JPH10264299A - Coated metal plate with excellent stain resistance and its manufacture - Google Patents
Coated metal plate with excellent stain resistance and its manufactureInfo
- Publication number
- JPH10264299A JPH10264299A JP9073835A JP7383597A JPH10264299A JP H10264299 A JPH10264299 A JP H10264299A JP 9073835 A JP9073835 A JP 9073835A JP 7383597 A JP7383597 A JP 7383597A JP H10264299 A JPH10264299 A JP H10264299A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic pigment
- photocatalyst
- layer
- stain resistance
- coated metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 36
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 31
- 239000010959 steel Substances 0.000 claims abstract description 30
- 239000011941 photocatalyst Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000011109 contamination Methods 0.000 claims description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 35
- 239000011248 coating agent Substances 0.000 abstract description 34
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract 1
- 239000002987 primer (paints) Substances 0.000 description 35
- 238000012360 testing method Methods 0.000 description 9
- 239000004566 building material Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- -1 silane compound Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、外装建材等に使用され
る耐汚染性に優れた塗装金属板及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated metal sheet excellent in stain resistance used for exterior building materials and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】意匠性，耐候性，耐食性等を改善するた
め、合成樹脂を主成分とする組成物で外装建材の表面を
被覆することが知られている。なかでも、フッ素樹脂，
アクリルウレタン樹脂，メラミン樹脂，アクリルシリコ
ン樹脂等の架橋構造をもつ樹脂は、優れた耐候性を呈す
る塗膜を形成することから、高耐候性樹脂として使用さ
れている。ところで、最近の大都市周辺では煤煙，排気
ガス等の大気汚染がひどく、それに伴って外装建材の汚
れが目立ってきている。特に、疎水性合成樹脂塗膜を設
けた外装建材が雨に曝されると、雨水による斑点状の汚
れが疎水性合成樹脂塗膜の表面に発生し易い。また、窓
枠の下等の雨水が集まって流れる部分では、スジ状の汚
れ（以下、雨筋汚れという）が発生し易い。雨筋汚れは
容易に洗浄除去できるが、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
困難な作業にもなる。塗装金属板の表面に発生する汚れ
を抑制する方法として、ポリフルオロカーボン鎖及び親
水基をもつ重合体を添加した塗料組成物が特開平１−１
９８６５３号公報で紹介されている。また、その改良と
して、加水分解性シラン化合物等を加えた親水性，撥油
性のフッ素系塗膜が特開平７−３３１１３６号公報，特
開平８−１２９２１号公報，特開平８−１２９２２号公
報等で紹介されている。2. Description of the Related Art In order to improve design, weather resistance, corrosion resistance, etc., it is known to coat the surface of exterior building materials with a composition containing a synthetic resin as a main component. Above all, fluorine resin,
A resin having a crosslinked structure, such as an acrylic urethane resin, a melamine resin, and an acrylic silicone resin, is used as a highly weather-resistant resin because it forms a coating film having excellent weather resistance. By the way, recently, air pollution such as smoke and exhaust gas has been severe in the vicinity of large cities, and contaminants on exterior building materials have been conspicuous accordingly. In particular, when an exterior building material provided with a hydrophobic synthetic resin coating film is exposed to rain, spot-like stains due to rainwater are likely to be generated on the surface of the hydrophobic synthetic resin coating film. In a portion where rainwater gathers and flows, such as under a window frame, streak-like dirt (hereinafter referred to as rain streak dirt) is likely to occur. Rain streaks can be easily washed and removed, but repeated washing is not only complicated, but also a dangerous and difficult operation for large buildings such as buildings. As a method for suppressing stains generated on the surface of a coated metal plate, a coating composition containing a polymer having a polyfluorocarbon chain and a hydrophilic group is disclosed in
No. 986553. As an improvement thereof, a hydrophilic and oil-repellent fluorine-based coating film to which a hydrolyzable silane compound or the like is added is disclosed in JP-A-7-331136, JP-A-8-12921, JP-A-8-12922, and the like. Introduced in
【０００３】[0003]
【発明が解決しようとする課題】前掲の各公報で紹介さ
れている塗膜は、雨水に由来する斑点状汚れの発生を防
止する上では有効である。しかし、外装建材の窓枠の下
等のように雨水が集まって流れる部分に発生する雨筋汚
れに対しては、十分な抑制作用を呈さない。この部分に
雨筋汚れがあると、清潔感を損ねることになる。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、特定されたプライマー層及びトップ層を組み合わせ
ることにより、表面汚れは勿論、雨筋汚れに対しても強
い抑制作用を長期間にわたって維持する耐汚染性に優れ
た塗装金属板を提供することを目的とする。The coatings described in the above publications are effective in preventing spot-like stains caused by rainwater. However, it does not exhibit sufficient suppression of rain streak generated in a portion where rainwater gathers and flows, such as under a window frame of an exterior building material. If there is rain streak dirt on this part, it will impair cleanliness. The present invention has been devised to solve such a problem, and by combining the specified primer layer and top layer, a long-lasting effect of suppressing not only surface dirt but also rain streak dirt can be obtained. An object of the present invention is to provide a coated metal sheet having excellent stain resistance which is maintained over a period.
【０００４】[0004]
【課題を解決するための手段】本発明の塗装金属板は、
その目的を達成するため、シリカ系のプライマー層及び
トップ層が下地鋼の上に順次形成されており、プライマ
ー層が無機系顔料を含み、トップ層が光触媒及び無機系
顔料を含むことを特徴とする。プライマー層及びトップ
層は、それぞれ１０μｍ以上及び０．５μｍ以上の膜厚
をもつことが好ましい。プライマー層には、５〜８０重
量％の無機系顔料が含まれる。トップ層には、光触媒及
び無機系顔料の合計含有量が５〜８０重量％で、５重量
％以上の光触媒が含まれる。この塗装金属板は、鋼板表
面に無機系顔料含有オルガノシリカゾルを塗布し、Ｓｉ
Ｏ2 前駆体からなるプライマー層を鋼板表面に形成する
熱処理を施した後、光触媒及び無機系顔料を含むオルガ
ノシリカゾルを塗布し、光触媒活性層を形成する熱処理
を施すことにより製造される。無機系顔料含有オルガノ
シリカゾルの塗布に先立って、鋼板表面を脱脂し、表面
調整及び／又はクロメート処理することが好ましい。オ
ルガノシリカゾルとしては、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及び水に溶解させたものが使
用される。The coated metal sheet of the present invention comprises:
In order to achieve the object, a silica-based primer layer and a top layer are sequentially formed on a base steel, the primer layer contains an inorganic pigment, and the top layer contains a photocatalyst and an inorganic pigment. I do. It is preferable that the primer layer and the top layer have a thickness of 10 μm or more and 0.5 μm or more, respectively. The primer layer contains 5-80% by weight of an inorganic pigment. The top layer has a total content of the photocatalyst and the inorganic pigment of 5 to 80% by weight, and contains a photocatalyst of 5% by weight or more. This coated metal plate is prepared by applying an inorganic pigment-containing organosilica sol to the surface of
It is manufactured by applying a heat treatment for forming a primer layer composed of an O 2 precursor on the surface of a steel sheet, applying an organosilica sol containing a photocatalyst and an inorganic pigment, and performing a heat treatment for forming a photocatalytic active layer. Prior to the application of the inorganic pigment-containing organosilica sol, the surface of the steel sheet is preferably degreased, and the surface is adjusted and / or chromate-treated. As the organosilica sol, one obtained by dissolving an organosilicate having a structure of R 1 Si (OR 2 ) 3 (where R 1 and R 2 represent alkyl groups) in an organic solvent and water is used.
【０００５】[0005]
【作用】本発明者等は、光触媒機能によって耐汚染性を
塗装金属板に付与することを検討し、且つ外装建材とし
て要求される密着性，隠蔽性，耐食性，耐候性に優れた
塗装金属板を製造する方法を種々調査・研究した。その
結果、オルガノシリカゾルに無機系顔料を分散させた溶
液を前処理した鋼板表面に塗布した後、熱処理すること
によりプライマー層を形成し、次いで光触媒及び無機系
顔料を含むオルガノシリカゾルを塗布し熱処理すること
によりトップ層を形成すると、耐汚染性，密着性，隠蔽
性，耐食性，耐候性に優れた塗装金属板が得られること
を見い出した。鋼板表面を脱脂した後、リン酸塩処理等
の表面調整及び／又はクロメート処理を施すと共に、Ｒ
1 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及び水
に溶解させたものをオルガノシリカゾルとして使用する
ことにより、下地鋼板に対するプライマー層の密着性が
改善される。このオルガノシリケートを使用すると、加
熱後の有機残留分が数％以下に抑えられる。そのため、
光触媒を含有しているにも拘らず塗膜の分解が起こら
ず、光触媒活性を示す塗膜が長期間にわたって安定に保
持される。The present inventors have studied the application of stain resistance to a coated metal sheet by a photocatalytic function, and have obtained a coated metal sheet having excellent adhesion, concealment, corrosion resistance and weather resistance required for exterior building materials. Various investigations and researches were conducted on the method of producing. As a result, after a solution in which an inorganic pigment is dispersed in an organosilica sol is applied to the surface of a pre-treated steel sheet, a primer layer is formed by heat treatment, and then an organosilica sol containing a photocatalyst and an inorganic pigment is applied and heat treated. As a result, it has been found that when the top layer is formed, a coated metal sheet excellent in stain resistance, adhesion, concealment, corrosion resistance and weather resistance can be obtained. After degreasing the surface of the steel sheet, the steel sheet is subjected to surface adjustment such as phosphate treatment and / or chromate treatment.
By dissolving an organosilicate having a structure of 1 Si (OR 2 ) 3 (wherein R 1 and R 2 represent alkyl groups) in an organic solvent and water, and using as an organosilica sol, a primer for the base steel sheet The adhesion of the layer is improved. When this organosilicate is used, the organic residue after heating can be suppressed to several percent or less. for that reason,
Despite containing the photocatalyst, the coating does not decompose, and the coating exhibiting photocatalytic activity is stably maintained for a long period of time.
【０００６】調製されたオルガノシリカゾルは、塗膜を
分解することがなく、また光触媒を覆って光触媒活性を
低下させることもない。これは、オルガノシリカゾルか
ら得られるシリカ系塗膜の表面に微視的な細孔が形成さ
れていることに起因するものと推察される。これに対
し、光触媒を分散させた有機系塗料で塗膜を形成する
と、光触媒が樹脂で覆われるため光触媒活性がほとんど
発現しない。このようにして塗膜が形成された塗装金属
板が良好な耐汚染性を示す理由は、次のように考えられ
る。汚れの成分は、排ガス等に由来する有機系成分及び
砂塵等の無機系成分からなっている。通常、塗膜表面と
有機系成分が強固に結合することにより汚れが発生し、
塗膜表面が黒色になる。塗膜表面を親水性にする方法で
は、雨水と共に有機系成分が洗い流されるように有機系
成分の付着抑制を狙っている。しかし、完全な撥油性が
付与されないため、塗膜の汚染を完全に防止することは
できない。[0006] The prepared organosilica sol does not decompose the coating film and does not cover the photocatalyst and reduce the photocatalytic activity. This is presumed to be due to the formation of microscopic pores on the surface of the silica-based coating film obtained from the organosilica sol. On the other hand, when a coating film is formed with an organic paint in which a photocatalyst is dispersed, the photocatalyst is covered with a resin, so that the photocatalytic activity hardly appears. The reason why the coated metal plate on which the coating film is formed exhibits good stain resistance is considered as follows. The dirt components are composed of organic components derived from exhaust gas and the like and inorganic components such as dust. Usually, stains occur due to the strong bond between the coating surface and organic components,
The coating surface turns black. The method for making the coating film surface hydrophilic aims at suppressing the adhesion of the organic components so that the organic components are washed away together with the rainwater. However, since complete oil repellency is not provided, contamination of the coating film cannot be completely prevented.
【０００７】これに対し、本発明では、塗膜表面に光触
媒を担持させており、光触媒作用によって汚れ中の有機
系成分を完全に分解している。光触媒反応後の塗膜表面
に残留する無機系成分は、塗膜表面との結合力がないの
で、雨水と共に簡単に流される。その結果、本発明の塗
装金属板は、長期間にわたって全く汚染のない表面状態
を維持するものと推察される。なお、隠蔽性は、塗膜に
配合される無機系顔料の含有量によって調整できる。ま
た、本発明の塗装金属板では、塗膜がほとんど無機系で
あるため、耐食性及び耐候性は従来の塗装金属板よりも
優れている。On the other hand, in the present invention, a photocatalyst is carried on the surface of the coating film, and the organic components in the stain are completely decomposed by the photocatalysis. The inorganic components remaining on the surface of the coating film after the photocatalytic reaction have no binding force with the surface of the coating film, and thus are easily washed away with rainwater. As a result, it is presumed that the coated metal sheet of the present invention maintains a surface state free from contamination for a long period of time. Note that the hiding power can be adjusted by the content of the inorganic pigment blended in the coating film. Further, in the coated metal sheet of the present invention, since the coating film is almost inorganic, the corrosion resistance and weather resistance are superior to those of the conventional coated metal sheet.
【０００８】[0008]
【実施の形態】前処理した金属板の表面に無機系顔料を
含むシリカ系プライマー層を形成し、その上に光触媒及
び無機系顔料を含むシリカ系トップ層を形成すると、密
着性，隠蔽性，耐食性，耐候性に優れ、光触媒作用によ
る耐汚染性が付与された塗装金属板となる。この塗装金
属板を外装建材等に使用すると、通常の表面汚れは勿
論、雨筋汚れの発生が長期間にわたって防止される。基
材となる金属板には、普通鋼板，ステンレス鋼板，Ｚｎ
めっき鋼板，Ａｌめっき鋼板，アルミ板等が使用され
る。基材表面に塗装を施すことにより耐汚染性が付与さ
れるが、塗膜には、基材に対する良好な密着性，隠蔽性
及び耐光性が要求される。そこで、脱脂後にリン酸塩処
理等の表面処理及び／又はクロメート処理により金属板
を前処理することが好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS A silica-based primer layer containing an inorganic pigment is formed on the surface of a pretreated metal plate, and a silica-based top layer containing a photocatalyst and an inorganic pigment is formed thereon. The coated metal sheet has excellent corrosion resistance and weather resistance and is provided with stain resistance due to photocatalysis. When this painted metal plate is used for an exterior building material or the like, the occurrence of rain streak contamination as well as ordinary surface contamination is prevented for a long period of time. The metal plate used as the base material includes ordinary steel plate, stainless steel plate, Zn
A plated steel sheet, an Al-plated steel sheet, an aluminum sheet, or the like is used. Stain resistance is imparted by applying a coating to the surface of the substrate, but the coating film is required to have good adhesion to the substrate, concealment, and light resistance. Therefore, it is preferable to pre-treat the metal plate by a surface treatment such as a phosphate treatment and / or a chromate treatment after degreasing.
【０００９】無機系顔料を含むオルガノシリカゾルを前
処理した金属板に塗布した後、熱処理すると、隠蔽性を
もつＳｉＯ2 前駆体からなるプライマー層が形成され
る。このプライマー層の上に光触媒及び無機系顔料を含
むオルガノシリカゾルを塗布して熱処理すると、光触媒
作用を呈するトップ層が形成される。オルガノシリカゾ
ルとしては、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
有機溶媒及び水に溶解させたものが使用される。アルキ
ル基は、特に制約されるものではないが、熱処理後に残
留する有機分が少なくなることから、炭素数が少ないも
のほど好ましい。なかでも、メチル基が好適である。プ
ライマー層に隠蔽性を付与するため、プライマー層中の
重量基準で５〜８０重量％（好ましくは３０〜７０重量
％）の無機系顔料をプライマー塗料に含ませている。無
機系顔料の含有量が５重量％に満たないと十分な隠蔽性
が得られず、逆に８０重量％を超える多量の無機系顔料
が含まれると基材に対する密着性が不十分になる。When an organosilica sol containing an inorganic pigment is applied to a pretreated metal plate and then heat-treated, a primer layer made of a SiO 2 precursor having concealing properties is formed. When an organosilica sol containing a photocatalyst and an inorganic pigment is applied on this primer layer and heat-treated, a top layer exhibiting a photocatalytic action is formed. As the organosilica sol, one obtained by dissolving an organosilicate having a structure of R 1 Si (OR 2 ) 3 (where R 1 and R 2 represent alkyl groups) in an organic solvent and water is used. The alkyl group is not particularly limited, but is preferably one having a smaller number of carbon atoms because the amount of organic components remaining after the heat treatment is reduced. Among them, a methyl group is preferred. In order to impart hiding power to the primer layer, the primer coating contains 5-80% by weight (preferably 30-70% by weight) of an inorganic pigment based on the weight of the primer layer. If the content of the inorganic pigment is less than 5% by weight, sufficient hiding properties cannot be obtained, and if the content of the inorganic pigment exceeds 80% by weight, the adhesion to the substrate becomes insufficient.
【００１０】トップ層に十分な密着性及び光触媒活性を
付与するため、トップ層中の重量基準で５重量％以上の
光触媒を含ませ、光触媒と無機系顔料の合計含有量を５
〜８０重量％（好ましくは２０〜５０重量％）の範囲に
調整する。光触媒の含有量が５重量％に満たないと、十
分な耐汚染性が得られない。しかし、光触媒と無機系顔
料の合計含有量が８０重量％を超えると、トップ層の密
着性が低下する。光触媒としては、ＴｉＯ2 ，ＺｎＯ，
ＷＯ3 ，Ｆｅ2 Ｏ3 ，ＦｅＴｉＯ3 ，ＳｒＴｉＯ3 等の
１種又は２種以上が使用される。なかでも、化学的に安
定で、しかも安価に活性度の高い微粒子が得られること
から、アナターゼ型のＴｉＯ2 が好ましい。In order to impart sufficient adhesion and photocatalytic activity to the top layer, a photocatalyst of 5% by weight or more in the top layer is contained, and the total content of the photocatalyst and the inorganic pigment is 5%.
The content is adjusted to a range of about 80% by weight (preferably 20 to 50% by weight). If the content of the photocatalyst is less than 5% by weight, sufficient stain resistance cannot be obtained. However, if the total content of the photocatalyst and the inorganic pigment exceeds 80% by weight, the adhesion of the top layer is reduced. As the photocatalyst, TiO 2 , ZnO,
WO 3, Fe 2 O 3, FeTiO 3, SrTiO 3 1 , two or more of the like. Above all, anatase-type TiO 2 is preferable since fine particles having high activity can be obtained at low cost and chemically stable.
【００１１】プライマー層形成時の熱処理温度は、６０
〜３５０℃の範囲で選定される。熱処理温度が６０℃に
達しないと、乾燥が不十分となり、トップ層を形成する
際にムラが発生する。逆に、プライマー層形成時の熱処
理温度が３５０℃を超えると、クラックが発生し、基材
表面から塗膜が剥離し易くなる。トップ層形成時の熱処
理温度は、１５０〜４００℃の範囲で選定される。熱処
理温度が１５０℃に達しないと、シリカ系塗膜の縮重合
が不十分となり、密着不良を引き起こし易い。逆に、４
００℃を超える熱処理温度では、クラックが発生し易く
なる傾向が見られる。トップ層形成時の熱処理温度は、
プライマー層形成時の熱処理温度よりも高く設定するこ
とが好ましい。より好ましくは、専ら塗膜を乾燥させる
ためプライマー層形成時の温度を８０〜１２０℃とし、
トップ層形成時の熱処理温度を１５０〜２５０℃に設定
する。この温度設定により、プライマー層形成後にはア
ルキル基が多く残存するため、トップ層との強固な結合
が得られ、トップ層形成時の熱処理でプライマー層とト
ップ層との密着性が良好となる。したがって、基材に対
する密着性が良好で、優れた耐汚染性を呈するクラック
のない塗膜が形成される。The heat treatment temperature for forming the primer layer is 60
It is selected in the range of -350 ° C. If the heat treatment temperature does not reach 60 ° C., drying becomes insufficient and unevenness occurs when forming the top layer. Conversely, if the heat treatment temperature at the time of forming the primer layer exceeds 350 ° C., cracks occur, and the coating film is easily peeled off from the substrate surface. The heat treatment temperature at the time of forming the top layer is selected in the range of 150 to 400 ° C. If the heat treatment temperature does not reach 150 ° C., the polycondensation of the silica-based coating film becomes insufficient, and poor adhesion is likely to occur. Conversely, 4
At a heat treatment temperature higher than 00 ° C., cracks tend to occur easily. The heat treatment temperature when forming the top layer is
It is preferable to set higher than the heat treatment temperature at the time of forming the primer layer. More preferably, the temperature at the time of forming the primer layer is 80 to 120 ° C. in order to exclusively dry the coating film,
The heat treatment temperature for forming the top layer is set to 150 to 250 ° C. By this temperature setting, since a large amount of alkyl groups remain after the formation of the primer layer, a strong bond with the top layer is obtained, and the adhesion between the primer layer and the top layer is improved by heat treatment during the formation of the top layer. Accordingly, a crack-free coating film having good adhesion to the substrate and exhibiting excellent stain resistance is formed.
【００１２】[0012]
【実施例】ブチルセロソルブ及びイソプロパノールの混
合溶媒にメチルトリメトキシシリケートを溶解し、水を
加えて加水分解を進行させることによりオルガノシリカ
ゾルを調製した。得られたオルガノシリカゾルに白色顔
料であるＡｌ2 Ｏ3 処理ＴｉＯ2 粉末を分散させ、プラ
イマー塗料を調製した。トップ塗料は、同じオルガノシ
リカゾルに粒径２０ｎｍのアナターゼ型ＴｉＯ2 粉末を
分散させることにより調製した。塗装原板にはＺｎめっ
き鋼板を使用し、脱脂，表面調製，クロメート処理等の
前処理を施した。塗装原板にプライマー塗料をスプレー
塗布し、８０℃での乾燥によりプライマー層を形成し
た。プライマー層の上にトップ塗料をスプレー塗布し、
２００℃×１０分の熱処理でトップ層を形成した。得ら
れた塗装鋼板は、図１に示すように下地鋼１の表面にプ
ライマー層２及びトップ層３が順次形成された層構造を
もっていた。EXAMPLE An organosilica sol was prepared by dissolving methyltrimethoxysilicate in a mixed solvent of butyl cellosolve and isopropanol and adding water to promote hydrolysis. Al 2 O 3 -treated TiO 2 powder as a white pigment was dispersed in the obtained organosilica sol to prepare a primer coating. The top paint was prepared by dispersing an anatase type TiO 2 powder having a particle size of 20 nm in the same organosilica sol. A Zn-plated steel sheet was used as a coating base sheet, and was subjected to pretreatments such as degreasing, surface preparation, and chromate treatment. A primer coating was spray-coated on the original coating plate and dried at 80 ° C. to form a primer layer. Spray the top paint over the primer layer,
A top layer was formed by a heat treatment at 200 ° C. for 10 minutes. The obtained coated steel sheet had a layer structure in which a primer layer 2 and a top layer 3 were sequentially formed on the surface of a base steel 1 as shown in FIG.
【００１３】プライマー層２は、下地鋼１に対して十分
な密着性を呈し、且つ隠蔽性をもつことが要求される。
トップ層３は、耐汚染性に寄与することが要求される。
全体としての塗装鋼板は、耐食性及び耐候性を兼ね備え
ることが要求される。そこで、プライマー層２及びトッ
プ層３に含まれる無機系顔料，光触媒の含有量を種々変
化させ、無機系顔料，光触媒の含有量が塗膜物性に及ぼ
す影響を調査した。調査結果を表１に示す。なお。密着
性は碁盤目状テープ剥離試験で評価し、塗膜が全く剥離
しないものを○，少しでも剥離したものを×として判定
した。隠蔽性は色彩測定によるＬ値で評価し、完全に下
地が見えない状態のＬ値を基準としてΔＬが±１以内の
ものを○，±１を超えるものを×と判定した。耐食性は
５％塩水噴霧試験で評価し、試験１０００時間後に赤錆
が発生しないものを○，赤錆が発生したものを×と判定
した。耐候性はサンシャインウェザー試験で評価し、試
験１０００時間後に光沢や色彩が変化しなかったものを
○，変化したものを×と判定した。耐汚染性について
は、塗装鋼板に雨筋が垂れるように波板を取り付けた塗
装鋼板を地面に対し９０度で設置した暴露試験で評価
し、取付け直後と３か月経過後のΔＬ値が±１以内のも
のを○，±１を超えるものを×と判定した。The primer layer 2 is required to exhibit sufficient adhesion to the base steel 1 and have concealing properties.
The top layer 3 is required to contribute to stain resistance.
The coated steel sheet as a whole is required to have both corrosion resistance and weather resistance. Then, the contents of the inorganic pigment and the photocatalyst contained in the primer layer 2 and the top layer 3 were variously changed, and the influence of the contents of the inorganic pigment and the photocatalyst on the physical properties of the coating film was investigated. Table 1 shows the survey results. In addition. The adhesiveness was evaluated by a cross-cut tape peeling test, and a sample in which the coating film was not peeled at all was evaluated as ，, and a sample in which the coating film was slightly peeled was evaluated as ×. The concealability was evaluated based on the L value obtained by color measurement. Based on the L value in a state where the base was completely invisible, Δ was within ± 1 and Δ exceeded ± 1 as ×. The corrosion resistance was evaluated by a 5% salt spray test, and when red rust did not occur after 1000 hours of the test, it was judged as ○, and when red rust occurred, it was judged as ×. The weather resistance was evaluated by a sunshine weather test. When the gloss and color did not change 1000 hours after the test, it was judged as ○. Contamination resistance was evaluated by an exposure test in which a coated steel sheet with a corrugated sheet attached to the coated steel sheet at 90 degrees to the ground so that the rain streak hanged down. Those within 1 were evaluated as ○, and those exceeding ± 1 were evaluated as ×.
【００１４】 [0014]
【００１５】表１から明らかなように、顔料含有量５〜
８０重量％のプライマー層を１０μｍ以上の膜厚で形成
し、ＴｉＯ2 含有量５重量％以上のトップ層を０．５μ
ｍ以上の膜厚で形成すると、塗装鋼板に良好な耐汚染性
が付与されることが判る。また、試験番号８の塗装鋼板
を使用し、雨筋暴露試験での色彩測定によりＬ値の経時
変化を調査した。調査結果を、通常使用されているフッ
素樹脂被覆鋼板を比較例として図２に示す。図２にみら
れるように、フッ素樹脂被覆鋼板では試験開始から３か
月経過した時点で表面がかなり汚れているのに対し、本
発明に従った塗装鋼板は取付け時と変化のない表面を維
持していることが判る。更に、同じプライマー塗料及び
トップ塗料を使用し、熱処理温度を種々変更してプライ
マー層及びトップ層を形成することにより、熱処理温度
が密着性に及ぼす影響を調査した。なお、この場合に
は、プライマー層中の顔料含有量を７５重量％，膜厚を
２０μｍの一定値に、トップ層中のＴｉＯ2 含有量を５
０重量％，膜厚を１０μｍの一定値にした。表２の調査
結果にみられるように、プライマー層の熱処理温度を６
０〜３５０℃、トップ層の熱処理温度を１５０〜４００
℃の範囲で選定することにより、密着性に優れた耐汚染
性塗装鋼板が得られることが判った。As is apparent from Table 1, the pigment content is 5 to 5.
A primer layer of 80% by weight is formed with a thickness of 10 μm or more, and a top layer having a TiO 2 content of 5% by weight or more is formed of 0.5 μm.
It can be seen that when formed with a film thickness of at least m, the coated steel sheet is given good stain resistance. Further, using the coated steel sheet of Test No. 8, the time-dependent change of the L value was examined by color measurement in a rain streak exposure test. The investigation results are shown in FIG. 2 using a commonly used fluororesin-coated steel sheet as a comparative example. As shown in FIG. 2, the surface of the fluororesin-coated steel sheet is considerably dirty after three months from the start of the test, while the coated steel sheet according to the present invention maintains the surface unchanged from that at the time of installation. You can see that it is. Further, the influence of the heat treatment temperature on the adhesion was investigated by forming the primer layer and the top layer by using the same primer paint and the top paint and changing the heat treatment temperature variously. In this case, the pigment content in the primer layer was set to a constant value of 75% by weight, the film thickness was set to a constant value of 20 μm, and the TiO 2 content in the top layer was set to 5%.
0 wt%, and the film thickness was set to a constant value of 10 μm. As can be seen from the survey results in Table 2, the heat treatment temperature of the primer layer was 6
0-350 ° C, heat treatment temperature of top layer is 150-400
It was found that by selecting a temperature within the range of ° C., a stain-resistant coated steel sheet having excellent adhesion can be obtained.
【００１６】 [0016]
【００１７】[0017]
【発明の効果】以上に説明したように、本発明の塗装金
属板は、無機系顔料を含むシリカ系プライマー層の上に
無機系顔料及び光触媒を含むシリカ系トップ層を形成
し、光触媒作用によって塗膜表面に付着した有機物を分
解させることにより耐汚染性を向上させている。また、
シリカ系をベースとした塗膜であるため、隠蔽性や耐光
性にも優れている。このようにして、本発明の塗装金属
板は、通常の汚れは勿論、雨筋汚れも防止され、長期間
にわたって美麗な表面を呈する外装建材等として使用さ
れる。As described above, the coated metal plate of the present invention has a silica-based primer layer containing an inorganic pigment and a silica-based top layer containing an inorganic pigment and a photocatalyst formed thereon. The stain resistance is improved by decomposing organic substances attached to the coating film surface. Also,
Since it is a silica-based coating film, it has excellent hiding properties and light resistance. In this way, the coated metal sheet of the present invention can be used as an exterior building material or the like which has a beautiful surface for a long period of time by preventing not only ordinary dirt but also rain streak dirt.
【図１】 プライマー層及びトップ層が積層された塗装
金属板FIG. 1 A painted metal plate on which a primer layer and a top layer are laminated
【図２】 本発明の塗装金属板が耐汚染性に優れている
ことを、フッ素樹脂被覆鋼板と比較して示したグラフFIG. 2 is a graph showing that the coated metal sheet of the present invention is excellent in stain resistance in comparison with a fluororesin-coated steel sheet.
１：下地鋼 ２：プライマー層 ３：トッ
プ層1: Base steel 2: Primer layer 3: Top layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂戸 健二 千葉県市川市高谷新町７番１号 日新製鋼 株式会社技術研究所内 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kenji Sakado 7-1, Takayashinmachi, Ichikawa-shi, Chiba Nisshin Steel Co., Ltd.
Claims (7)
下地鋼の上に順次形成されており、プライマー層が無機
系顔料を含み、トップ層が光触媒及び無機系顔料を含む
ことを特徴とする耐汚染性に優れた塗装金属板。A silica-based primer layer and a top layer are sequentially formed on a base steel, the primer layer contains an inorganic pigment, and the top layer contains a photocatalyst and an inorganic pigment. Painted metal plate with excellent contamination.
厚０．５μｍ以上のトップ層が形成されている請求項１
記載の耐汚染性に優れた塗装金属板。2. A primer layer having a thickness of 10 μm or more and a top layer having a thickness of 0.5 μm or more are formed.
Painted metal sheet with excellent stain resistance.
顔料を含んでいる請求項１又は２記載の耐汚染性に優れ
た塗装金属板。3. The coated metal plate having excellent stain resistance according to claim 1, wherein the primer layer contains 5 to 80% by weight of an inorganic pigment.
び無機系顔料の合計含有量が５〜８０重量％であるトッ
プ層が形成されている請求項１又は２記載の耐汚染性に
優れた塗装金属板。4. The excellent stain resistance according to claim 1, wherein a top layer containing 5% by weight or more of a photocatalyst and having a total content of the photocatalyst and the inorganic pigment of 5 to 80% by weight is formed. Painted metal plate.
カゾルを塗布し、ＳｉＯ2 前駆体からなるプライマー層
を鋼板表面に形成する熱処理を施した後、光触媒及び無
機系顔料を含むオルガノシリカゾルを塗布し、光触媒活
性層を形成する熱処理を施すことを特徴とする耐汚染性
に優れた塗装金属板の製造方法。5. An organosilica sol containing an inorganic pigment is applied to the surface of a steel sheet, and a heat treatment for forming a primer layer composed of a SiO 2 precursor on the surface of the steel sheet is performed, and then an organosilica sol containing a photocatalyst and an inorganic pigment is applied. And a heat treatment for forming a photocatalytically active layer. A method for producing a coated metal sheet having excellent stain resistance.
布に先立って、鋼板表面を脱脂し、表面調整及び／又は
クロメート処理する請求項５記載の耐汚染性に優れた塗
装金属板の製造方法。6. The method for producing a coated metal sheet excellent in stain resistance according to claim 5, wherein the surface of the steel sheet is degreased, surface-adjusted and / or chromate-treated before the application of the inorganic pigment-containing organosilica sol.
はアルキル基を示す）の構造をもつオルガノシリケート
を有機溶媒及び水に溶解させたものをオルガノシリカゾ
ルとして使用する請求項５記載の耐汚染性に優れた塗装
金属板の製造方法。7. R 1 Si (OR 2 ) 3 (where R 1 , R 2
The method for producing a coated metal sheet excellent in stain resistance according to claim 5, wherein a solution obtained by dissolving an organosilicate having a structure of (a) represents an alkyl group) in an organic solvent and water is used as the organosilica sol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07383597A JP3384945B2 (en) | 1997-03-26 | 1997-03-26 | Painted metal sheet excellent in stain resistance and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07383597A JP3384945B2 (en) | 1997-03-26 | 1997-03-26 | Painted metal sheet excellent in stain resistance and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10264299A true JPH10264299A (en) | 1998-10-06 |
| JP3384945B2 JP3384945B2 (en) | 2003-03-10 |
Family
ID=13529605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07383597A Expired - Fee Related JP3384945B2 (en) | 1997-03-26 | 1997-03-26 | Painted metal sheet excellent in stain resistance and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3384945B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1110782A (en) * | 1997-06-26 | 1999-01-19 | Nisshin Steel Co Ltd | Highly pollution-resistant metal panel |
| JP2001105535A (en) * | 1999-10-13 | 2001-04-17 | Hiraoka & Co Ltd | Colored sheet excellent in discoloration preventing property |
| JP2001199014A (en) * | 1999-11-08 | 2001-07-24 | Hiraoka & Co Ltd | Antistaining sheet |
| JP2003181998A (en) * | 2002-09-24 | 2003-07-03 | Hiraoka & Co Ltd | Colored sheet with outstanding anti-discoloring and fading properties |
| JP2004001502A (en) * | 1999-11-08 | 2004-01-08 | Hiraoka & Co Ltd | Stainproof sheet |
| JP2004058673A (en) * | 1999-11-08 | 2004-02-26 | Hiraoka & Co Ltd | Stainproof sheet |
| JP2004058672A (en) * | 1999-11-08 | 2004-02-26 | Hiraoka & Co Ltd | Stainproof sheet |
| WO2022270283A1 (en) * | 2021-06-25 | 2022-12-29 | 日本製鉄株式会社 | Coated metal sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH09613A (en) * | 1995-06-16 | 1997-01-07 | Titan Kogyo Kk | Article with silica film containing powder of functional substance |
-
1997
- 1997-03-26 JP JP07383597A patent/JP3384945B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
| JPH09613A (en) * | 1995-06-16 | 1997-01-07 | Titan Kogyo Kk | Article with silica film containing powder of functional substance |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1110782A (en) * | 1997-06-26 | 1999-01-19 | Nisshin Steel Co Ltd | Highly pollution-resistant metal panel |
| JP2001105535A (en) * | 1999-10-13 | 2001-04-17 | Hiraoka & Co Ltd | Colored sheet excellent in discoloration preventing property |
| JP2001199014A (en) * | 1999-11-08 | 2001-07-24 | Hiraoka & Co Ltd | Antistaining sheet |
| JP2004001502A (en) * | 1999-11-08 | 2004-01-08 | Hiraoka & Co Ltd | Stainproof sheet |
| JP2004058673A (en) * | 1999-11-08 | 2004-02-26 | Hiraoka & Co Ltd | Stainproof sheet |
| JP2004058672A (en) * | 1999-11-08 | 2004-02-26 | Hiraoka & Co Ltd | Stainproof sheet |
| JP2003181998A (en) * | 2002-09-24 | 2003-07-03 | Hiraoka & Co Ltd | Colored sheet with outstanding anti-discoloring and fading properties |
| WO2022270283A1 (en) * | 2021-06-25 | 2022-12-29 | 日本製鉄株式会社 | Coated metal sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3384945B2 (en) | 2003-03-10 |
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