００１７】（中間層５を介した光触媒層４の形成）ス
テンレス鋼板１と光触媒層４との間に中間層５を介在さ
せる以外は、同様にして光触媒層４を形成した。中間層
５としては、コロイダルシリカ，オルガノアルコキシシ
ランを主成分とするシリカゾルをステンレス鋼板１にス
プレー塗装し、１４０℃×２０分の焼成によりシリカ層
を形成した。(Formation of Photocatalyst Layer 4 with Intermediate Layer 5) The photocatalyst layer 4 was formed in the same manner except that the intermediate layer 5 was interposed between the stainless steel plate 1 and the photocatalyst layer 4. As the intermediate layer 5, a silica sol containing colloidal silica and organoalkoxysilane as a main component was spray-coated on the stainless steel plate 1 and baked at 140 ° C. for 20 minutes to form a silica layer.
【００１８】（比較例）他の表面仕上げを施したステン
レス鋼板１を基材に使用し、同様な条件下で光触媒層４
を鋼板表面に形成した。この場合、ステンレス鋼板１の
表面粗さは表面仕上げの種類によって異なり、ＢＡ仕上
げではＲmax ０．１μｍ，２Ｂ仕上げではＲmax ０．５
μｍ，２Ｄ仕上げではＲmax １．５μｍ，＃４研磨仕上
げではＲ max ８．３μｍ，ヘアライン仕上げではＲmax
１０．５μｍであった。(Comparative Example) Stainless steel having another surface finish
Using the less steel plate 1 as a base material, the photocatalyst layer 4 is used under the same conditions.
Was formed on the steel plate surface. In this case, the stainless steel plate 1
Surface roughness depends on the type of surface finish, and BA finish
G is Rmax 0.1 μm, R for 2B finishmax 0.5
μm, R for 2D finishmax 1.5μm, # 4 polishing finish
G is R max 8.3 μm, R for hairline finishmax
It was 10.5 μm.
【００１９】光触媒層４が形成された各ステンレス鋼板
から試験片を切り出し、油質分解性能試験及び外観試験
に供した。油質分解性能試験では、付着量０．２ｍｇ／
ｃｍ2 でサラダ油を試験片に付着させ、ブラックライト
（波長３６５ｎｍ，紫外線強度３ｍＷ／ｃｍ2 ）を用い
て試験片を２４時間紫外線照射した。そして、紫外線照
射前後の試験片の重量から重量変化を求め、重量変化か
ら油分解率を算出した。外観試験では、種々の角度から
試験片を目視観察し、干渉色を調査した。観察角度に関
わらず干渉色が検出されなかったものを◎，正面からの
観察では干渉色が検出されなかったが、水平方向から観
察したとき僅かに干渉色が検出されたものを○，何れの
方向から観察しても干渉色が検出されたものを×と評価
した。A test piece was cut out from each stainless steel plate on which the photocatalyst layer 4 was formed and subjected to an oily decomposition performance test and an appearance test. In the oil quality decomposition performance test, the attached amount was 0.2 mg /
Salad oil was attached to the test piece in cm 2 , and the test piece was subjected to ultraviolet irradiation for 24 hours using black light (wavelength 365 nm, ultraviolet intensity 3 mW / cm 2 ). Then, the weight change was obtained from the weight of the test piece before and after the ultraviolet irradiation, and the oil decomposition rate was calculated from the weight change. In the appearance test, the interference color was investigated by visually observing the test piece from various angles. No interference color was detected regardless of the observation angle, ⊚, no interference color was detected when observing from the front, but slightly interference color was detected when observing from the horizontal direction. When the interference color was detected even when observed from the direction, it was evaluated as x.
【００２０】表１の調査結果にみられるように、エンボ
ス仕上げを除く表面仕上げを施したステンレス鋼の上に
光触媒層を形成した比較例では、表面仕上げの種類に関
わらず何れの場合にも干渉色に起因する色ムラが観察さ
れた。これに対し、エンボス加工されたステンレス鋼板
の上に光触媒層を形成し、或いは中間層及び光触媒層を
形成したものでは、干渉色の発現が抑えられ、油分解率
も高い値を示した。なかでも、中間層５を介在させる
と、干渉色の発現が皆無になった。薄い光触媒層を形成
した場合（試験番号３）でも、エンボス模様により干渉
色の発現が防止されていた。As can be seen from the investigation results in Table 1, in the comparative example in which the photocatalyst layer was formed on the stainless steel having the surface finish excluding the embossed finish, the interference occurred in any case regardless of the kind of the surface finish. Color unevenness due to color was observed. On the other hand, in the case where the photocatalyst layer was formed on the embossed stainless steel plate, or the intermediate layer and the photocatalyst layer were formed, the appearance of interference color was suppressed and the oil decomposition rate was high. In particular, when the intermediate layer 5 was interposed, no interference color was developed. Even when a thin photocatalyst layer was formed (Test No. 3), the embossed pattern prevented the development of interference colors.
【００２１】 [0021]
【００２２】[0022]
【発明の効果】以上に説明したように、本発明において
は、エンボス加工したステンレス鋼板の表面に光触媒層
を設けているので、光触媒層の実効表面積を大きくで
き、光触媒層を薄膜化しても高い光触媒活性がステンレ
ス鋼板の表面に付与される。また、エンボス模様によっ
て光の乱反射が促進され、反射光の光路差が大きくなる
ため、干渉色の発現が抑えられ、色ムラのない外装材，
内装材，表装材等に好適な建材が得られる。As described above, in the present invention, since the photocatalyst layer is provided on the surface of the embossed stainless steel plate, the effective surface area of the photocatalyst layer can be increased, and the photocatalyst layer can be made thin even if it is thin. Photocatalytic activity is imparted to the surface of the stainless steel plate. Further, since the irregular reflection of light is promoted by the embossed pattern and the optical path difference of the reflected light becomes large, the appearance of interference colors is suppressed, and the exterior material without color unevenness,
It is possible to obtain building materials suitable for interior and exterior materials.
【図面の簡単な説明】[Brief description of drawings]
【図１】 エンボス加工されたステンレス鋼板の一部断
面Fig. 1 Partial cross section of embossed stainless steel plate
【図２】 エンボス加工されたステンレス鋼板の上に形
成された光触媒層FIG. 2 Photocatalytic layer formed on an embossed stainless steel plate
【図３】 中間層を介して光触媒層が形成されたステン
レス鋼板FIG. 3 is a stainless steel plate having a photocatalyst layer formed through an intermediate layer.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平９−313780（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 1/00 - 35/00 C09D 1/00 - 201/10 B01J 21/00 - 35/02 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-9-313780 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B32B 1/00-35/00 C09D 1 / 00-201/10 B01J 21/00-35/02
Claims (3)
長さ０.２〜２.０ｍｍ及び凸部エッジ部長さ３０〜２０
０μｍのエンボス模様を形成したステンレス鋼板を基材
とし、エンボス模様形成面に光触媒層が設けられている
ことを特徴とする光触媒活性に優れ色ムラのないエンボ
ス加工ステンレス鋼板。1. An embossing depth of 5 to 50 μm, a flat portion of a convex portion
Length 0.2-2.0mm and convex edge length 30-20
An embossed stainless steel plate excellent in photocatalytic activity and having no color unevenness, which is characterized in that a photocatalyst layer is provided on the embossed pattern forming surface of a stainless steel plate having a 0 μm embossed pattern formed as a base material.
クリアな中間層が設けられている請求項１記載の光触媒
活性に優れ色ムラのないエンボス加工ステンレス鋼板。2. The embossed stainless steel plate having excellent photocatalytic activity and no color unevenness according to claim 1, wherein a clear intermediate layer is provided between the embossed pattern forming surface and the photocatalyst layer.
中間層が形成されている請求項２記載の光触媒活性に優
れ色ムラのないエンボス加工ステンレス鋼板。3. The embossed stainless steel plate having excellent photocatalytic activity and no color unevenness according to claim 2, wherein an intermediate layer having a refractive index smaller than that of the photocatalytic layer is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19305699A JP3371096B2 (en) | 1999-07-07 | 1999-07-07 | Embossed stainless steel plate with excellent photocatalytic activity and no color unevenness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19305699A JP3371096B2 (en) | 1999-07-07 | 1999-07-07 | Embossed stainless steel plate with excellent photocatalytic activity and no color unevenness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001018323A JP2001018323A (en) | 2001-01-23 |
| JP3371096B2 true JP3371096B2 (en) | 2003-01-27 |
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ID=16301467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19305699A Expired - Fee Related JP3371096B2 (en) | 1999-07-07 | 1999-07-07 | Embossed stainless steel plate with excellent photocatalytic activity and no color unevenness |
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| Country | Link |
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| JP (1) | JP3371096B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002200696A (en) * | 2000-12-28 | 2002-07-16 | Mitsubishi Plastics Ind Ltd | Decorative metallic plate |
| US8273425B2 (en) | 2009-05-14 | 2012-09-25 | Empire Technology Development Llc | Nanotube assisted self-cleaning material |
| US8075980B2 (en) * | 2009-05-14 | 2011-12-13 | Empire Technology Development Llc | Diffraction grating assisted self-cleaning material |
| JP5789862B2 (en) * | 2011-03-30 | 2015-10-07 | 日新製鋼株式会社 | Painted embossed stainless steel sheet and manufacturing method thereof |
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1999
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Also Published As
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| JP2001018323A (en) | 2001-01-23 |
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