JP6030292B2 - Multifunctional pre-coated steel sheet - Google Patents
Multifunctional pre-coated steel sheet Download PDFInfo
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- JP6030292B2 JP6030292B2 JP2011188694A JP2011188694A JP6030292B2 JP 6030292 B2 JP6030292 B2 JP 6030292B2 JP 2011188694 A JP2011188694 A JP 2011188694A JP 2011188694 A JP2011188694 A JP 2011188694A JP 6030292 B2 JP6030292 B2 JP 6030292B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 67
- 239000010959 steel Substances 0.000 title claims description 67
- 239000011941 photocatalyst Substances 0.000 claims description 150
- 238000000576 coating method Methods 0.000 claims description 112
- 239000011248 coating agent Substances 0.000 claims description 102
- 239000011247 coating layer Substances 0.000 claims description 96
- 239000010410 layer Substances 0.000 claims description 55
- 239000003973 paint Substances 0.000 claims description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 46
- 229910052731 fluorine Inorganic materials 0.000 claims description 46
- 239000011737 fluorine Substances 0.000 claims description 46
- 229920000554 ionomer Polymers 0.000 claims description 45
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 33
- 229920001225 polyester resin Polymers 0.000 claims description 31
- 239000004645 polyester resin Substances 0.000 claims description 30
- 230000001699 photocatalysis Effects 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 20
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- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000000539 amino acid group Chemical group 0.000 claims description 4
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000002987 primer (paints) Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
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- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- 101150038956 cup-4 gene Proteins 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Description
本発明は生産性、加工性、耐久性に優れる、多機能プレコート鋼板に関する。 The present invention relates to a multifunctional precoated steel sheet that is excellent in productivity, workability, and durability.
プレコート鋼板（「プレコートメタル」、「ＰＣＭ」、「塗装鋼板」等とも称する。以下、単に「ＰＣＭ」と称する。）は、基材である鋼板の表面に、予めポリエステル樹脂材料等の有機塗膜層（着色塗膜層）が焼付塗装で形成される。
ＰＣＭは通常、コイルコーティングラインにおいて連続高速生産されるため、ポストコートと比較して塗料ロスが少なく、塗料回収率も高く、良好な生産性を期待できる。塗膜厚のバラツキが少なく塗膜物性が均一であり、安定的品質が確保できる。鋼板の表面には、着色塗膜層ごとエンボスや梨地等の表面加工が施される場合もある。ユーザーは購入したＰＣＭをそのままの形態で利用できるほか、工業用用途としての利用度も高範囲にわたる。主な用途としては、屋根や金属成形板、パーティション等の外装・内装を含む各種建材、冷蔵庫や洗濯機、エアコン等の家電製品等が挙げられる。
A pre-coated steel plate (also referred to as “pre-coated metal”, “PCM”, “painted steel plate”, etc., hereinafter simply referred to as “PCM”) is an organic coating film such as a polyester resin material in advance on the surface of the steel plate as a base material. A layer (colored coating layer) is formed by baking.
Since PCM is normally continuously produced at a high speed in the coil coating line, paint loss is low and paint recovery is high compared to post-coating, and good productivity can be expected. There is little variation in coating thickness, and the coating properties are uniform, ensuring stable quality. The surface of the steel sheet may be subjected to surface processing such as embossing or satin finish together with the colored coating layer. The user can use the purchased PCM as it is and also has a high range of industrial use. Major applications include various building materials including exteriors and interiors such as roofs, metal molded plates, partitions, etc., and home appliances such as refrigerators, washing machines, and air conditioners.
ところで近年において、建築物外装には埃、雨筋、カビ、藻が付着・発生しにくい性能（防汚染性）及びＮＯｘなど有機物を分解する空気浄化機能が望まれている。また、室内環境下においては、シックハウス症候群の原因であるＶＯＣ除去、抗ウイルス性、抗菌性及び防臭等が要請されている。
一般的にこれらの機能を要する内装仕上げ材、外装仕上げ材には、これらの機能を有した光触媒塗料をスプレー、刷毛、ローラーなどの塗装器具でポストコート（加工、施工後に塗装）しているが、スプレー塗装の場合、塗着率が悪く使用塗料の約半数しか付着しないためコストＵＰになること及び乾燥までに時間が掛かるのなど作業性とコストに問題があることから、内・外装に施工した時点で、機能が発揮されるプレコート鋼板（ＰＣＭ）の開発が望まれている。
ＰＣＭに上記した多機能を付与する手段として、ＰＣＭ表面への光触媒効果の付与が考えられている（特許文献１、２等）。光触媒は酸化チタンなどの金属酸化物からなり、励起状態では酸化還元反応を生じて汚染物質の有機物を分解するため、耐汚染性や抗菌性、消臭等に優れた機能を発揮する。
By the way, in recent years, it has been desired that the exterior of a building has a performance (contamination resistance) in which dust, rain stripes, mold, and algae are less likely to adhere and generate and an air purification function that decomposes organic matter such as NOx. Further, under indoor environment, VOC removal, antiviral properties, antibacterial properties, deodorization, and the like that cause sick house syndrome are required.
In general, for interior finish materials and exterior finish materials that require these functions, photocatalyst paints with these functions are post-coated (painted after processing and construction) with spraying tools such as sprays, brushes, and rollers. In the case of spray coating, the coating rate is poor and only about half of the paint used is attached, which increases costs and takes time to dry. At that time, development of a pre-coated steel plate (PCM) that exhibits its function is desired.
As a means for imparting the above-mentioned multi-functionality to PCM, it is considered that a photocatalytic effect is imparted to the PCM surface (Patent Documents 1 and 2). The photocatalyst is made of a metal oxide such as titanium oxide, and in an excited state, it produces a redox reaction and decomposes organic substances as pollutants. Therefore, the photocatalyst exhibits excellent functions such as contamination resistance, antibacterial properties, and deodorization.
しかしながら光触媒により酸化還元反応が生じ、ＰＣＭ表面に有機塗膜層が形成されている場合塗膜が分解されて劣化するため、耐久性の問題がある。このため、光触媒を含む塗膜に有機樹脂成分を入れることは一般に非常に困難である（特許文献１、２を参照）。
この問題に対し、例えば特許文献３に示すように、光触媒反応に対して耐久性を持つバインダとして、シリカゾルやシロキサン等の無機高分子を用いてなる光触媒塗料が開発されている。
However, when a redox reaction is caused by the photocatalyst and an organic coating layer is formed on the surface of the PCM, the coating layer is decomposed and deteriorates, which causes a problem of durability. For this reason, it is generally very difficult to add an organic resin component to a coating film containing a photocatalyst (see Patent Documents 1 and 2).
In response to this problem, for example, as shown in Patent Document 3, a photocatalyst coating material using an inorganic polymer such as silica sol or siloxane has been developed as a binder having durability against photocatalytic reaction.
ＰＣＭに光触媒塗料を適用する場合において、未だ以下の課題がある。
第一に、ＰＣＭには加工性が要求される。ＰＣＭには曲げ加工等の加工を行う事が多く、鋼板と一体化された塗膜にも加工性を有することが必要である。しかしながら特許文献３のように無機高分子を用いた光触媒層を形成すると、十分な加工性が得られない。このため光触媒層に曲げ加工の応力が及んだり、運搬時に外部と擦れると、光触媒層が容易に剥離や損傷を生じる恐れがある。これは特に、過酷な曲げ加工を伴う建材にＰＣＭを適用する場合において考慮すべき課題である。
When applying a photocatalytic coating to PCM, there are still the following problems.
First, processability is required for PCM. PCM often performs processes such as bending, and the coating film integrated with the steel sheet must also have processability. However, when a photocatalyst layer using an inorganic polymer is formed as in Patent Document 3, sufficient processability cannot be obtained. For this reason, if the bending stress is applied to the photocatalyst layer or the photocatalyst layer is rubbed with the outside during transportation, the photocatalyst layer may be easily peeled off or damaged. This is a problem to be considered particularly when PCM is applied to building materials that involve severe bending.
第二に、バリアコートの課題である。特許文献１、２に記載されるように、一般に光触媒塗膜を形成する場合には、光触媒が下地を劣化させる、いわゆる裏反応を生じる可能性があるため、バリアコートの形成が不可欠である。バリアコートの塗装に伴い塗装工程が煩雑になり、歩留まりが低下するほか、生産コストも上昇を来たす。
第三に、コイルコーティングライン塗装適性の課題である。無機高分子を用いた塗料は不揮発分が少なく粘度が非常に低い。このため連続生産における塗料の塗布量の管理が難しく、厳格な塗布量の制御を必要とし、コイルコーティングラインでの連続生産を行うのは難しい。また、無機高分子は最終硬化するまでに長時間を有するため、塗膜品質が安定せず、製品完成後の品質管理や即出荷時の出荷検査に不利である。
Second, it is a problem of barrier coating. As described in Patent Documents 1 and 2, in general, when a photocatalyst coating film is formed, formation of a barrier coat is indispensable because the photocatalyst may cause a so-called back reaction that degrades the base. The barrier coating process complicates the coating process, lowers yield, and increases production costs.
Third, it is a problem of suitability for coil coating line painting. Paints using inorganic polymers have a low nonvolatile content and a very low viscosity. For this reason, it is difficult to manage the coating amount in the continuous production, and it is necessary to strictly control the coating amount, and it is difficult to perform continuous production in the coil coating line. Further, since the inorganic polymer has a long time until final curing, the coating film quality is not stable, which is disadvantageous for quality control after product completion and shipping inspection at the time of immediate shipment.
本発明は上記した各課題に鑑みてなされたものであって、バリアコートを形成しなくても長期にわたり良好な光触媒機能を発揮し、コイルコーティングラインで製造することが可能な多機能ＰＣＭとその製造方法を提供することを目的とする。 The present invention has been made in view of the above-described problems, and exhibits a good photocatalytic function over a long period of time without forming a barrier coat, and a multi-functional PCM that can be manufactured on a coil coating line and its An object is to provide a manufacturing method.
上記課題を解決するために本発明は、鋼板と、前記鋼板表面に形成された有機塗膜層と、前記有機塗膜層表面に形成された光触媒塗膜層とを有し、前記光触媒塗膜層は、光触媒成分とバインダ成分を含んでなり、前記バインダ成分は、ポリエステル樹脂ディスパージョン及びフッ化度４０％以上のフッ素アイオノマーを含有し、前記光触媒成分は前記フッ素アイオノマーに内包されており、前記有機塗膜層及び前記光触媒塗膜層が、ともに熱可塑性を利用して形成される光触媒塗膜付ＰＣＭ鋼板とした。 In order to solve the above problems, the present invention includes a steel plate, an organic coating layer formed on the surface of the steel plate, and a photocatalytic coating layer formed on the surface of the organic coating layer. The layer comprises a photocatalyst component and a binder component, and the binder component contains a polyester resin dispersion and a fluorine ionomer having a fluorination degree of 40% or more, and the photocatalyst component is included in the fluorine ionomer, Both the organic coating layer and the photocatalytic coating layer were PCM steel plates with a photocatalytic coating formed by utilizing thermoplasticity.
本願発明者らがＰＣＭに適した光触媒塗料について鋭意検討した結果、バインダ成分として、フッ化度４０％以上のフッ素アイオノマー、及びポリエステル樹脂ディスパージョンを用いれば、優れた光触媒機能の発揮とともに、良好な加工性、並びに耐久性を持つ光触媒塗膜付ＰＣＭが得られることを見出した。本発明はこれの知見に基づくものである。
すなわち本発明の光触媒塗膜付ＰＣＭでは、フッ素アイオノマーの効果により、使用時に光触媒塗膜（層）の表面に雨滴等の水が付着すると、当該層の表面全体に薄い平坦な水膜が形成される。光触媒層の表面に付着していた汚染物質はこの水膜により浮き上がり、水と共に除去される。また、光触媒塗膜層が太陽等により光照射されると、光触媒が励起して光触媒反応を生じ、汚染物質が分解除去される。また、可視光応答型光触媒を使用した場合、室内において、蛍光灯の光源の下、光触媒反応により、抗菌性及びウィルス不活性化の機能を有する。
As a result of intensive studies on the photocatalyst coating material suitable for PCM by the present inventors, if a fluorine ionomer having a degree of fluorination of 40% or more and a polyester resin dispersion are used as the binder component, the photocatalyst function is excellent and excellent. It has been found that a PCM with a photocatalytic coating film having workability and durability can be obtained. The present invention is based on this finding.
That is, in the PCM with a photocatalyst coating film of the present invention, when water such as raindrops adheres to the surface of the photocatalyst coating film (layer) during use due to the effect of the fluorine ionomer, a thin flat water film is formed on the entire surface of the layer. The Contaminants adhering to the surface of the photocatalyst layer are lifted by this water film and removed together with water. Further, when the photocatalyst coating layer is irradiated with light from the sun or the like, the photocatalyst is excited to cause a photocatalytic reaction, and the contaminants are decomposed and removed. Further, when a visible light responsive photocatalyst is used, it has a function of antibacterial activity and virus inactivation by a photocatalytic reaction indoors under a light source of a fluorescent lamp.
一方、光触媒層はバインダ成分にポリエステル樹脂を含んでおり、高度な加工性を呈する。このため、曲げプレス加工等の強い応力が及んでも、鋼板の変形に追従して光触媒塗膜層も柔軟に伸縮・変形し、容易に剥離や損傷を生じることがない。従って、従来と同様、ＰＣＭの加工性や色相・形状の制約を受けることがない。
また、本発明の有機塗膜層は熱硬化反応、光触媒層は熱可塑性によって形成できるため、焼き付け塗装が可能であるほか、有機材料で構成されているため、無機材料に比べて塗料粘度調整も容易である。
On the other hand, the photocatalyst layer contains a polyester resin as a binder component and exhibits high processability. For this reason, even if strong stress such as bending press processing is applied, the photocatalyst coating layer flexibly expands and contracts following the deformation of the steel sheet, and does not easily peel or damage. Therefore, as in the prior art, there are no restrictions on PCM processability, hue, or shape.
In addition, since the organic coating layer of the present invention can be formed by a thermosetting reaction and the photocatalyst layer can be formed by thermoplasticity, it can be baked and painted, and since it is made of an organic material, the viscosity of the coating can be adjusted compared to an inorganic material. Easy.
よって、本発明は高速生産性に優れ、焼付塗装工程を経るコイルコーティングライン等に適用可能である。さらにバインダ成分に添加するポリエステル樹脂ディスパージョンは、フッ素アイオノマーとの相溶性が良好であり、光触媒塗膜層において良好な塗膜を構成することが可能である。
また、本発明ではＣ−Ｃ結合に比べて化学安定性に優れるＣ−Ｆ結合を豊富に有する、４０％以上のフッ化度を持つフッ素アイオノマーを所定の添加量にてバインダ成分に利用し、当該フッ素アイオノマーで光触媒を内包させている。これにより光触媒反応を生じても光触媒塗膜層が容易に自己分解しないほか、光触媒が下地に直接触れるのがフッ素アイオノマーにより防止されるため、バリアコートを用いる必要がない。これにより光触媒塗膜層を長期にわたり維持でき、美観に優れるＰＣＭを低コストで効率よく実現できる。
Therefore, the present invention is excellent in high-speed productivity, and can be applied to a coil coating line that undergoes a baking coating process. Furthermore, the polyester resin dispersion added to the binder component has good compatibility with the fluorine ionomer, and can form a good coating film in the photocatalytic coating film layer.
Further, in the present invention, a fluorine ionomer having a fluorination degree of 40% or more, which has abundant C—F bonds that are excellent in chemical stability as compared with C—C bonds, is used as a binder component at a predetermined addition amount, The photocatalyst is included in the fluorine ionomer. As a result, even if a photocatalytic reaction occurs, the photocatalyst coating layer does not easily self-decompose, and the fluorine ionomer prevents the photocatalyst from coming into direct contact with the base, so there is no need to use a barrier coat. As a result, the photocatalyst coating layer can be maintained over a long period of time, and PCM with excellent aesthetics can be efficiently realized at low cost.
＜発明の各態様＞
本発明の一態様は、鋼板と、前記鋼板表面に形成された有機層と、前記有機層表面に形成された光触媒層とを有し、前記光触媒層は、光触媒成分とバインダ成分を含んでなり、前記バインダ成分は、ポリエステル樹脂ディスパージョン及びフッ化度４０％以上のフッ素アイオノマーを含有し、前記光触媒成分は前記フッ素アイオノマーに内包されており、前記光触媒層が、熱可塑性で形成されている光触媒塗膜付ＰＣＭ鋼板とする。
<Each aspect of the invention>
One aspect of the present invention includes a steel plate, an organic layer formed on the surface of the steel plate, and a photocatalyst layer formed on the surface of the organic layer, and the photocatalyst layer includes a photocatalyst component and a binder component. The binder component contains a polyester resin dispersion and a fluorine ionomer having a degree of fluorination of 40% or more, the photocatalyst component is included in the fluorine ionomer, and the photocatalyst layer is formed of a thermoplastic material. A coated PCM steel sheet.
ここで本発明の別の態様として、前記バインダ成分は、樹脂不揮発成分換算において、前記ポリエステル樹脂ディスパージョンと前記フッ素アイオノマーとの重量比率が２０：８０〜７０：３０の範囲であり、且つ、前記フッ素アイオノマーと前記光触媒との重量比率が３０：７０〜６０：４０の範囲である構成とすることもできる。
また本発明の別の態様として、前記フッ素アイオノマーは、ポリテトラフルオロエチレンの側鎖にスルホン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にカルボン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にアミノ基を有するグラフト重合体、末端にリン酸エステルを有するパーフルオロアルキルオリゴマー、末端にスルホン酸基を有するパーフルオロアルキルオリゴマー、末端にカルボン酸基を有するパーフルオロアルキルオリゴマー、末端にアミノ酸基を有するパーフルオロアルキルオリゴマー、パーフルオロアルキルエチレン付加物の中から選択される、１種または２種以上の混合物とすることもできる。
Here, as another aspect of the present invention, the binder component has a weight ratio of the polyester resin dispersion to the fluorine ionomer in the range of 20:80 to 70:30 in terms of a resin non-volatile component, and The weight ratio between the fluorine ionomer and the photocatalyst may be in the range of 30:70 to 60:40.
As another aspect of the present invention, the fluorine ionomer includes a graft polymer having a sulfonic acid in the side chain of polytetrafluoroethylene, a graft polymer having a carboxylic acid in the side chain of polytetrafluoroethylene, and polytetrafluoroethylene. A graft polymer having an amino group in the side chain, a perfluoroalkyl oligomer having a phosphate ester at a terminal, a perfluoroalkyl oligomer having a sulfonic acid group at a terminal, a perfluoroalkyl oligomer having a carboxylic acid group at a terminal, One or a mixture of two or more selected from perfluoroalkyl oligomers having amino acid groups and perfluoroalkylethylene adducts can also be used.
また、本発明の別の態様として、前記ポリエステル樹脂ディスパージョンは、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートの中から選んだ１種または２種以上の混合物とすることもできる。
また、本発明の別の態様として、前記光触媒層の膜厚を０．５μｍ以上５μｍ以下とすることもできる。
As another aspect of the present invention, the polyester resin dispersion may be one or a mixture of two or more selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. .
Moreover, as another aspect of the present invention, the film thickness of the photocatalyst layer may be 0.5 μm or more and 5 μm or less.
次に本発明の一態様である光触媒塗膜付ＰＣＭ鋼板の製造方法は、鋼板の表面に有機塗料を塗布する第一塗布工程と、前記塗布した有機塗料を焼付して有機層を形成する第一焼付工程と、前記有機層の上に、光触媒塗料を塗布する第二塗布工程と、前記塗布した光触媒塗料を焼付して光触媒層を形成する第二焼付工程と、を順次経るものとし、前記第二塗布工程では、前記有機塗料として、ポリエステル樹脂ディスパージョンとフッ化度４０％以上のフッ素アイオノマーをバインダ成分として含有する塗料を用いるものとする。 Next, a method for producing a PCM steel sheet with a photocatalyst coating film according to one aspect of the present invention includes a first application step of applying an organic paint to the surface of the steel sheet, and an organic layer formed by baking the applied organic paint. One baking step, a second application step of applying a photocatalyst paint on the organic layer, and a second baking step of baking the applied photocatalyst paint to form a photocatalyst layer, sequentially, In the second coating step, a paint containing a polyester resin dispersion and a fluorine ionomer having a degree of fluorination of 40% or more as a binder component is used as the organic paint.
ここで本発明の別の態様として、前記第二塗布工程及び前記第二焼付工程では、光触媒を前記フッ素アイオノマーで内包することもできる。
また本発明の別の態様として、前記光触媒塗布工程では、前記光触媒層中の樹脂不揮発成分換算として、前記ポリエステル樹脂ディスパージョンと前記フッ素アイオノマーとの重量比率が２０：８０〜７０：３０の範囲であり、且つ、前記フッ素アイオノマーと前記光触媒との重量比率が３０：７０〜６０：４０の範囲となるように調整された前記バインダ成分を用いることもできる。
Here, as another aspect of the present invention, in the second coating step and the second baking step, a photocatalyst can be included in the fluorine ionomer.
As another aspect of the present invention, in the photocatalyst coating step, the weight ratio of the polyester resin dispersion to the fluorine ionomer is in the range of 20:80 to 70:30 in terms of the resin non-volatile component in the photocatalyst layer. In addition, the binder component adjusted so that the weight ratio of the fluorine ionomer to the photocatalyst is in the range of 30:70 to 60:40 can also be used.
また、本発明の別の態様として、前記フッ素アイオノマーは、ポリテトラフルオロエチレンの側鎖にスルホン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にカルボン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にアミノ基を有するグラフト重合体、末端にリン酸エステルを有するパーフルオロアルキルオリゴマー、末端にスルホン酸基を有するパーフルオロアルキルオリゴマー、末端にカルボン酸基を有するパーフルオロアルキルオリゴマー、末端にアミノ酸基を有するパーフルオロアルキルオリゴマー、パーフルオロアルキルエチレン付加物の中から選択される、１種または２種以上の混合物とすることもできる。 As another aspect of the present invention, the fluorine ionomer includes a graft polymer having a sulfonic acid in the side chain of polytetrafluoroethylene, a graft polymer having a carboxylic acid in the side chain of polytetrafluoroethylene, and a polytetrafluoroethylene. A graft polymer having an amino group in the side chain of ethylene, a perfluoroalkyl oligomer having a phosphate ester at a terminal, a perfluoroalkyl oligomer having a sulfonic acid group at a terminal, a perfluoroalkyl oligomer having a carboxylic acid group at a terminal, a terminal It is also possible to use one or a mixture of two or more selected from perfluoroalkyl oligomers having an amino acid group and perfluoroalkylethylene adduct.
以下に、本発明の各実施の形態を説明するが、当然ながら本発明はこれらの形式に限定されるものでなく、本発明の技術的範囲を逸脱しない範囲で適宜変更して実施することができる。
＜実施の形態１＞
［光触媒塗膜付ＰＣＭ鋼板の構成］
図１（ａ）は本発明の実施の形態１に係る、光触媒塗膜付ＰＣＭ鋼板１（以下、「ＰＣＭ１」と称する。）の構成を示す、模式断面図である。
Each embodiment of the present invention will be described below, but the present invention is naturally not limited to these forms, and may be appropriately modified and implemented without departing from the technical scope of the present invention. it can.
<Embodiment 1>
[Configuration of PCM steel sheet with photocatalyst coating]
FIG. 1A is a schematic cross-sectional view showing a configuration of a PCM steel plate 1 with a photocatalyst coating film (hereinafter referred to as “PCM1”) according to Embodiment 1 of the present invention.
ＰＣＭ１は、鋼板１０の片面に対し、下塗層２０、中塗層３０、光触媒層（光触媒塗膜）４０を順次形成してなる。
鋼板１０は厚みが１ｍｍ以下（例えば０．２７ｍｍ）の鋼板であり、ＰＣＭ１の主たる構成要素である。好適な素材として、亜鉛−アルミニウム合金めっき鋼板を例示できる。この場合、市販品としては、亜鉛−５５％アルミニウム合金めっき鋼板である、「ガルバリウム鋼板」を利用できる。その他の好ましい例として、アルミニウムめっき鋼板、亜鉛めっき鋼板、ステンレス、アルミ合金等のいずれかを挙げることができる。鋼板１０の素材はこれらに限定されない。また、異種金属の積層板として鋼板１０を構成することもできる。
The PCM 1 is formed by sequentially forming an undercoat layer 20, an intermediate coat layer 30, and a photocatalyst layer (photocatalyst coating film) 40 on one surface of the steel plate 10.
The steel plate 10 is a steel plate having a thickness of 1 mm or less (for example, 0.27 mm), and is a main component of the PCM 1. As a suitable material, a zinc-aluminum alloy plated steel sheet can be exemplified. In this case, as a commercial product, a “galvalume steel plate” which is a zinc-55% aluminum alloy plated steel plate can be used. Other preferable examples include any of an aluminum-plated steel sheet, a galvanized steel sheet, stainless steel, and an aluminum alloy. The material of the steel plate 10 is not limited to these. Moreover, the steel plate 10 can also be comprised as a laminated board of a dissimilar metal.
なお、本発明で言及する「鋼板」とは、各種金属材料及び合金材料を含む、広く金属板一般を指すものとする。
下塗り塗膜層２０及び中塗り塗膜層３０は、ともに有機塗料を焼付塗装してなる有機塗膜層である。
下塗塗膜層２０は、着色塗膜層の一層目に相当し、熱硬化性樹脂を主成分とする厚み数μｍ程度（例えば約２μｍ）のプライマー層である。主にＰＣＭ１における中塗塗膜層３０の塗膜耐久性を向上させる目的で設けられる。また、中塗塗膜層３０の発色性確保や、防錆機能、或いは遮熱機能を付与する目的で設けられる場合もある。この場合、熱硬化性樹脂に発色剤や防錆材等の機能付与剤を添加する。また、消泡剤、レベリング材、顔料等を添加できる。
The “steel plate” mentioned in the present invention refers to a general metal plate including various metal materials and alloy materials.
The undercoat coating layer 20 and the intermediate coating layer 30 are both organic coating layers formed by baking an organic coating.
The undercoat coating layer 20 corresponds to the first layer of the colored coating layer, and is a primer layer having a thermosetting resin as a main component and a thickness of about several μm (for example, about 2 μm). It is provided mainly for the purpose of improving the coating film durability of the intermediate coating film layer 30 in PCM1. Moreover, it may be provided for the purpose of ensuring the color developability of the intermediate coating layer 30 and providing a rust preventive function or a heat shield function. In this case, a function-imparting agent such as a color former or a rust preventive is added to the thermosetting resin. Moreover, an antifoamer, a leveling material, a pigment, etc. can be added.
熱硬化性樹脂には公知材料を利用でき、ポリエステル系樹脂、エポキシ系樹脂、及びこれらを含む樹脂等を例示できる。また、硬化剤も公知材料を利用でき、アミノ系材料、ポリイソシアネート系材料を例示できる。
中塗塗膜層３０はＰＣＭ１の主たる着色塗膜層であり、所定の顔料成分と、前記下塗り塗膜層２０と良好に密着する樹脂材料を含んでなる。中塗塗膜層３０の厚みは、十分な発色が得られ、且つ、加工時に剥離等を生じない範囲で調節する。具体的には一例として数μｍ〜数十μｍに設定できる。成分としてはその他、光沢調整剤、艶消し剤、消泡剤等を含むこともできる。
Known materials can be used for the thermosetting resin, and examples thereof include polyester resins, epoxy resins, and resins containing these. Moreover, a well-known material can be utilized also as a hardening | curing agent, An amino material and a polyisocyanate type material can be illustrated.
The intermediate coating layer 30 is a main colored coating layer of the PCM 1 and includes a predetermined pigment component and a resin material that adheres well to the undercoat coating layer 20. The thickness of the intermediate coating layer 30 is adjusted within a range where sufficient color development is obtained and peeling does not occur during processing. Specifically, it can be set to several μm to several tens of μm as an example. In addition, the composition can also include a gloss adjusting agent, a matting agent, an antifoaming agent, and the like.
この中塗塗膜層３０の樹脂についても公知の原料を利用できる。例えば着色性、耐久性の向上を期待できる樹脂として、ポリエステル系樹脂、フッ素系樹脂、アクリル系樹脂、ウレタン系樹脂等を利用できる。これらの樹脂を選ぶ目安として、鋼板に対して連続的に塗布し、焼き付け塗装する、いわゆるコイルコーティングラインへ良好に適用できるものを選ぶ。ここで、ポリエステル系樹脂はＰＣＭ塗料としては、一般的かつ公知に使用されており、これらの要求を良好に満足するため特に望ましい。 A known raw material can also be used for the resin of the intermediate coating layer 30. For example, a polyester resin, a fluorine resin, an acrylic resin, a urethane resin, or the like can be used as a resin that can be expected to improve colorability and durability. As a guideline for selecting these resins, those that can be applied satisfactorily to a so-called coil coating line, which are continuously applied to a steel plate and baked and painted, are selected. Here, polyester-based resins are generally and commonly used as PCM paints, and are particularly desirable in order to satisfactorily satisfy these requirements.
光触媒塗膜層４０は、ＰＣＭ１の主たる特徴部分であって、光触媒粒子４０１とバインダ成分４０２を含み、膜厚が０．５μｍ以上５μｍ以下の塗膜である。前記バインダ成分４０２は、本発明の特徴として、ポリエステル樹脂ディスパージョン及びフッ化度４０％以上のフッ素アイオノマーを含有して構成される。これにより光触媒塗膜層４０は熱可塑性の塗膜として成膜されている。 The photocatalyst coating layer 40 is a main characteristic portion of the PCM 1 and includes a photocatalyst particle 401 and a binder component 402, and is a coating film having a thickness of 0.5 μm or more and 5 μm or less. The binder component 402 includes a polyester resin dispersion and a fluorine ionomer having a degree of fluorination of 40% or more as a feature of the present invention. Thereby, the photocatalyst coating film layer 40 is formed as a thermoplastic coating film.
前記バインダ成分４０２においては、樹脂不揮発成分換算において、前記ポリエステル樹脂ディスパージョンと前記フッ素アイオノマーとの重量比率が２０：８０〜７０：３０の範囲であり、且つ、前記フッ素アイオノマーと前記光触媒（光触媒粒子４０１）との重量比率が３０：７０〜６０：４０の範囲となるように設定されている。
フッ素アイオノマーとしては、ポリテトラフルオロエチレン（ＰＴＦＥ）の側鎖にスルホン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にカルボン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にアミノ基を有するグラフト重合体、末端にリン酸エステルを有するパーフルオロアルキルオリゴマー、末端にスルホン酸基を有するパーフルオロアルキルオリゴマー、末端にカルボン酸基を有するパーフルオロアルキルオリゴマー、末端にアミノ酸基を有するパーフルオロアルキルオリゴマー、パーフルオロアルキルエチレン付加物の中から選択される、１種または２種以上の混合物を挙げることができる。
In the binder component 402, the weight ratio of the polyester resin dispersion to the fluorine ionomer is in the range of 20:80 to 70:30 in terms of resin non-volatile component, and the fluorine ionomer and the photocatalyst (photocatalyst particles). 401) is set to be in a range of 30:70 to 60:40.
The fluorine ionomer includes a graft polymer having sulfonic acid in the side chain of polytetrafluoroethylene (PTFE), a graft polymer having carboxylic acid in the side chain of polytetrafluoroethylene, and an amino group in the side chain of polytetrafluoroethylene. A perfluoroalkyl oligomer having a phosphate ester at a terminal, a perfluoroalkyl oligomer having a sulfonic acid group at a terminal, a perfluoroalkyl oligomer having a carboxylic acid group at a terminal, and a perfluoro having an amino acid group at a terminal Examples thereof include one or a mixture of two or more selected from alkyl oligomers and perfluoroalkylethylene adducts.
光触媒反応は根源的には水の分解反応であるため、反応種である水が光触媒粒子４０１近傍に集中し易いように、光触媒塗膜層４０ではこのようなフッ素アイオノマーをバインダ成分４０２に用いている。
なお、フッ素アイオノマーが上記重量比率で含まれていれば、その他のフッ素樹脂、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体の内の１種乃至２種以上の混合物が光触媒塗膜層４０中に含まれていても良い。
Since the photocatalytic reaction is fundamentally a decomposition reaction of water, the photocatalyst coating layer 40 uses such a fluorine ionomer as the binder component 402 so that the reactive species water can easily concentrate in the vicinity of the photocatalyst particles 401. Yes.
If the fluorine ionomer is contained in the above weight ratio, other fluororesins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene copolymer, fluoride A mixture of one or more of the vinylidene-hexafluoropropylene copolymers may be contained in the photocatalyst coating layer 40.
本発明で利用可能なフッ素樹脂は多岐にわたるが、本願発明者らが厳密に検討した結果、上記重量比率に基づいて光触媒塗膜層４０中に所定のフッ素樹脂を適量添加することで、光触媒反応に対して十分な耐久性を発揮するだけでなく、光触媒機能を維持しつつ、バインダ成分４０２として共存するポリエステル樹脂ディスパージョンや、中塗塗膜層４０の劣化を効果的に抑制することが可能となっている。 Although there are a wide variety of fluororesins that can be used in the present invention, as a result of rigorous studies by the inventors of the present application, by adding an appropriate amount of a predetermined fluororesin to the photocatalyst coating layer 40 based on the weight ratio, the photocatalytic reaction In addition to exhibiting sufficient durability, it is possible to effectively suppress deterioration of the polyester resin dispersion coexisting as the binder component 402 and the intermediate coating layer 40 while maintaining the photocatalytic function. It has become.
フッ素樹脂は豊富なＣ−Ｆ結合を有しており、化学的に安定である。具体的には、Ｃ−Ｆ結合の結合エネルギーは、Ｃ−Ｈ結合（４１５ｋＪ／ｍｏｌ）やＣ−Ｃ結合（３４７ｋＪ／ｍｏｌ）のいずれの結合エネルギーに対しても十分大きい（約５００ｋＪ／ｍｏｌ）。従って、フッ素樹脂を用いることで化学的に安定性の高い分子鎖を形成できる。この化学安定性により、本発明では長期にわたり、光触媒粒子４０１による分解反応を受けずに安定に光触媒塗膜層４０を保持できる。また、フッ素樹脂は優れた耐薬品性、耐候性をも示し、電気化学反応に対しても高度に安定である。これに加え、低表面張力、低摩擦係数という性質をも示すが、これはＦ原子が小さな原子半径と低い分極性を持つことから、分子間凝集力が低く、優れた柔軟性を有するためと考えられる（プラスチック・機能性高分子材料事典：産業調査会事典出版センター発行（２００４年）の３０６頁参照）。 The fluororesin has abundant C—F bonds and is chemically stable. Specifically, the bond energy of the C—F bond is sufficiently large (about 500 kJ / mol) for any bond energy of the C—H bond (415 kJ / mol) and the C—C bond (347 kJ / mol). . Therefore, a chemically stable molecular chain can be formed by using a fluororesin. Due to this chemical stability, in the present invention, the photocatalyst coating layer 40 can be stably held without being subjected to the decomposition reaction by the photocatalyst particles 401 over a long period of time. In addition, the fluororesin also exhibits excellent chemical resistance and weather resistance, and is highly stable against electrochemical reactions. In addition to this, it also has the properties of low surface tension and low friction coefficient, because the F atom has a small atomic radius and low polarizability, so it has low intermolecular cohesion and excellent flexibility. Possible (Refer to page 306 of the Encyclopedia of Plastics and Functional Polymer Materials: Issued by the Industry Research Association Encyclopedia Publishing Center (2004)).
ポリエステル樹脂ディスパージョンは、高度な加工性を付与するために用いられ、例えばポリエチレンテレフタレート（ＰＥＴ）、ポリトリメチレンテレフタレート（ＰＴＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）の中から選んだ１種または２種以上の混合物等を例示できる。ポリエステル樹脂ディスパージョンの化学構造としては直鎖、分岐、環状のいずれでもよい。 The polyester resin dispersion is used for imparting a high degree of processability, and is selected from, for example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Examples thereof include one kind or a mixture of two or more kinds. The chemical structure of the polyester resin dispersion may be linear, branched or cyclic.
ここでバインダ成分４０２の前記フッ素アイオノマーは、スルホン酸基やカルボン酸基において親水性を呈する一方、それ以外の部位において疎水性を呈する両極性樹脂である。このため、前記親水性フッ素樹脂とともに配合する樹脂成分には、親水性フッ素樹脂との相溶性が求められる。この点を本願発明者らが鋭意検討した結果、ポリエステル樹脂ディスパージョンであればフッ素アイオノマーに対して良好な相溶性を発揮し、当該ポリエステル樹脂ディスパージョンを所定量用いれば、良好なバインダ成分を構成できることを見出した。これにより、光触媒塗料を構成でき、塗膜形成後において優れた光触媒塗膜層４０を実現している。 Here, the fluorine ionomer of the binder component 402 is an ambipolar resin that exhibits hydrophilicity in a sulfonic acid group or a carboxylic acid group, and exhibits hydrophobicity in other portions. For this reason, compatibility with a hydrophilic fluororesin is calculated | required by the resin component mix | blended with the said hydrophilic fluororesin. As a result of intensive studies by the present inventors on this point, if a polyester resin dispersion is used, good compatibility with a fluorine ionomer is exhibited, and if a predetermined amount of the polyester resin dispersion is used, a good binder component is formed. I found out that I can do it. Thereby, a photocatalyst coating material can be comprised and the photocatalyst coating film layer 40 excellent after coating film formation is implement | achieved.
次に、光触媒粒子４０１の種類は特に限定されない。例えばＴｉＯ２、ＺｎＯ、ＷＯ３、ＳｎＯ２、ＳｒＴｉＯ３、Ｂｉ２Ｏ３、Ｆｅ２Ｏ３から選択される１種または２種以上の金属酸化物を挙げることができる。このうち、酸化チタン（ＴｉＯ２）は光触媒機能が安定であり、容易に入手可能で市販品も多いため好適である。光触媒塗膜層４０に添加する際の光触媒の形態は限定されないが、粒径が揃った光触媒粒子４０１を用いると、光触媒塗膜層４０全体で均一な光触媒機能を期待できる。具体的には、平均粒径が約７ｎｍの一次粒子が、平均粒径２００〜３００ｎｍ程度に凝集してなる二次及び三次粒子として、光触媒粒子４０１を光触媒塗膜層４０中に分散させるようにするとよい。なお、光触媒塗膜層４０への光触媒粒子４０１の添加量は、発揮させたい光触媒効果等に合わせて適宜調整可能であるが、例えば光触媒塗膜層４０において１０ｗｔ％〜５０ｗｔ％の割合で添加することができる。 Next, the kind of photocatalyst particle 401 is not particularly limited. For example, one or more metal oxides selected from TiO 2 , ZnO, WO 3 , SnO 2 , SrTiO 3 , Bi 2 O 3 , and Fe 2 O 3 can be given. Of these, titanium oxide (TiO 2 ) is suitable because it has a stable photocatalytic function, is readily available, and has many commercial products. Although the form of the photocatalyst at the time of adding to the photocatalyst coating layer 40 is not limited, when the photocatalyst particle 401 having a uniform particle diameter is used, a uniform photocatalytic function can be expected in the entire photocatalyst coating layer 40. Specifically, the photocatalyst particles 401 are dispersed in the photocatalyst coating layer 40 as secondary and tertiary particles in which primary particles having an average particle diameter of about 7 nm are aggregated to an average particle diameter of about 200 to 300 nm. Good. The amount of the photocatalyst particles 401 added to the photocatalyst coating layer 40 can be appropriately adjusted according to the photocatalytic effect desired to be exhibited. For example, the photocatalyst coating layer 40 is added at a rate of 10 wt% to 50 wt%. be able to.
ここで光触媒塗膜層４０の特徴として、光触媒粒子４０１は、バインダ成分４０２におけるフッ素アイオノマーに内包されている。これは前記した水を反応種とする光触媒反応を起こしやすくするとともに、フッ素アイオノマーの強固なＣ−Ｆ結合を利用して、前記光触媒反応により不要な自己分解反応を適切に防止するためである。
なお、このような光触媒効果を良好に得るためには、ＰＣＭ１において、光触媒塗膜層４０を最上層として設けることが好適である。
Here, as a feature of the photocatalyst coating layer 40, the photocatalyst particles 401 are included in the fluorine ionomer in the binder component 402. This is to facilitate the photocatalytic reaction using water as a reactive species and to appropriately prevent unnecessary self-decomposing reaction by the photocatalytic reaction by utilizing the strong CF bond of the fluorine ionomer.
In order to obtain such a photocatalytic effect satisfactorily, it is preferable to provide the photocatalyst coating layer 40 as the uppermost layer in PCM1.
なお、特に図示しないが、ＰＣＭ１の裏面には下塗り層２０、中塗り層３０の各塗料の少なくともいずれかを用い、サービス塗膜を形成してもよい。
（ＰＣＭ１の効果について）
以上構成を持つＰＣＭ１では、使用時に光触媒塗膜層４０の表面に水が付着すると、フッ素アイオノマーの効果により光触媒塗膜層４０の表面全体に平坦な水膜が形成される。この時の様子を、図１（ｂ）に示す。当図は、図１（ａ）の光触媒塗膜層４０表面付近における領域Ａの拡大断面図である。
Although not specifically shown, a service coating film may be formed on the back surface of the PCM 1 using at least one of the paints of the undercoat layer 20 and the intermediate coat layer 30.
(About the effect of PCM1)
In the PCM 1 having the above configuration, when water adheres to the surface of the photocatalytic coating layer 40 during use, a flat water film is formed on the entire surface of the photocatalytic coating layer 40 due to the effect of the fluorine ionomer. A state at this time is shown in FIG. This figure is an enlarged cross-sectional view of the region A in the vicinity of the surface of the photocatalyst coating layer 40 of FIG.
このような状態で光触媒塗膜層４０に親油性の汚染物質が付着する。ここで図１（ｂ）のように、光触媒塗膜層４０の表面に水分が付着すると、フッ素アイオノマーの効果により、速やかに水膜が形成される。これにより汚染物質は水膜に浮き上がり、水と共に流れて除かれる。これと同様の原理で、汚染物質が付着した後に光触媒塗膜層４０の表面に雨水滴が付着すれば、水膜が形成されて汚染物質を除去することができる。 In such a state, lipophilic contaminants adhere to the photocatalyst coating layer 40. Here, as shown in FIG. 1B, when moisture adheres to the surface of the photocatalyst coating layer 40, a water film is rapidly formed by the effect of the fluorine ionomer. As a result, pollutants float on the water film and flow away with the water. Based on the same principle, if rainwater droplets adhere to the surface of the photocatalyst coating layer 40 after the contaminants adhere, a water film is formed and the contaminants can be removed.
一方、光触媒塗膜層４０中に分散配置された光触媒粒子４０１は、外部からの光照射により励起される。この励起により、大気に近接する光触媒塗膜層４０の表面付近では、大気中の酸素が光触媒からエネルギーを受けて活性酸素に変化する。活性酸素は、光触媒塗膜層４０の表面またはその近傍において、親油性の汚染物質を分解し、付着力を弱め、容易に除去されるように作用する。これにより、雨等が光触媒塗膜層４０に当たっても、汚染物質は容易に洗い流される。 On the other hand, the photocatalyst particles 401 dispersed and arranged in the photocatalyst coating layer 40 are excited by light irradiation from the outside. By this excitation, oxygen in the atmosphere receives energy from the photocatalyst and changes into active oxygen near the surface of the photocatalytic coating layer 40 close to the atmosphere. Active oxygen acts on the surface of the photocatalyst coating layer 40 or in the vicinity thereof to decompose lipophilic contaminants, weaken adhesion, and be easily removed. Thereby, even if rain hits the photocatalyst coating layer 40, the contaminant is easily washed away.
また、光触媒塗膜層４０はバインダ成分４０２にポリエステル樹脂ディスパージョンを含んでいるため、高度な加工性を呈する。これにより、ＰＣＭ１を曲げ及びプレス加工等で変形させる場合でも、鋼板１０の変形に追従して光触媒塗膜層４０も柔軟に曲がり、容易に割れや剥がれを生じることがない。このような追従性・加工性は特許文献１、２のような無機材料のみを用いてなる光触媒塗膜層には見られない優位性であり、ＰＣＭ１の加工性や外観の制約をほとんど受けることなく、優れた生産性を発揮できる。 Moreover, since the photocatalyst coating layer 40 contains the polyester resin dispersion in the binder component 402, it exhibits high processability. As a result, even when the PCM 1 is deformed by bending or pressing, the photocatalyst coating layer 40 flexes flexibly following the deformation of the steel plate 10 and does not easily crack or peel off. Such followability and workability are advantages that cannot be seen in the photocatalyst coating layer using only inorganic materials as in Patent Documents 1 and 2, and are almost subject to restrictions on the workability and appearance of PCM1. And can exhibit excellent productivity.
なお特許文献１、２では、光触媒反応により光触媒塗膜に有機バインダ成分を添加できない旨が記載されているが、本発明はきわめて化学的安定性に優れる４０％以上のフッ化度を持つフッ素アイオノマーをバインダ成分４０２に利用している。これにより、激烈な光触媒反応にも耐えうる光触媒塗膜層４０を実現したものであり、この点において従来技術よりも画期的な優位性を有している。 Patent Documents 1 and 2 describe that an organic binder component cannot be added to a photocatalyst coating film by a photocatalytic reaction, but the present invention is a fluorine ionomer having a degree of fluorination of 40% or more that is extremely excellent in chemical stability. Is used for the binder component 402. Thereby, the photocatalyst coating layer 40 that can withstand a severe photocatalytic reaction is realized, and in this respect, it has an epoch-making advantage over the prior art.
さらに光触媒層４０には、前記フッ素アイオノマーの存在により摩擦係数が非常に小さく、良好な耐摩耗性が付与されており、外部接触時の表面摩擦を極めて小さく抑制できる。その結果、多少の外部接触があっても光触媒塗膜層４０の割れや剥がれを回避でき、長期にわたる光触媒機能を期待できる。これはＰＣＭ１を家電製品の外板等に利用する場合に特に有効である。 Furthermore, the photocatalyst layer 40 has a very small coefficient of friction due to the presence of the fluorine ionomer and is imparted with good wear resistance, so that surface friction at the time of external contact can be suppressed to a very low level. As a result, even if there is some external contact, the photocatalyst coating layer 40 can be prevented from cracking and peeling, and a photocatalytic function over a long period can be expected. This is particularly effective when the PCM 1 is used as an outer plate of a home appliance.
以下、本発明のその他の実施の形態について、実施の形態１との差異を中心に説明する。
＜実施の形態２＞
図１（ｃ）は実施の形態２に係る、ＰＣＭ１Ａの構成を示す模式的な断面図である。
ＰＣＭ１Ａでは、鋼板１０Ａを鋼板本体１１及び化成処理層１２の積層体で構成している。着色層２０、３０、光触媒塗膜層４０は、化成処理層１２の表面上に同順に形成される。
Hereinafter, other embodiments of the present invention will be described focusing on differences from the first embodiment.
<Embodiment 2>
FIG. 1C is a schematic cross-sectional view showing the configuration of PCM 1A according to the second embodiment.
In PCM1A, the steel plate 10A is formed of a laminate of a steel plate body 11 and a chemical conversion treatment layer 12. The colored layers 20 and 30 and the photocatalyst coating layer 40 are formed on the surface of the chemical conversion treatment layer 12 in the same order.
化成処理層１２は、ここでは鋼板本体１１の表面をクロメート処理して形成された被膜であり、クロム微粒子が有機バインダで分散されてなる。当該化成処理層１２は鋼板１０Ａに防錆効果を付与し、下塗塗膜層２０の密着性向上を目的として形成している。前記有機バインダは、下塗塗膜層２０の焼き付け塗装時の高温に耐えられる耐熱性を有する材料、例えばエポキシ系樹脂、ポリエステル系樹脂、ウレタン系樹脂等を用いる。 Here, the chemical conversion treatment layer 12 is a film formed by subjecting the surface of the steel plate body 11 to chromate treatment, and chromium fine particles are dispersed with an organic binder. The chemical conversion treatment layer 12 is formed for the purpose of imparting a rust prevention effect to the steel sheet 10 </ b> A and improving the adhesion of the undercoat coating layer 20. As the organic binder, a heat-resistant material that can withstand a high temperature during the baking coating of the undercoat coating layer 20, for example, an epoxy resin, a polyester resin, a urethane resin, or the like is used.
このような構成を持つＰＣＭ１Ａにおいても、実施の形態１のＰＣＭ１とほぼ同様の諸効果を期待できる。
なお、クロメート処理の代わりにクロムを含有しない防錆剤（クロメートフリー系防錆剤）を用いて被膜形成することもできる。例えばモリブデン酸化合物、バナジン酸化物等を利用できる。
Even in the PCM 1A having such a configuration, various effects similar to those of the PCM 1 of the first embodiment can be expected.
In addition, it can also form a film using the rust preventive agent (chromate free type | system | group antirust agent) which does not contain chromium instead of a chromate process. For example, a molybdate compound, vanadium oxide, or the like can be used.
なお、化成処理層１２はクロメート処理で形成された被膜に限定されない。例えば、リン酸亜鉛処理、粗面処理等、公知の各種表面処理で形成された被膜であっても良い。
＜実施の形態３＞
次に示す図１（ｄ）は実施の形態３に係る、ＰＣＭ１Ｂの構成に係る模式的な断面図である。
In addition, the chemical conversion treatment layer 12 is not limited to the film formed by the chromate treatment. For example, it may be a coating formed by various known surface treatments such as zinc phosphate treatment and rough surface treatment.
<Embodiment 3>
FIG. 1D shown next is a schematic cross-sectional view relating to the configuration of the PCM 1B according to the third embodiment.
ＰＣＭ１ＢはＰＣＭ１を基本構造とし、下塗塗膜層２０を省略した構成である。基材１０に対して中塗塗膜層３０が直接良好に塗膜形成できる場合等には、このような構成としてもよい。ＰＣＭ１Ｂにおいても、ＰＣＭ１とほぼ同様の効果を期待することができる。
＜実施の形態４＞
次に示す図２（ａ）は、実施の形態４に係る、加工済ＰＣＭ１Ｃの外観図である。図２（ｂ）は、ＰＣＭ１Ｃの加工部（プレス部）を厚み方向から見た部分拡大図である。
PCM1B has a configuration in which PCM1 is a basic structure and the undercoat coating layer 20 is omitted. Such a configuration may be used when the intermediate coating layer 30 can directly and satisfactorily form a coating film on the substrate 10. In PCM1B, the same effect as PCM1 can be expected.
<Embodiment 4>
FIG. 2A shown below is an external view of a processed PCM 1C according to the fourth embodiment. FIG. 2B is a partially enlarged view of the processed part (press part) of the PCM 1C as seen from the thickness direction.
ＰＣＭ１Ｃは、ＰＣＭ１を基本構造とし、複数個所において厚み（Ｚ）方向に凹凸処理を行い、ストライプ状の加工部（プレス部）５０を有する波型鋼板としたものである。この凹凸加工を行うため、光触媒塗膜層４０の表面から厚み方向に所定の金型でプレス加工を施しているが、前述のように光触媒塗膜層４０がポリエステル樹脂ディスパージョンを含んで構成されているため、前記凹凸処理においても何ら損傷することなく柔軟に変形し、良好な密着状態を保っている。これにより、加工後も光触媒塗膜層４０の割れや剥がれの恐れがなく安定した形態を保ち、長期にわたり光触媒機能の発揮を期待できる。 PCM1C is a corrugated steel sheet having PCM1 as a basic structure, subjected to unevenness processing in a thickness (Z) direction at a plurality of locations, and having striped processed portions (pressed portions) 50. In order to perform this unevenness processing, press processing is performed with a predetermined mold in the thickness direction from the surface of the photocatalyst coating layer 40. As described above, the photocatalyst coating layer 40 includes a polyester resin dispersion. Therefore, it is deformed flexibly without any damage even in the uneven processing, and maintains a good adhesion state. Thereby, even after processing, the photocatalyst coating layer 40 can be expected to exhibit a photocatalytic function over a long period of time without fear of cracking or peeling off.
なお、加工部５０は角型断面形状としているが、当然ながらこれ以外の形状でもよく、例えば丸波型、リブ波型としてもよい。
＜光触媒塗膜付ＰＣＭの製造方法＞
図３は、本発明の光触媒塗膜付ＰＣＭの製造方法の流れを示すフロー図である。ここでは実施の形態１のＰＣＭ１の製造方法を例示するが、基本的にその他の実施の形態のＰＣＭの製造方法とも共通する。
In addition, although the process part 50 is made into the square cross-sectional shape, naturally other shapes may be sufficient, for example, it is good also as a round wave type and a rib wave type.
<Method for producing PCM with photocatalyst coating>
FIG. 3 is a flowchart showing the flow of the method for producing the PCM with a photocatalyst coating film of the present invention. Here, the manufacturing method of PCM 1 of the first embodiment is illustrated, but basically, it is also common to the manufacturing methods of PCM of the other embodiments.
当図に示す例では、鋼板の表面を前処理する前処理工程（Ｓ１）、オプションとして鋼板表面に化成処理層を形成する後処理工程（Ｓ２）、中塗塗膜層形成のためのプライマー層である下塗塗膜層形成工程（Ｓ３）を順次経る。
その後、中塗塗膜層を形成し（Ｓ４）、その表面に光触媒塗膜層を形成する（Ｓ５）。ここで本発明の特徴として、中塗塗膜層の上に直接光触媒塗膜層を形成でき、従来のようにバリアコートを形成する工程は不要である。その後、出荷前に各工程を経る（Ｓ６）。
In the example shown in the figure, a pretreatment step (S1) for pretreating the surface of the steel plate, a post treatment step (S2) for forming a chemical conversion treatment layer on the steel plate surface as an option, and a primer layer for forming an intermediate coating layer A certain undercoat coating film layer forming step (S3) is sequentially performed.
Thereafter, an intermediate coating layer is formed (S4), and a photocatalytic coating layer is formed on the surface (S5). Here, as a feature of the present invention, a photocatalyst coating layer can be formed directly on the intermediate coating layer, and a step of forming a barrier coat as in the prior art is unnecessary. Thereafter, each process is performed before shipping (S6).
ここでＳ１〜Ｓ５の工程は、例えばコイルコーティングラインにおいて連続的に実施できる。コイルコーティングラインでは、下塗塗膜層、中塗塗膜層、光触媒塗膜層をそれぞれ形成する場合、３コート３ベーク方式を採用する。下塗塗膜層が不要の場合は、２コート２ベーク方式を実施することもできる。
以下、各工程を順に説明する。
Here, the process of S1-S5 can be continuously implemented, for example in a coil coating line. In the coil coating line, a three-coat three-bake method is employed when forming an undercoat coating layer, an intermediate coating layer, and a photocatalytic coating layer, respectively. When an undercoat coating layer is not required, a 2-coat 2-bake method can be carried out.
Hereinafter, each process is demonstrated in order.
前処理工程及び後処理工程について、図４のフロー図を用いて説明する。
（前処理工程Ｓ１）
まず、鋼板の表面に付着している埃、汚れ、油分等を除去する（脱脂（アルカリ脱脂）工程Ｓ１１）。
次に、脱脂液の付着した鋼板を水で洗浄する（水洗工程Ｓ１２）。この後、鋼板の表面を酸処理して粗面化し、塗料との密着性を向上させる（表面処理Ｓ１３）。次に鋼板を温め、後処理をし易い状態にする（湯洗処理Ｓ１４）。以上で前処理工程を終了する。
A pre-processing process and a post-processing process are demonstrated using the flowchart of FIG.
(Pretreatment step S1)
First, dust, dirt, oil, etc. adhering to the surface of the steel sheet are removed (degreasing (alkali degreasing) step S11).
Next, the steel sheet to which the degreasing liquid is adhered is washed with water (water washing step S12). Thereafter, the surface of the steel sheet is acid-treated and roughened to improve the adhesion with the paint (surface treatment S13). Next, the steel plate is warmed to make it easy to perform post-treatment (hot water treatment S14). The pretreatment process is thus completed.
（後処理工程Ｓ２）
表面処理Ｓ１３、湯洗処理Ｓ１４を経る代わりに、Ｓ１２を実施後、鋼板の表面に防錆処理や塗料との密着性向上を図るための処理を行い、化成処理層を形成することもできる。一例として塗布型クロメート処理Ｓ１５を実施し、塗膜に乾燥処理Ｓ１６を実施し、冷却処理（空冷／ミスト噴霧）Ｓ１７を経ることで、化成処理層を形成する。
(Post-processing step S2)
Instead of undergoing the surface treatment S13 and the hot water washing treatment S14, after carrying out S12, the surface of the steel sheet can be subjected to a treatment for improving the anti-corrosion treatment and the adhesion to the paint, thereby forming a chemical conversion treatment layer. As an example, a coating-type chromate treatment S15 is performed, a drying treatment S16 is performed on the coating film, and a chemical conversion treatment layer is formed through a cooling treatment (air cooling / mist spraying) S17.
Ｓ１４またはＳ１７の処理を終了したら、図３に戻り、下塗層形成工程Ｓ３に移行する。
（下塗塗膜層形成工程Ｓ３）
まず、下塗塗料を調整する。粘度をフォードカップＮｏ．４で、７０〜１２０秒に調整する。
When the process of S14 or S17 is completed, the process returns to FIG. 3 and proceeds to the undercoat layer forming step S3.
(Undercoat layer formation step S3)
First, the primer coating is adjusted. Viscosity was measured using Ford Cup 4. Adjust to 70-120 seconds.
続いて表面塗膜の一層目として、下塗塗料を塗装する。組その後、塗膜を焼き付け乾燥させる。乾燥後はエアー及びミスト噴霧により冷却処理する。これにより下塗塗膜層を形成する。
（中塗塗膜層形成工程Ｓ４）
中塗塗料を調整する。粘度をフォードカップＮ０．４で、７０〜１２０秒に調整する。表面塗膜の二層目として、中塗塗料を塗装する。その後、塗膜を焼き付け乾燥させる。乾燥後はエアー及びミスト噴霧により冷却処理する。これにより中塗塗膜層を形成する。
（光触媒塗膜層形成工程Ｓ５）
光触媒、バインダ成分（フッ素アイオノマー及びポリエステル樹脂ディスパージョン）、溶媒を用いて光触媒塗料を調整する。ここで本発明では、樹脂不揮発成分換算において、ポリエステル樹脂ディスパージョンと前記フッ素アイオノマーとの重量比率を２０：８０〜７０：３０の範囲とする。また前記フッ素アイオノマーと前記光触媒との重量比率を３０：７０〜６０：４０の範囲とする。
Subsequently, a primer coating is applied as the first layer of the surface coating. After that, the coating film is baked and dried. After drying, it is cooled by air and mist spraying. Thereby, an undercoat coating film layer is formed.
(Intermediate coating film layer forming step S4)
Adjust the intermediate coating. The viscosity is adjusted to 70-120 seconds with a Ford Cup N0.4. An intermediate coating is applied as the second layer of the surface coating. Thereafter, the coating film is baked and dried. After drying, it is cooled by air and mist spraying. This forms an intermediate coating layer.
(Photocatalyst coating layer forming step S5)
A photocatalyst paint is prepared using a photocatalyst, a binder component (fluorine ionomer and polyester resin dispersion), and a solvent. Here, in the present invention, the weight ratio of the polyester resin dispersion to the fluorine ionomer is set in the range of 20:80 to 70:30 in terms of resin non-volatile components. The weight ratio of the fluorine ionomer to the photocatalyst is in the range of 30:70 to 60:40.
光触媒としては、平均粒径（１．０μｍ以下）に分散したＴｉＯ２粒子を最終塗膜換算で１０ｗｔ％程度になるように添加する。また溶媒の量の調整により、塗料粘度を２０〜５０ｍＰａ・ｓ程度に調整する。
ここで、ＴｉＯ２粒子を親水性フッ素樹脂に内包させるため、予めＴｉＯ２粒子とフッ素アイオノマーを混合しておくとよい。
As a photocatalyst, TiO 2 particles dispersed in an average particle size (1.0 μm or less) are added so as to be about 10 wt% in terms of the final coating film. Further, the viscosity of the paint is adjusted to about 20 to 50 mPa · s by adjusting the amount of the solvent.
Here, in order to encapsulate the TiO 2 particles in the hydrophilic fluororesin, the TiO 2 particles and the fluorine ionomer may be mixed in advance.
光触媒塗料を中塗り層の表面に所定の方法で塗布し、続いてこれを焼き付ける。焼き付け条件は適宜調整が可能であるが、例えば乾燥炉雰囲気中において、１４０℃以上３００℃以下の温度範囲で焼付時間３０〜９０秒、好ましくは３０秒程度の焼付時間とすることができる。この設定条件とすることで、コイルコーティングラインの乾燥炉にて十分な焼き付けが可能となる。 A photocatalyst paint is applied to the surface of the intermediate coating layer by a predetermined method, followed by baking. The baking conditions can be appropriately adjusted. For example, in a drying furnace atmosphere, a baking time of 30 to 90 seconds, preferably about 30 seconds can be set in a temperature range of 140 ° C. to 300 ° C. By setting it as this setting condition, sufficient baking can be performed in the drying furnace of the coil coating line.
以下、表１に市販製品の鋼板材料を用いた場合のコイルコーティングラインにおける操業条件を例示する。表中、「種類」は（塗料名）、「トップオーブン」は（中塗乾燥炉）、プライムオーブンは（下塗乾燥炉）、「ＰＭＴ」は（最高到達板表面温度）を示す。また「Ｎｏ．２」、「Ｎｏ．３」、「Ｎｏ．４」はそれぞれ（乾燥炉中の雰囲気温度）を示す。 Hereinafter, Table 1 exemplifies operating conditions in the coil coating line when a commercially available steel plate material is used. In the table, "type" indicates (paint name), "top oven" indicates (intercoat drying oven), prime oven indicates (prime drying oven), and "PMT" indicates (maximum reached plate surface temperature). “No. 2”, “No. 3”, and “No. 4” indicate (atmosphere temperature in the drying furnace), respectively.
（各塗料の塗装方法について）
本発明における下塗塗料、中塗塗料、光触媒塗料の塗装方法に関しては、コイルコーティングラインの場合、基本的には塗装ロール（アプリケーターロール）、鉄ロール（ピックアップロール）、ミータリングロール（塗布量制御を測るドクターロール）等を用いた、公知のロール塗装法を採用できる。
(About the painting method of each paint)
Regarding the coating method of the undercoat paint, the intermediate coat paint, and the photocatalyst paint in the present invention, in the case of the coil coating line, basically, a paint roll (applicator roll), an iron roll (pickup roll), and a metering roll (apply amount control) are measured. A known roll coating method using a doctor roll or the like can be employed.
この場合、各ロールの回転方向には特に限定されず、フルリバース塗装、リバース塗装（ピックアップフィード及びトップフィードのいずれも可能）、ナチュラル塗装、のいずれの方法であってもよい。
このうち、フルリバース塗装は、塗装方向性（ロール目）が無くなり塗装面が平滑に仕上り、厚膜形成に適している。ここで図４は、フルリバース塗装装置ＦＲの構成を模式的に示す図である。図中、Ｄｂはドクターブレード、Ｍｅはミータリングロール、Ｐｉはピックアップロール、ＡＰはアプリケーターロール、Ｃｖは搬送ロール、矢印は各ロールの回転方向、Ｂは塗料トレイをそれぞれ示す。当図ではコイルコーティングラインを想定し、塗装対象として帯状鋼板を図示しているが、搬送ベルトを用いて切り出した鋼板を連続的に搬送することも可能である。
In this case, the direction of rotation of each roll is not particularly limited, and may be any of full reverse painting, reverse painting (both pickup feed and top feed are possible), and natural painting.
Among these, full reverse coating is suitable for forming a thick film because there is no coating direction (roll eyes) and the painted surface is finished smoothly. Here, FIG. 4 is a diagram schematically showing the configuration of the full reverse coating apparatus FR. In the figure, Db is a doctor blade, Me is a metering roll, Pi is a pick-up roll, AP is an applicator roll, Cv is a transport roll, an arrow is a rotation direction of each roll, and B is a paint tray. In this figure, a strip-shaped steel plate is illustrated as an object to be coated on the assumption that a coil coating line is used, but it is also possible to continuously transport a steel plate cut out using a transport belt.
このような構成のフルリバース塗装装置ＦＲでは、予め塗料トレイＢ中に塗料を入れておき、鋼板を搬送ロールＣｖとアプリケーターロールＡＰの間に挿通させる。塗料トレイＢ中の塗料はピックアップローラＰｉにより掬い上げられ、ミータリングローラーＭｅ及びドクターブレードＤｂにより量を調節された後、アプリケーターロールＡＰの表面に載せられる。そして当該アプリケーターロールＡＰの回転により、適量の塗料が鋼板の片面に連続的に塗布されることとなる。 In the full reverse coating apparatus FR having such a configuration, the paint is put in the paint tray B in advance, and the steel plate is inserted between the transport roll Cv and the applicator roll AP. The paint in the paint tray B is scooped up by the pick-up roller Pi, adjusted in amount by the metering roller Me and the doctor blade Db, and then placed on the surface of the applicator roll AP. And by the rotation of the applicator roll AP, an appropriate amount of coating material is continuously applied to one side of the steel plate.
フルリバース塗装は、塗装面を比較的平滑に仕上げることができる。ナチュラル塗装は塗装の方向性は残るものの、薄膜形成、プライマー、サービスコート（裏面塗装）等の塗装に適している。
なお、コイルコーティングライン以外でＰＣＭを製造する場合、例えば切断した鋼板を用いてＰＣＭを製造する場合等には、下塗塗料、中塗塗料、光触媒塗料の塗装方法をロール塗装法に限定しない。例えばスプレー塗装、粉体塗装、電着塗装、カーテンコート等、いずれの塗装法も採用できる。
Full reverse painting can finish the painted surface relatively smoothly. Natural painting is suitable for painting thin films, primers, and service coats (reverse coating), although the direction of painting remains.
In addition, when manufacturing PCM other than a coil coating line, for example, when manufacturing PCM using the cut steel plate, the coating method of undercoat paint, intermediate coating paint, and photocatalyst paint is not limited to roll coating method. For example, any coating method such as spray coating, powder coating, electrodeposition coating, curtain coating, etc. can be adopted.
以上でＰＣＭ１が完成する。
（外観検査・梱包・出荷検査Ｓ６）
完成したＰＣＭ１を必要に合わせて所定サイズに切断する。製品の塗膜面の品質確認を行い、梱包紙で包む。出荷検査として、顧客要求の諸性能と所定の品質をクリアできているかを確認する。
＜性能評価試験＞
以下の表２に示す各サンプル光触媒塗料(内装用)、光触媒塗料(外装用)、現行品を作製した。表中、光触媒塗料(内装用)は（可視光応答型光触媒）、光触媒塗料(外装用)は（紫外光応答型光触媒）の成分からなる。
Thus, PCM1 is completed.
(Appearance inspection / packaging / shipping inspection S6)
The completed PCM 1 is cut into a predetermined size as necessary. Check the quality of the coated surface of the product and wrap it with packing paper. As a shipment inspection, it is checked whether various performances and predetermined quality requested by customers have been cleared.
<Performance evaluation test>
Each sample photocatalyst paint (for interior use), photocatalyst paint (for exterior use), and current products shown in Table 2 below were prepared. In the table, the photocatalyst paint (for interior use) is composed of (visible light responsive photocatalyst), and the photocatalyst paint (for exterior use) is composed of (ultraviolet light responsive photocatalyst).
上記作製した各サンプル光触媒塗料(内装用)、光触媒塗料(外装用)、現行品について、表３に示す各実験を実施した。
Each experiment shown in Table 3 was carried out for each sample photocatalyst paint (for interior use), photocatalyst paint (for exterior use), and current products prepared above.
表３に示すように、いずれのサンプル光触媒塗料(内装用)、光触媒塗料(外装用)も、光触媒層を形成していない現行品とほぼ同様の耐久性を有し、安定した塗膜を構成していることが分かった。
As shown in Table 3, all sample photocatalyst paints (for interior use) and photocatalyst paints (for exterior use) have almost the same durability as current products that do not have a photocatalyst layer, and constitute a stable coating film. I found out that
鉛筆硬度試験、コインスクラッチ試験、デュポン衝撃試験、折曲げ試験、溶剤耐性、碁盤目エリクセン試験については、いずれのサンプルの光触媒塗料(内装用)、光触媒塗料(外装用)も、現行品と同レベルの評価となった。このように上記試験の範囲では、いずれのサンプルも塗膜に引っかき傷や割れ、剥れがほとんど生じないことが分かった。
なお表３には表示しないが、サンプル光触媒塗料(内装用)、光触媒塗料(外装用)と現行品について塩水噴霧試験、複合サイクル試験、ＳＵＶ試験を実施したところ、これらの各実験結果もサンプル光触媒塗料(内装用)、光触媒(外装用)は現行品と同レベルの評価となった。
For the pencil hardness test, coin scratch test, DuPont impact test, bending test, solvent resistance, cross-cut Eriksen test, all samples of photocatalyst paint (for interior) and photocatalyst paint (for exterior) are at the same level as the current product It became evaluation of. Thus, in the range of the said test, it turned out that any sample hardly scars, cracks, and peels off to a coating film.
Although not shown in Table 3, a salt spray test, a combined cycle test, and an SUV test were conducted on the sample photocatalyst paint (for interior use), photocatalyst paint (for exterior use) and the current product. The paint (for interior) and photocatalyst (for exterior) were evaluated at the same level as the current product.
次に、本発明の光触媒塗膜層を形成したＰＣＭと、比較例のＰＣＭ（光触媒塗膜層なしの現行品）を屋外（東邦シートフレーム株式会社八千代工場 本事務所東側の壁面に約１８９日間暴露した（平成２２年７月１５日〜平成２３年１月２０日）。その後の各鋼板の様子を図６に示す。
当図６（ｂ）に示すように、試験後の比較例では汚染物質を含む雨筋が確認できる。これに対し、図６（ａ）に示すように、試験後の実施例では雨筋は確認されず、清浄な表面を保っている。また、光触媒塗膜層の表面に亀裂や損傷も存在していない。この結果から、実施例では長期の屋外使用にも関わらず、良好な光触媒機能が安定して発揮されていることが分かる。
Next, the PCM with the photocatalyst coating layer of the present invention and the PCM of the comparative example (current product without the photocatalyst coating layer) are outdoors (Toho Seat Frame Co., Ltd. Yachiyo Factory on the east wall of the office for about 189 days. It was exposed (July 15, 2010 to January 20, 2011).
As shown in FIG. 6B, rain lines containing pollutants can be confirmed in the comparative example after the test. On the other hand, as shown in FIG. 6A, rain streaks are not confirmed in the example after the test, and a clean surface is maintained. Further, there is no crack or damage on the surface of the photocatalyst coating layer. From this result, it can be seen that in the examples, a good photocatalytic function is stably exhibited despite long-term outdoor use.
以上の各試験結果より、本発明の優位性が確認された。
＜その他の事項＞
上記実施の形態では、着色塗膜層を有機塗膜層として形成したが、加工性がそれほど問題にならない場合等には、無機塗膜層、または有機塗膜層と無機塗膜層の積層、あるいは有機成分と無機成分の両方を含む層として、着色塗膜層を形成してもよい。
From the above test results, the superiority of the present invention was confirmed.
<Other matters>
In the above embodiment, the colored coating layer is formed as an organic coating layer, but when the processability is not so much a problem, an inorganic coating layer, or a laminate of an organic coating layer and an inorganic coating layer, Or you may form a colored coating-film layer as a layer containing both an organic component and an inorganic component.
また、光触媒塗膜層４０のバインダ成分４０２はフッ素アイオノマーやポリエステル樹脂ディスパージョン等の有機材料を利用したが、ＰＣＭの加工性がそれほど問題にならない場合には、無機材料をバインダ成分４０２に用いても良い。
光触媒塗料には、さらに別途、酸化亜鉛、酸化チタン、酸化セリウム等の無機系紫外線吸収剤、ベンゾトリアゾール系、サリチル酸系、ベンゾフェノン系等の有機紫外線吸収剤、ヒンダードアミン系等の光安定化剤から選択される化合物を添加してもよい。これにより、光触媒塗膜層４０に紫外線防止機能が付与される。但し、添加物質や添加量によっては、光触媒層４０の透明性が低下する場合があるので留意する。
The binder component 402 of the photocatalyst coating layer 40 uses an organic material such as a fluorine ionomer or a polyester resin dispersion. However, if the processability of PCM is not a problem, an inorganic material is used as the binder component 402. Also good.
For photocatalyst coating materials, select from inorganic UV absorbers such as zinc oxide, titanium oxide, and cerium oxide, organic UV absorbers such as benzotriazole, salicylic acid, and benzophenone, and light stabilizers such as hindered amines. A compound to be prepared may be added. Thereby, the ultraviolet protection function is imparted to the photocatalyst coating layer 40. However, it should be noted that the transparency of the photocatalyst layer 40 may be reduced depending on the additive substance and the addition amount.
下塗塗膜層及び中塗塗膜層の少なくとも一方には、公知の骨材を添加し、表面粗度を向上させてアンカー効果を発揮させ、上方に設ける層との密着性を向上させてもよい。その他、各層には公知の各種機能性添加剤（紫外線吸収剤、防錆剤等）を添加してもよい。 A known aggregate may be added to at least one of the undercoating coating layer and the intermediate coating coating layer to improve the surface roughness, exhibit an anchor effect, and improve the adhesion with the layer provided above. . In addition, you may add various well-known functional additives (an ultraviolet absorber, a rust preventive agent, etc.) to each layer.
本発明の光触媒塗膜付ＰＣＭは、たとえばサイディング、住宅用ドア、パーティション、ロッカー等の建築材料や配電盤、スチール机、ベンチの他、クーラー、冷蔵庫等の電化製品の外装材などに利用でき、その産業上の利用可能性は極めて幅広いと言える。 The PCM with a photocatalyst coating film of the present invention can be used for, for example, building materials such as siding, residential doors, partitions, lockers, switchboards, steel desks, benches, and exterior materials for electrical appliances such as coolers and refrigerators. The industrial applicability is very wide.
１、１Ａ、１Ｂ、１Ｃ 光触媒塗膜付ＰＣＭ
１０、１０Ａ 鋼板
１１ 鋼板本体
１２ 化成処理層
２０ 着色塗膜層（下塗塗膜層）
３０ 着色塗膜層（中塗塗膜層）
４０ 光触媒塗膜層
５０ 加工部（プレス部）
４０１ 光触媒粒子
４０２ バインダ成分
1, 1A, 1B, 1C PCM with photocatalyst coating
10, 10A Steel plate 11 Steel plate body 12 Chemical conversion layer 20 Colored coating layer (undercoat coating layer)
30 Colored coating layer (intermediate coating layer)
40 Photocatalyst coating layer 50 Processing part (press part)
401 Photocatalyst particles 402 Binder component
Claims (9)
前記光触媒塗膜層は、光触媒成分とバインダ成分を含んでなり、
前記バインダ成分は、ポリエステル樹脂ディスパージョン及びフッ化度４０％以上のフッ素アイオノマーを含有し、前記光触媒成分は前記フッ素アイオノマーに内包されており、樹脂不揮発成分換算において、前記ポリエステル樹脂ディスパージョンと前記フッ素アイオノマーとの重量比率が７０：３０であり、
前記光触媒塗膜層が、熱可塑性により形成されている
ことを特徴とする、光触媒塗膜付ＰＣＭ鋼板。 A steel plate, an organic coating layer formed on the surface of the steel plate, and a photocatalytic coating layer formed on the surface of the organic coating layer,
The photocatalyst coating layer comprises a photocatalyst component and a binder component,
The binder component contains a polyester resin dispersion and a fluorine ionomer having a degree of fluorination of 40% or more, the photocatalyst component is included in the fluorine ionomer, and the polyester resin dispersion and the fluorine in terms of a resin non-volatile component. weight ratio of the ionomer 70: 3 0,
The photocatalyst coating layer is formed of thermoplasticity. A PCM steel sheet with a photocatalyst coating.
ことを特徴とする、請求項１に記載の光触媒塗膜付ＰＣＭ鋼板。 The weight ratio of the said fluorine ionomer and the said photocatalyst is the range of 30: 70-60: 40. The PCM steel plate with a photocatalyst coating film of Claim 1 characterized by the above-mentioned.
ポリテトラフルオロエチレンの側鎖にスルホン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にカルボン酸を有するグラフト重合体、ポリテトラフルオロエチレンの側鎖にアミノ基を有するグラフト重合体、末端にリン酸エステルを有するパーフルオロアルキルオリゴマー、末端にスルホン酸基を有するパーフルオロアルキルオリゴマー、末端にカルボン酸基を有するパーフルオロアルキルオリゴマー、末端にアミノ酸基を有するパーフルオロアルキルオリゴマーの中から選択される、１種または２種以上の混合物である
ことを特徴とする、請求項１または２に記載の光触媒塗膜付ＰＣＭ鋼板。 The fluorine ionomer is
A graft polymer having a sulfonic acid in the side chain of polytetrafluoroethylene, a graft polymer having a carboxylic acid in the side chain of polytetrafluoroethylene, a graft polymer having an amino group in the side chain of polytetrafluoroethylene, and a terminal A perfluoroalkyl oligomer having a phosphate ester, a perfluoroalkyl oligomer having a sulfonic acid group at a terminal, a perfluoroalkyl oligomer having a carboxylic acid group at a terminal, or a perfluoroalkyl oligomer having an amino acid group at a terminal It is a 1 type, or 2 or more types of mixture. The PCM steel plate with a photocatalyst coating film of Claim 1 or 2 characterized by the above-mentioned.
ことを特徴とする、請求項１〜３のいずれかに記載の光触媒塗膜付ＰＣＭ鋼板。 The polyester resin dispersion is one or a mixture of two or more selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. A PCM steel sheet with a photocatalyst coating film according to claim 1.
ことを特徴とする、請求項１〜４のいずれかに記載の光触媒塗膜付ＰＣＭ鋼板。 The film thickness of the said photocatalyst coating film layer is 0.5 micrometer or more and 5 micrometers or less. The PCM steel plate with a photocatalyst coating film in any one of Claims 1-4 characterized by the above-mentioned.
前記塗布した有機塗料を焼付して有機層を形成する第一焼付工程と、
前記有機層の上に、光触媒塗料を塗布する第二塗装工程と、
前記塗布した光触媒塗料を焼付して光触媒塗膜層を形成する第二焼付工程と、
を順次経るものとし、
前記第二塗装工程では、前記光触媒塗料として、ポリエステル樹脂ディスパージョンとフッ化度４０％以上のフッ素アイオノマーをバインダ成分として含有する塗料を用い、
前記バインダ成分は、樹脂不揮発成分換算として、前記ポリエステル樹脂ディスパージョンと前記フッ素アイオノマーとの重量比率が７０：３０である
ことを特徴とする、光触媒塗膜付ＰＣＭ鋼板の製造方法。 A first painting step of applying an organic paint to the surface of the steel sheet;
A first baking step of baking the applied organic paint to form an organic layer;
A second coating step of applying a photocatalytic coating on the organic layer;
A second baking step of baking the applied photocatalytic coating to form a photocatalytic coating layer;
Through the
In the second coating step, as the photocatalytic paint, a paint containing a polyester resin dispersion and a fluorine ionomer having a degree of fluorination of 40% or more as a binder component is used.
The binder component is a resin nonvolatile component basis, the polyester resin dispersion and the weight ratio of the fluorine ionomer 70: characterized in that 3 is 0, the manufacturing method of the photocatalytic film-coated PCM steel.
ことを特徴とする、請求項６に記載の光触媒塗膜付ＰＣＭ鋼板の製造方法。 The said 2nd coating process uses the said binder component adjusted so that the weight ratio of the said fluorine ionomer and the said photocatalyst may become the range of 30: 70-60: 40. The manufacturing method of the PCM steel plate with a photocatalyst coating film.
ことを特徴とする、請求項６又は７に記載の光触媒塗膜付ＰＣＭ鋼板の製造方法。 8. The method for producing a PCM steel sheet with a photocatalyst coating film according to claim 6, wherein in the second coating step, the viscosity of the photocatalyst paint is adjusted to 20 to 50 mPa · s.
ことを特徴とする、請求項６から８の何れか１項に記載の光触媒塗膜付ＰＣＭ鋼板の製造方法。 In the said 2nd painting process, the said photocatalyst coating material is apply | coated by the roll coating method in a coil coating line. The manufacture of the PCM steel plate with a photocatalyst coating film in any one of Claim 6 to 8 characterized by the above-mentioned. Method.
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