JP4837337B2 - Painted plate excellent in processability and scratch resistance and method for producing the same - Google Patents
Painted plate excellent in processability and scratch resistance and method for producing the same Download PDFInfo
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Description
本発明は加工性、耐傷付性に優れた塗装板に関する。本発明の塗装板は、塗膜外観が凹凸状のうねりを示す柚子肌状であり、汚れが付着しても沈着しにくく、表面に傷がついても目立たないという優れた特徴を有する。また本発明は、特に多層同時塗布法により容易に柚子肌状凹凸外観を形成出来る塗装板の製造方法に関する。 The present invention relates to a coated plate having excellent workability and scratch resistance. The coated plate of the present invention has an excellent characteristic that the appearance of the coating film is a cocoon-skin shape showing uneven waviness, hardly deposits even if dirt is attached, and is inconspicuous even if the surface is scratched. The present invention also relates to a method for producing a coated plate that can easily form a cocoon skin-like irregular appearance by a multi-layer simultaneous coating method.
ここでの「塗装板」とは、基板の少なくとも片面に塗膜を形成した板材料として定義され、基板としては、金属、紙、木材、合板等のほか、ポリプロピレン(PP)、ポリエチレンテレフタレート(PET)を始めとする樹脂等の板を使用することができる。 The term “painted plate” as used herein is defined as a plate material in which a coating film is formed on at least one side of the substrate. As the substrate, in addition to metal, paper, wood, plywood, etc., polypropylene (PP), polyethylene terephthalate (PET ) And other resin plates can be used.
塗装板の代表例の一つである塗装金属板は、建築物、船舶、橋梁等の大きなものから各種機械、自動車、家具、電気製品等の小物、及び生活用品にまで幅広く使用されている。 A painted metal plate, which is one of the representative examples of the painted plate, is widely used for large items such as buildings, ships, bridges, etc., small items such as various machines, automobiles, furniture, electrical products, and daily necessities.
一般にこれらの金属板の塗装はポストコートと呼ばれ、加工・組立後に塗装が行われている。ポストコートでは、被塗物の形状が立体的であるため、溶剤系塗料のスプレーコートや粉体塗料の静電塗装等の非接触式塗装が適用されてきた。家電やOA機器の筐体、屋根や壁、室内の内壁などの建材、雑貨、自動車部品やその筐体などの分野では、表面欠陥の目立ち難い柚子肌状の塗膜外観が求められている。スプレーコートや粉体塗料の静電塗装等の非接触式塗装では、塗料のレベリング不足のため塗装面が独特の柚子肌外観となりやすく、容易に柚子肌の形成が可能であった。 In general, the coating of these metal plates is called post-coating and is performed after processing and assembly. In post-coating, since the shape of the object to be coated is three-dimensional, non-contact coating such as spray coating of solvent-based paint and electrostatic coating of powder paint has been applied. In fields such as housings for home appliances and office automation equipment, roofs and walls, interior walls such as indoor walls, miscellaneous goods, automobile parts and their housings, there is a demand for a cocoon-skin-like coating film appearance in which surface defects are not noticeable. In non-contact coating such as spray coating and electrostatic coating of powder paint, the paint surface tends to have a unique cocoon skin appearance due to insufficient leveling of the paint, and cocoon skin can be easily formed.
最近では、建材、家電、雑貨、自動車などの分野において、金属板を成形加工して組立てた後に塗装するという従来のポストコート方式に変わって、あらかじめ塗装された金属板(プレコート金属板、PCMと略す)を成形加工し、接合して製品とするプレコート方式が多く採用されている。プレコート方式の導入には、需要家での塗装工程が省略でき、塗装廃棄物等による公害・環境問題の解決が図られ、更に塗装のための作業スペースを他の用途に転用できるなどのメリットがある。 Recently, in the fields of building materials, home appliances, miscellaneous goods, automobiles, etc., instead of the conventional post-coating method in which metal plates are molded and assembled and then painted, pre-painted metal plates (pre-coated metal plates, PCM and A pre-coating method in which a product is formed by molding and bonding to a product is often employed. The introduction of the pre-coating method has the advantage that the painting process at the customer can be omitted, pollution and environmental problems due to painting waste, etc. can be solved, and the work space for painting can be diverted to other uses. is there.
ところが、特にプレコート鋼板の分野では、製品特性として加工性が強く要求されるため、立体感や肉もち感のある柚子肌状塗膜の導入は容易ではない。従来の柚子肌状外観の塗膜形成方法としては、(1)樹脂ビーズを含有する塗料を使用する方法、(2)無機系ビーズを含有する塗料を用いる方法、(3)印刷を利用する方法、(4)メッシュロールを用いる方法、(5)静電粉体塗装を用いる方法、などがある。 However, particularly in the field of pre-coated steel sheets, workability is strongly required as a product characteristic, and therefore it is not easy to introduce a cocoon skin-like coating film having a three-dimensional feeling or a meaty feeling. As a conventional method for forming a coating film having a cocoon skin-like appearance, (1) a method using a paint containing resin beads, (2) a method using a paint containing inorganic beads, (3) a method using printing , (4) a method using a mesh roll, and (5) a method using electrostatic powder coating.
例えば、特許文献1には、平均粒径10〜50μmの熱可塑性樹脂粉末を含有する塗料組成物を使って、柚子肌状の外観の塗膜を得る方法(樹脂ビーズ法)が記載されている。特許文献1の方法では、ビヒクル樹脂との溶解度パラメータの差を規定し、塗膜焼付温度における前記樹脂粉末の溶解粘度を規定している。また、塗料組成物を被塗物に塗装し焼き付けた塗膜を、断面において樹脂粉末がある程度溶融して扁平状になり、その上にビヒクル樹脂が硬化して膜を形成すること、こうして得られる柚子肌状の塗膜において、最も低い塗膜面から測定した凸部の高さは2〜50μm程度、1つの凸部の幅(凸部の広がりを示す径)は1〜10mm程度となることが記載されている。 For example, Patent Document 1 describes a method (resin bead method) for obtaining a coating film having a cocoon skin-like appearance using a coating composition containing a thermoplastic resin powder having an average particle size of 10 to 50 μm. . In the method of Patent Document 1, a difference in solubility parameter from the vehicle resin is defined, and the dissolution viscosity of the resin powder at the coating film baking temperature is defined. In addition, a coating film obtained by coating and baking a coating composition on an object to be coated is obtained by melting the resin powder to a certain extent in a cross section to form a flat shape, and then curing the vehicle resin thereon to form a film. In a cocoon skin-like coating film, the height of the convex portion measured from the lowest coating surface is about 2 to 50 μm, and the width of one convex portion (diameter indicating the extent of the convex portion) is about 1 to 10 mm. Is described.
特許文献2にも樹脂ビーズ法が記載され、この方法では、熱硬化性樹脂と、熱硬化性樹脂よりも表面自由エネルギーの低いアミノ樹脂と、塗膜焼付け時には溶融し、かつ塗料には溶解しない樹脂ビーズとを含有する塗料組成物を塗布、焼付する。 Patent Document 2 also describes a resin bead method. In this method, a thermosetting resin, an amino resin having a surface free energy lower than that of the thermosetting resin, and melted when the coating film is baked and not dissolved in the paint. A coating composition containing resin beads is applied and baked.
特許文献3には、無機ビーズ法が記載され、この方法では、粒径0.3mm未満のガラスビーズと150〜200メッシュの有色骨材を特定比率で配合した塗料組成物が使用される。
特許文献4には、塗膜厚が少なくとも2μm以上の立体模様を印刷法により部分的に形成した後、全面にトップコート層を形成する印刷法が記載されている。
特許文献5には、塗料樹脂(ベース樹脂)に溶解度パラメータが異なる添加剤を含有させた塗料を、メッシュロールを用いて塗布して、造膜過程でベース樹脂と相溶性の悪い添加剤が分離してはじき状意匠性外観が形成されるメッシュロール法が開示されている。 In Patent Document 5, a paint in which an additive having a different solubility parameter is added to a paint resin (base resin) is applied using a mesh roll, and an additive that is not compatible with the base resin is separated during the film formation process. In addition, a mesh roll method is disclosed in which a repellent design appearance is formed.
従来の樹脂ビーズ含有塗膜を使用する方法には、加熱過程での模様の再現性が必ずしも良くない、加熱パターンにより微妙な膜厚を調整することが困難、塗料の安定性が悪い、塗料の切り替え時の洗浄が必須(ビーズが原因の塗装不良が発生)などの問題がある。 In the conventional method using a resin bead-containing coating film, the reproducibility of the pattern in the heating process is not necessarily good, it is difficult to adjust the subtle film thickness by the heating pattern, the stability of the paint is poor, the paint There is a problem that cleaning at the time of switching is essential (painting failure due to beads).
無機系ビーズ含有塗料を用いて柚子肌を形成する方法には、塗膜表面に露出するビーズが多くなり、ビーズの脱落による塗膜の劣化や、塗膜の加工性が悪いなどの問題がある。また、固体ビーズを塗料中に安定して懸濁させるのが困難という問題もある。更に、塗膜表面にざらざら感が残るのも難点である。 In the method of forming cocoon skin using a coating containing inorganic beads, there are many beads exposed on the surface of the coating film, and there are problems such as deterioration of the coating film due to dropping of the beads and poor processability of the coating film. . Another problem is that it is difficult to stably suspend the solid beads in the paint. Furthermore, it is also difficult to have a rough feeling on the surface of the coating film.
印刷法では、立体模様を印刷後に加熱乾燥し、トップコート層を形成後に再度加熱乾燥する2コート2ベークが基本になる。このため、塗装工程が煩雑になり、コスト高となる。 The printing method is basically a two-coat two-bake in which a three-dimensional pattern is heated and dried after printing, and a top coat layer is formed and then dried again by heating. For this reason, the coating process becomes complicated and the cost increases.
メッシュロール法の場合、均一な膜厚の調整がしにくく、部分的に膜厚の薄い部分が発生するため、塗装金属板の耐食性に問題がある。 In the case of the mesh roll method, it is difficult to adjust the uniform film thickness, and a portion having a thin film thickness is partially generated, which causes a problem in the corrosion resistance of the coated metal plate.
静電粉体塗装法では、ラインスピードが10〜20m/分と小さいために生産性が低く、コスト高になってしまう。 In the electrostatic powder coating method, the line speed is as low as 10 to 20 m / min, so the productivity is low and the cost is high.
本発明は、柚子肌状の塗装外観を有し、加工性、耐傷付性に優れた塗装金属板その他の塗装板と、このような塗装板の簡便な製造方法の提供を目的とする。 An object of the present invention is to provide a coated metal plate or other coated plate having an insulator-like painted appearance and excellent workability and scratch resistance, and a simple method for producing such a coated plate.
本発明者らは、性質の異なる塗料から形成した層を積層した多層塗膜が、加熱乾燥時に積層塗膜の境界層を乱して塗料の不均一流れを発生する現象に着目した。そして本発明者らは、この不均一流れは塗膜内の微細な対流現象ではあるが、塗膜の最外表層面に数ミリメートル単位の大きな凹凸変化を誘起することを発見した。本発明者らは鋭意研究を進め、各層を形成する塗料の表面張力と塗膜の加熱条件を最適化することにより、柚子肌状のなめらかな凹凸を塗膜表面に形成させることに成功し、本発明を完成させた。 The present inventors paid attention to a phenomenon in which a multilayer coating film in which layers formed from paints having different properties are laminated disturbs the boundary layer of the laminate paint film during heating and drying and generates a non-uniform flow of the paint. The present inventors have found that this non-uniform flow is a fine convection phenomenon in the coating film but induces a large unevenness change of several millimeters on the outermost surface of the coating film. The inventors proceeded with earnest research and succeeded in forming smooth skin-like irregularities on the coating film surface by optimizing the surface tension of the paint forming each layer and the heating conditions of the coating film, The present invention has been completed.
本発明による塗装板は、塗膜最表層が柚子肌形状であり、しかも最表層塗膜とその下層塗膜との境界面がほぼ又は完全に連続した波状構造を有し、すなわち境界面がほぼ又は完全に連続した波状構造の面となっていて下層塗膜にも最表層塗膜にも不連続な部位がなく、基板の全面がそれらにより実質的に覆われているため、加工性、耐傷付性にも優れた塗装板である。 The coated plate according to the present invention has a wavy structure in which the outermost layer of the coating film has a cocoon skin shape, and the boundary surface between the outermost layer coating film and the lower layer coating film is almost or completely continuous, that is, the boundary surface is almost the same. Or because it has a completely continuous wavy surface, there are no discontinuous parts in the lower layer coating and the outermost layer coating, and the entire surface of the substrate is substantially covered by them, so that workability and scratch resistance It is a coated plate with excellent adhesion.
本発明の要旨は以下の通りである。
(1) 塗膜最外表面のろ波うねり中心線平均(Wca)が0.35μm≦Wca≦1.25μmで、且つろ波うねり平均山間隔(Wc-sm)が2800μm≦Wc-sm≦12500μmであり、最表層塗膜とその下層塗膜との境界面が波状構造を有し、最表層塗膜とその下層塗膜との境界面を塗膜厚み方向断面で観察した時に現れる波形の曲線が、
(i) 塗膜最外表面と境界面の波形曲線との距離をA、最表層塗膜の平均膜厚をBとして、A≦0.8Bの領域を持つとして定義される大波を含むこと、
(ii) 大波間の平均距離が750μm以下であること、
という条件を満足することを特徴とする加工性、耐傷付性に優れた塗装板。
(2) 最表層塗膜と下層塗膜との境界面が連続した波状構造の面であることを特徴とする、上記(1)に記載の加工性、耐傷付性に優れた塗装板。
(3) 最表層塗膜とその下層塗膜を同色の熱硬化性樹脂とすることを特徴とする、上記(1)又は(2)に記載の加工性、耐傷付性に優れた塗装板。
(4) 最表層塗膜とその下層塗膜の合計膜厚が乾燥塗膜厚みで5〜50μmであることを特徴とする、上記(1)〜(3)のいずれか1つに記載の加工性、耐傷付性に優れた塗装板。
(5) 下層塗膜と基板との間に更に1又は2以上の塗膜を有することを特徴とする、上記(1)〜(4)のいずれか1つに記載の加工性、耐傷付性に優れた塗装板。
(6) 基板上に下層塗膜を形成する塗料と最表層塗膜を形成する塗料をともにウェット状態で塗布して塗膜を形成後、これらの塗膜を同時に加熱乾燥することと、最表層塗膜を形成する塗料は、その表面張力を５回測定したとき、得られる測定値の最大値と最小値の差が2mN/m以上であることを特徴とする、上記(1)に記載の加工性、耐傷付性に優れた塗装板の製造方法。
(7) 基板上に下層塗膜を形成する塗料と最表層塗膜を形成する塗料をともにウェット状態で塗布して塗膜を形成後、これらの塗膜を同時に加熱乾燥することと、最表層塗膜の塗料の表面張力δａと下層塗膜の塗料の表面張力δｂの差の絶対値が、0.1mN／ｍ≦｜δａ−δｂ｜≦5.0mN／ｍの範囲内にあることを特徴とする、上記(1)に記載の加工性、耐傷付性に優れた塗装板の製造方法。
(8) 下層塗膜を形成する塗料及び最表層塗膜を形成する塗料の塗布をウェットオンウェット塗布または同時多層塗布により行うことを特徴とする、上記(6)又は(7)に記載の加工性、耐傷付性に優れた塗装板の製造方法。
(9) 塗膜の加熱乾燥を誘導加熱、通電加熱又は超音波加熱により行うことを特徴とする、上記(6)〜(8)のいずれか1つに記載の加工性、耐傷付性に優れた塗装板の製造方法。
(10) 最表層塗膜を形成する塗料中に表面張力が異なる2種類以上の界面活性剤を含有させることを特徴とする、上記(6)〜(9)のいずれか1つに記載の加工性、耐傷付性に優れた塗装板の製造方法。
(11) 最表層塗膜の塗料の表面張力と下層塗膜の塗料の表面張力の少なくとも一方を添加剤の添加により調整することを特徴とする、上記(7)に記載の加工性、耐傷付性に優れた塗装板の製造方法。
(12) 添加剤が界面活性剤、配合溶剤又はレベラーであることを特徴とする、上記(11)に記載の加工性、耐傷付性に優れた塗装板の製造方法。
(13) 塗料中に界面活性剤を0.4mass%以下含有させることを特徴とする、上記(10)又は(11)に記載の加工性、耐傷付性に優れた塗装板の製造方法。
(14) 誘導加熱装置を用い、1.0℃/秒〜20℃/秒の範囲の加熱速度で基板を加熱することにより塗膜の同時加熱乾燥を行うことを特徴とする、上記(6)〜(13)のいずれか1つに記載の加工性、耐傷付性に優れた塗装板の製造方法。
(15) 最表層塗膜を形成する塗料とその下層塗膜を形成する塗料の粘度が0.2〜1.0Pa・sであることを特徴とする、上記(6)〜(14)のいずれか1つに記載の加工性、耐傷付性に優れた塗装板の製造方法。
The gist of the present invention is as follows.
(1) The filtered waviness centerline average (Wca) of the outermost surface of the coating film is 0.35 μm ≦ Wca ≦ 1.25 μm, and the waviness average peak spacing (Wc-sm) is 2800 μm ≦ Wc-sm ≦ 12500 μm. , the boundary surface between the outermost layer coating film and the underlying coating film have a corrugated structure, the curve of the waveforms appearing when observing the interface between the outermost layer coating film and the underlying coating in the coating thickness direction cross-section,
(i) including a large wave defined as having a region of A ≦ 0.8B, where A is the distance between the outermost surface of the coating film and the waveform curve of the boundary surface, B is the average film thickness of the outermost layer coating film,
(ii) The average distance between the large waves is 750 μm or less,
A paint plate with excellent workability and scratch resistance, characterized by satisfying the above conditions .
( 2 ) The coated plate having excellent workability and scratch resistance according to (1 ) above, wherein the boundary surface between the outermost layer coating film and the lower layer coating film has a continuous wave-like structure.
( 3 ) The coated plate excellent in workability and scratch resistance according to (1) or (2) above, wherein the outermost layer coating film and the lower layer coating film are thermosetting resins of the same color.
( 4 ) The processing according to any one of (1) to ( 3 ) above, wherein the total film thickness of the outermost layer coating film and the lower layer coating film is 5 to 50 μm in terms of dry coating thickness Coated plate with excellent resistance and scratch resistance.
( 5 ) The workability and scratch resistance according to any one of (1) to ( 4 ) above, further comprising one or more coating films between the lower coating film and the substrate Excellent painted board.
( 6 ) After coating both the paint for forming the lower layer coating on the substrate and the coating for forming the outermost layer coating in a wet state to form a coating, these coatings are simultaneously heated and dried, and the outermost layer is coated. The coating material for forming a coating film is characterized in that, when the surface tension is measured five times, the difference between the maximum value and the minimum value of the measurement value obtained is 2 mN / m or more . A method of manufacturing a coated plate with excellent workability and scratch resistance.
(7) Apply both the paint for forming the lower layer coating on the substrate and the coating for forming the outermost layer coating in a wet state to form a coating, and then heat drying these coatings at the same time. The absolute value of the difference between the surface tension δa of the coating material paint and the surface tension δb of the lower layer coating material is in the range of 0.1 mN / m ≦ | δa−δb | ≦ 5.0 mN / m. The method for producing a coated plate having excellent workability and scratch resistance as described in (1) above.
(8) The processing according to (6) or (7) above, wherein the coating for forming the lower layer coating and the coating for forming the outermost layer coating are performed by wet-on-wet coating or simultaneous multilayer coating. For producing coated plates with excellent heat resistance and scratch resistance.
(9) It is excellent in workability and scratch resistance according to any one of the above (6) to (8) , characterized in that the coating film is heated and dried by induction heating, electric heating or ultrasonic heating. A method of manufacturing painted plates.
(10) The processing according to any one of ( 6 ) to ( 9 ) above, wherein two or more kinds of surfactants having different surface tensions are contained in the coating material forming the outermost layer coating film. For producing coated plates with excellent heat resistance and scratch resistance.
( 11 ) The processability and scratch resistance according to ( 7 ) above, wherein at least one of the surface tension of the outermost layer coating and the surface tension of the lower layer coating is adjusted by addition of an additive. A method for producing coated plates with excellent properties.
( 12 ) The method for producing a coated plate having excellent processability and scratch resistance according to ( 11 ) above, wherein the additive is a surfactant, a compounding solvent or a leveler.
( 13 ) The method for producing a coated plate having excellent processability and scratch resistance according to ( 10 ) or ( 11 ) above, wherein a surfactant is contained in the paint in an amount of 0.4 mass% or less.
( 14 ) The above ( 6 ) to ( 6 ), wherein the coating film is simultaneously heated and dried by heating the substrate at a heating rate in the range of 1.0 ° C / second to 20 ° C / second using an induction heating device. The method for producing a coated plate having excellent workability and scratch resistance according to any one of 13 ).
( 15 ) Any one of the above ( 6 ) to ( 14 ), wherein the viscosity of the paint forming the outermost layer coating and the coating forming the lower layer coating is 0.2 to 1.0 Pa · s. The manufacturing method of the coating board excellent in workability and damage resistance as described in 1.
本発明の塗装板は、耐傷付性、加工性に優れた特性を示す上に、柚子肌状の立体感のある意匠性を示す。また、塗膜にビーズなどの分散物が存在しないため、極めて良好な加工性を示し、特にプレコート鋼板などへの適用が容易である。 The coated plate of the present invention exhibits characteristics excellent in scratch resistance and workability, and also exhibits design properties with a three-dimensional appearance of a cocoon skin shape. In addition, since there is no dispersion such as beads in the coating film, it exhibits extremely good workability and is particularly easy to apply to precoated steel sheets.
本発明の製造方法によれば、塗装ラインの生産性が向上し(ラインスピードが速く、2コート1ベークで塗膜を形成でき、下層塗膜の焼付工程が不要)、塗料の選択性も広い。そのため、製造コストを削減できる。更に、本発明によれば、塗料の変更や注文ロットの変更に際しても、ビーズなどの固形分がない塗料を使用するため、コータの洗浄などが容易であり、塗料変更作業による休止時間も短く、作業トラブルも生じにくい。 According to the production method of the present invention, the productivity of the coating line is improved (the line speed is fast, the coating can be formed by two coats and one bake, and the baking process of the lower layer coating is unnecessary), and the paint selectivity is also wide. . Therefore, the manufacturing cost can be reduced. Furthermore, according to the present invention, even when changing the paint or changing the order lot, since the paint having no solid content such as beads is used, it is easy to wash the coater and the downtime due to the paint change work is short, Work trouble is less likely to occur.
図1の模式図に示したように、本発明の塗装板10は、基板1と、基板1の上に形成した連続の下層塗膜3とその上に形成した連続の最表層塗膜5から構成される多層塗膜7とを有する。図1では、塗膜の構造を見やすくするため、基板1の平面方向に対し塗膜3、5の厚み方向(基板1の平面に垂直な方向)を大きく拡大している。本発明の塗装板の実際の塗膜断面を拡大して観察すると、図2に模式的に示したように見える。この図において、最表層塗膜5はほとんど平滑に見えるが、実際には柚子肌状の表面を呈している。
As shown in the schematic diagram of FIG. 1, the
図3に、樹脂ビーズを含む塗料を使って製造した従来の柚子肌状塗装板の模式図を示す。この図の塗装板100では、基板101の上に形成した塗膜103中に樹脂ビーズ105が分散している。このように、樹脂ビーズを用いた従来の柚子肌状塗装板では、樹脂ビーズが融解してある程度変形したとしても、それらは分散して存在し、また隣り合うビーズが合体して大きな粒子を形成したとしても、それらはやはり分散していて、連続した塗膜を形成するには至らない。
FIG. 3 shows a schematic diagram of a conventional cocoon skin-like paint plate manufactured using a paint containing resin beads. In the painted
それに対し、図1、2に示したように、本発明の柚子肌状塗装板では、下層塗膜と最表層塗膜との界面は塗膜加熱乾燥時に発生する乱流により乱れてはいるものの、ほぼ又は実質的に連続性を維持している。 On the other hand, as shown in FIGS. 1 and 2, in the insulator skin-like coated plate of the present invention, the interface between the lower layer coating and the outermost layer coating is disturbed by the turbulent flow generated during coating drying. , Approximately or substantially maintaining continuity.
樹脂ビーズを用いる従来技術の場合は、熱硬化性のバインダー中に熱可塑性樹脂ビーズを混合させるので両樹脂間の親和性が低く(むしろ両者が相溶しないことが求められるため)、塗装板の加工成形時に塗膜の欠陥を生じ易い。 In the case of the prior art using resin beads, since the thermoplastic resin beads are mixed in a thermosetting binder, the affinity between the two resins is low (rather, it is required that the two are not compatible) Defects in the coating are likely to occur during processing and molding.
それに対し、本発明の塗装板の塗膜には上下層とも熱硬化性樹脂を用いることができる。両者の表面張力が異なるように調整すれば、全く同一の樹脂であってもかまわない。従って上下層の塗膜は単一層に近い相互密着性を有することが可能である。また、同時乾燥するので、本発明では上下樹脂間の架橋度も高くなっていると思われる。 On the other hand, a thermosetting resin can be used for the upper and lower layers in the coating film of the coated plate of the present invention. If the two are adjusted so that their surface tensions are different, the same resin may be used. Accordingly, the upper and lower coating layers can have mutual adhesion close to a single layer. Moreover, since it dries simultaneously, it seems that the crosslinking degree between upper and lower resin is also high in this invention.
本発明で用いられる基板は特に限定されず、金属、紙、木材、合板等のほか、ポリプロピレン(PP)、ポリエチレンテレフタレート(PET)その他の樹脂等の板を使用することができる。 The substrate used in the present invention is not particularly limited, and plates such as metal, paper, wood, plywood, polypropylene (PP), polyethylene terephthalate (PET), and other resins can be used.
金属板としては、例えば鋼板、アルミニウム板、ステンレス鋼板、チタン板、銅板等が挙げられる。このうち鋼板の例として、冷延鋼板、熱延鋼板、亜鉛めっき鋼板、合金化亜鉛めっき鋼板、亜鉛-鉄合金めっき鋼板、亜鉛-アルミニウム合金めっき鋼板、アルミニウムめっき鋼板、クロムめっき鋼板、ニッケルめっき鋼板、亜鉛-ニッケル合金めっき鋼板、錫めっき鋼板等が挙げられる。 Examples of the metal plate include a steel plate, an aluminum plate, a stainless steel plate, a titanium plate, and a copper plate. Examples of steel plates include cold-rolled steel plates, hot-rolled steel plates, galvanized steel plates, alloyed galvanized steel plates, zinc-iron alloy-plated steel plates, zinc-aluminum alloy-plated steel plates, aluminum-plated steel plates, chrome-plated steel plates, nickel-plated steel plates. , Zinc-nickel alloy plated steel sheet, tin plated steel sheet and the like.
金属板には、必要に応じて前処理を施すことができる。前処理としては、水洗、湯洗、酸洗、アルカリ脱脂、研削、研磨、クロメート処理、リン酸亜鉛処理、複合酸化皮膜処理その他のノンクロメート型の処理等がある。これらを単独又は組み合わせて塗装前処理を行うことができる。塗装前処理の条件は適宜選択すればよい。 The metal plate can be pretreated as necessary. Examples of the pretreatment include water washing, hot water washing, pickling, alkali degreasing, grinding, polishing, chromate treatment, zinc phosphate treatment, composite oxide film treatment and other non-chromate treatments. These can be used alone or in combination for pre-coating treatment. What is necessary is just to select the conditions of pre-coating treatment suitably.
本発明に用いられる塗膜層(下層塗膜層、最表層塗膜層(上層塗膜層))には、加工性、硬度、耐汚染性、耐薬品性など多くの性能が要求されるため、塗膜層の形成に用いる塗料で使用する主樹脂の種類はポリエステル樹脂、アクリル樹脂、ウレタン樹脂、塩化ビニル樹脂、フッ素樹脂等が好適である。上下層の樹脂の組合せは、目的に応じて適宜選択すればよい。とりわけ加工性に優れ、硬度や耐汚染性など他の性能とのバランスがとりやすいポリエステル樹脂が最も適している。 The coating layer (lower coating layer, outermost coating layer (upper coating layer)) used in the present invention is required to have many performances such as processability, hardness, contamination resistance, chemical resistance, etc. The type of the main resin used in the paint used for forming the coating layer is preferably a polyester resin, an acrylic resin, a urethane resin, a vinyl chloride resin, a fluorine resin, or the like. What is necessary is just to select suitably the combination of resin of an upper and lower layer according to the objective. In particular, a polyester resin that is excellent in processability and easily balanced with other properties such as hardness and stain resistance is most suitable.
塗料で使用する架橋剤としては、メラミン樹脂、ベンゾグアナミン樹脂等のアミノ樹脂や、イソシアネート樹脂が、加工性と他の性能とのバランスの点で優れている。 As the crosslinking agent used in the paint, amino resins such as melamine resin and benzoguanamine resin and isocyanate resins are excellent in terms of the balance between processability and other performances.
塗料で用いられる溶剤は、特に限定されず、いずれの溶剤も使用可能である。溶剤の種類は、樹脂の溶解に支障ない範囲で選択することが望ましい。また、塗装する際に必要な粘度、塗装作業性を考慮してその種類や量を選択できる。 The solvent used in the paint is not particularly limited, and any solvent can be used. It is desirable to select the type of solvent as long as it does not hinder the dissolution of the resin. In addition, the type and amount can be selected in consideration of the viscosity required for coating and the coating workability.
上下層用の塗料は、任意の色を持つことができる。場合により、着色剤を使用して着色することもできる。また、上下層用の塗料は同一の色であってもよく、異なる色であってもよい。上下層の色を同一にする場合は、上下層それぞれの膜厚で単一層を形成させたときの塗膜の色差が、JIS Z 8730-6.1で規定される色差1.0以下の塗料を用いる。 The paint for the upper and lower layers can have any color. In some cases, coloring can also be performed using a coloring agent. The upper and lower layer coating materials may be the same color or different colors. When the upper and lower layers have the same color, a paint having a color difference of 1.0 or less as defined in JIS Z 8730-6.1 is used when the single layer is formed with the thickness of each of the upper and lower layers.
上下塗膜層の乾燥後合計膜厚を5μm以上にすると柚子肌の形成が容易である。更に好適には、乾燥後合計膜厚を8μm以上とする。乾燥後合計膜厚の上限は特に限定されないが、膜厚が厚くなると乾燥に時間がかかるため経済性と生産性の観点から50μm以下であることが望ましい。 If the total film thickness after drying of the upper and lower coating layers is 5 μm or more, the formation of cocoon skin is easy. More preferably, the total film thickness after drying is 8 μm or more. The upper limit of the total film thickness after drying is not particularly limited. However, when the film thickness is thick, it takes time for drying, so that it is preferably 50 μm or less from the viewpoint of economy and productivity.
必要に応じて、別の塗料を金属板上に塗布し、硬化乾燥させることにより追加塗膜を形成した後に、本発明の下層塗膜層、最表層塗膜層を形成することができる。追加塗膜用の塗料としては、種類は特に限定されないが、ポリエステル樹脂系、エポキシ樹脂系、ウレタン樹脂系、アクリル樹脂系等を挙げることができる。選択した塗料をロールコーター、カーテンフローコーター、ローラーカーテンコーター、静電塗装機、ハケ、ブレードコーター、ダイコーター等で必要な膜厚になるように塗装し、次いで常温放置であるいは熱風炉、誘導加熱炉、近赤外線炉、遠赤外線炉又はエネルギー線硬化炉等で硬化乾燥することによって追加塗膜層が得られる。 If necessary, after applying another coating material on a metal plate and curing and drying to form an additional coating film, the lower coating film layer and the outermost coating film layer of the present invention can be formed. The type of paint for the additional coating is not particularly limited, and examples thereof include polyester resin, epoxy resin, urethane resin, and acrylic resin. The selected paint is applied to the required film thickness using a roll coater, curtain flow coater, roller curtain coater, electrostatic coating machine, brush, blade coater, die coater, etc., then left at room temperature or in a hot air oven, induction heating The additional coating layer is obtained by curing and drying in an oven, a near infrared oven, a far infrared oven, an energy beam curing oven or the like.
追加塗膜層には、必要に応じて公知の顔料や添加剤を加えることができる。膜厚は任意であるが、塗装金属板においては1〜30μm程度、特に3〜12μmの乾燥膜厚が一般的である。乾燥条件は塗料の種類と得たい性能に応じて適宜選択すればよいが、熱風炉や誘導加熱炉、近赤外線炉等で最高到達板温150〜240℃、到達時間10〜200秒程度の条件が一般的である。追加塗膜層はなくてもよいし、1層であっても、多層であっても差し支えない。 A known pigment or additive can be added to the additional coating layer as necessary. The film thickness is arbitrary, but in the case of a coated metal plate, a dry film thickness of about 1 to 30 μm, particularly 3 to 12 μm is common. The drying conditions may be selected as appropriate according to the type of paint and the performance to be obtained. However, the maximum plate temperature is 150 to 240 ° C and the arrival time is about 10 to 200 seconds in a hot air furnace, induction heating furnace, near infrared furnace, etc. Is common. There may be no additional coating layer, and it may be a single layer or a multilayer.
本発明の塗装板は、塗膜最外表面のろ波うねり中心線平均(Wca)が0.35μm≦Wca≦1.25μmで、且つろ波うねり平均山間隔(Wc-sm)が2800μm≦Wc-sm≦12500μmであることを必要とする。Ｗcaが0.35μmより小さいと塗膜の平滑感が強くなり、Wc-smによらず柚子肌感が無くなる。一方、Ｗcaが1.25μmより大きいと、ざらつき感が強くなり、滑らかな印象が無くなる。Wc-smが2800μmより小さいと柚子肌感が強くなりすぎ、一方12500μmより大きくなると柚子肌感が無くなる。 The coated plate of the present invention has a filtered waviness centerline average (Wca) of the coating film outermost surface of 0.35 μm ≦ Wca ≦ 1.25 μm and a filtered waviness average peak interval (Wc-sm) of 2800 μm ≦ Wc-sm. ≦ 12500 μm is required. When Wca is smaller than 0.35 μm, the smoothness of the coating film becomes strong, and the cocoon skin feeling is lost regardless of Wc-sm. On the other hand, when Wca is larger than 1.25 μm, the feeling of roughness becomes strong and the smooth impression is lost. If Wc-sm is smaller than 2800 μm, the cocoon skin feeling becomes too strong, whereas if Wc-sm is larger than 12500 μm, the cocoon skin feeling is lost.
ろ波うねり中心線平均(Wca)とは、断面曲線から波長の短い表面粗さの成分を除いて得られる曲線からその中心線の方向に測定長さLの部分を抜き取り、その抜き取り部分の中心線をX軸、縦倍率の方向をZ軸とし、z=f(x)で表したとき、 Filtered waviness centerline average (Wca) is the measured length L in the direction of the centerline from the curve obtained by removing the surface roughness component with a short wavelength from the cross-sectional curve, and the center of the extracted portion When the line is the X axis, the direction of the vertical magnification is the Z axis, and z = f (x),
で定義される値である。波長の短い表面粗さ成分は80μm未満(カットオフ値80μm)とする。 It is a value defined by. The surface roughness component with a short wavelength is less than 80 μm (cut-off value 80 μm).
ろ波うねり平均山間隔(Wc-sm)とは、断面曲線から80μmをカットオフ値とした波長の短い表面粗さ成分を除去して得られる曲線(ろ波うねり曲線)から、ある測定長さLを抜き取り、その平均線を横切って山から谷へ向かう横断点(平均線との交点)から、次の山から谷へ向かう横断点までの間隔をSmiとするとき、間隔の総数をNとして、 Filtered waviness average peak spacing (Wc-sm) is a measured length from a curve (filtered waviness curve) obtained by removing a short-wavelength surface roughness component with a cut-off value of 80 μm from the cross-sectional curve. sampling L, and the from cutting points extending from its across the mean line peaks to valleys (the intersection of the mean line), when the distance to the crossing point towards the following peaks to valleys and Sm i, the total number of intervals N As
で定義される値である。 It is a value defined by.
ろ波うねり中心線平均(Wca)とろ波うねり平均山間隔(Wc-sm)の測定には、任意の5箇所のサンプルを測定してその平均を求めた。 For the measurement of the filtered waviness center line average (Wca) and the filtered waviness average peak interval (Wc-sm), five samples were measured and the average was obtained.
本発明の塗装板では、最表層塗膜とその下層塗膜との境界面の形状が重要であり、目標とする柚子肌を形成させるためにはこの境界面の形状を適正に管理し、境界面が波状構造を持つようにする必要がある。 In the coated plate of the present invention, the shape of the boundary surface between the outermost layer coating film and the lower layer coating film is important, and in order to form the target insulator skin, the shape of this boundary surface is properly managed, The surface must have a wavy structure.
具体的には、図4に示したように最表層塗膜43とその下層塗膜41との波状の境界面を塗膜厚み方向断面で観察した時に現れる波形の曲線Ｗが、
(1) 塗膜最外表面Sと境界面の波形曲線Wとの距離をA、最表層塗膜43の平均膜厚をBとして、A≦0.8Bの領域G(図中、斜線を施して示された領域)を持つとして定義される大波を含むこと、
(2) 大波間の距離(隣り合う大波の最大高さの点間の距離に相当し、図中ではX1、X2で表される)の平均が750μm以下であること、
という条件を満足する場合に、良好な柚子肌が形成される。塗膜断面に大波が認められなければ、良好な柚子肌の形成はおぼつかない。大波間の平均距離が750μmを超えている場合は、加熱乾燥時の塗膜内部の塗料の対流現象が沈静化しており、表面の柚子肌が不明瞭となっている。
Specifically, as shown in FIG. 4, the waveform curve W that appears when the wavy boundary surface between the outermost
(1) Assuming that the distance between the outermost surface S of the coating film S and the waveform curve W of the boundary surface is A, and the average film thickness of the outermost
(2) The average of the distance between the large waves (corresponding to the distance between the points of the maximum height of adjacent large waves, represented by X 1 and X 2 in the figure) is 750 μm or less,
When the above condition is satisfied, good cocoon skin is formed. If no large waves are observed in the cross section of the coating film, the formation of good cocoon skin will not be noticeable. When the average distance between the large waves exceeds 750 μm, the convection phenomenon of the paint inside the coating film during heating and drying is calmed down, and the cocoon skin on the surface is unclear.
境界面の断面波形曲線が上記の条件を満足するかどうかは、次のようにして判定することができる。
(a) まず塗装板上の任意の5箇所から3mm長の断面サンプルを5個採取する。
(b) 個々のサンプル断面を観察して、以下の手順により大波間の平均距離を計算する。
(1)最表層塗膜の平均膜厚Bを測定し、0.8Bを算出する。平均膜厚としては、1m2の単位面積当たりの塗膜の重量と塗膜の密度とから計算される値を採用する。
(2)塗膜最外表面と境界面の波状曲線との距離Aと前記0.8Bを比較し、大波の領域を決定する。
(3)各大波の領域の中で最も塗膜最外表層に近い部分を1点選び、その点を起点として隣り合う大波間の距離X1、X2、・・・・・・を測定する。
(4)各サンプル毎に大波間距離の平均値を求める。
(5)全サンプルの大波間距離を平均した値を、塗装板の大波間の平均距離とする。
Whether or not the cross-sectional waveform curve of the boundary surface satisfies the above conditions can be determined as follows.
(a) First, 5 cross-section samples with a length of 3 mm are taken from any 5 locations on the painted plate.
(b) Observe the cross section of each sample and calculate the average distance between large waves by the following procedure.
(1) Measure the average film thickness B of the outermost layer coating film and calculate 0.8B. As the average film thickness, a value calculated from the weight of the coating film per unit area of 1 m 2 and the density of the coating film is adopted.
(2) The distance A between the outermost surface of the coating film and the wavy curve at the boundary surface is compared with the 0.8B, and the large wave region is determined.
(3) Select one point that is closest to the outermost surface layer in the area of each large wave, and measure the distance X 1 , X 2 , ... between adjacent large waves starting from that point. .
(4) The average value of the distance between the large waves is obtained for each sample.
(5) The value obtained by averaging the distances between the large waves of all the samples is taken as the average distance between the large waves of the coated plate.
本発明において柚子肌が発生するメカニズムは明確ではないが、次のような機構が考えられる。
乾燥過程で塗膜の最外表層に何らかの原因で表面張力の高い部分と低い部分が発生し、表面張力の高い部分に塗膜が引っ張られて凹凸が形成される。凹凸が形成されると、表面の場所による溶剤の揮発速度差が生じ、それによって温度差もできるため、塗膜に対流が生じる。この対流によって、塗膜中の場所による溶剤濃度差が生じ、それによって表面張力差が生じ、この表面張力差によって、更に凹凸が生じる。このような現象の複合により、柚子肌が形成される。
In the present invention, the mechanism by which aubergine skin is generated is not clear, but the following mechanism is conceivable.
During the drying process, a portion having a high surface tension and a portion having a low surface tension are generated on the outermost surface layer of the coating film for some reason, and the coating film is pulled to a portion having a high surface tension to form irregularities. When the unevenness is formed, a difference in the volatilization rate of the solvent depending on the location of the surface is caused, and a temperature difference is thereby created, and thus convection is generated in the coating film. This convection causes a difference in solvent concentration depending on the location in the coating film, resulting in a difference in surface tension, and further unevenness is caused by this difference in surface tension. As a result of the combination of these phenomena, cocoon skin is formed.
本発明の柚子肌状塗装板の製造方法では、少なくとも上下二層の塗膜をウェット状態で形成し、同時に加熱乾燥することが必須である。塗膜形成のための塗料の塗布方法は、カーテンコーターやロールコーターによるウェットオンウェット法、又はスライドカーテンコーターによる多層同時塗布法でよく、後者がより好適である。 In the method for producing the aubergine-skin-coated sheet according to the present invention, it is essential to form at least two upper and lower coating films in a wet state and simultaneously heat-dry them. The coating method for forming the coating film may be a wet-on-wet method using a curtain coater or a roll coater, or a multilayer simultaneous coating method using a slide curtain coater, and the latter is more preferable.
本発明の方法では、最表層塗膜を形成する塗料中に表面張力が異なる2種類以上の界面活性剤を混入することができ、これによってより良好な柚子肌を得ることができる。理由は不明だが、表面張力が異なる界面活性剤は、塗膜表面で溶剤の揮発速度の差を生じさせて前述の如く微細な対流現象を誘起するものと思われる。 In the method of the present invention, two or more kinds of surfactants having different surface tensions can be mixed in the coating material forming the outermost layer coating film, and thereby, a better cocoon skin can be obtained. Although the reason is unknown, it is considered that surfactants having different surface tensions induce a difference in the volatilization rate of the solvent on the surface of the coating film and induce the fine convection phenomenon as described above.
界面活性剤としては、アクリル樹脂系、シリコーン系、フッ素系、炭化水素系などが好適であり、界面活性があれば他のものでもよい。界面活性剤には、消泡剤、レベリング剤、分散剤、滑剤、発泡剤など各種の目的に沿ったものがあるが、いずれも使用可能である。塗料中の界面活性剤の濃度は、0.4mass%以下であるのが好適である。0.4mass%を超える場合には、塗布時の作業性が悪くなる。例えば、塗料をカーテン塗布する場合にはカーテンの安定性が乱されやすくなり、ロール塗布の場合には柚子肌とは別のリビング(塗布方向にほぼ平行した筋模様、参考文献:色材協会誌、第73巻9号、p.461)などの欠陥の発生が目立ちやすくなる。 As the surfactant, acrylic resin-based, silicone-based, fluorine-based, hydrocarbon-based and the like are suitable, and other surfactants may be used as long as they have surface activity. There are surfactants that meet various purposes such as antifoaming agents, leveling agents, dispersants, lubricants, and foaming agents, and any of them can be used. The concentration of the surfactant in the paint is preferably 0.4 mass% or less. When it exceeds 0.4 mass%, workability at the time of application is deteriorated. For example, when curtains are applied, the stability of the curtain tends to be disturbed, and when rolls are applied, the living room is different from the cocoon skin (streaks that are almost parallel to the direction of application, Reference: Color Material Association Magazine). , Vol. 73, No. 9, p.461) and the like are more noticeable.
塗料で使用する溶剤の種類を変えることによっても、表面張力の調整が可能である。例えば、N-メチルピロリドンは約42mN/mと高い表面張力を示し、エトキシエチルプロピオネートは約27mN/m、キシレンは約32mN/mの表面張力を示す。 The surface tension can also be adjusted by changing the type of solvent used in the paint. For example, N-methylpyrrolidone has a high surface tension of about 42 mN / m, ethoxyethyl propionate has a surface tension of about 27 mN / m, and xylene has a surface tension of about 32 mN / m.
最表層塗膜を形成する塗料として、その表面張力を5回測定したとき、その最大値と最小値との差が2mN/m以上あるような塗料を使用することによっても、良好な柚子肌を得ることができる。この理由については不明であるが、例えば、以下のように考えられる。 As a paint that forms the outermost layer coating film, when the surface tension is measured 5 times, the use of a paint that has a difference between the maximum value and the minimum value of 2 mN / m or more can also provide good cocoon skin. Obtainable. Although the reason for this is unknown, it can be considered as follows, for example.
表面張力を複数回測定したとき、その値が大きくばらつく現象は、塗料中に表面張力のミクロ的な不均一性が生じていることを示す。最表層塗膜を形成する塗料中に表面張力のミクロ的不均一性が生ずると、それがきっかけとなって乾燥過程で最表層塗膜内に前述のような微細な対流現象が誘起され、良好な柚子肌が形成されるものと思われる。 When the surface tension is measured a plurality of times, the phenomenon that the value varies greatly indicates that micro-uniformity of the surface tension occurs in the paint. If the surface tension microscopic non-uniformity occurs in the coating that forms the outermost layer coating, it causes the fine convection phenomenon as described above to be induced in the outermost layer coating during the drying process. It seems that the coconut skin is formed.
良好な柚子肌を形成するためには、表面張力を連続して5回測定し、その最大値と最小値との差が2mN/m以上であることが好ましい。2mN/m未満であると、良好な柚子肌が得られないことがある。表面張力の最大値と最小値の差の上限値は、特に限定されないが、10mN/mを超える場合は塗料の攪拌が十分でない可能性が高いことから、10mN/m以下であることが望ましい。塗料の表面張力は、20℃での白金リング引き上げ法による静的表面張力の値を適用すればよい。 In order to form a good cocoon skin, it is preferable that the surface tension is continuously measured five times, and the difference between the maximum value and the minimum value is 2 mN / m or more. If it is less than 2 mN / m, good cocoon skin may not be obtained. The upper limit value of the difference between the maximum value and the minimum value of the surface tension is not particularly limited. However, if it exceeds 10 mN / m, it is highly possible that the paint is not sufficiently stirred, and therefore it is preferably 10 mN / m or less. As the surface tension of the paint, the value of the static surface tension by the platinum ring pulling method at 20 ° C. may be applied.
本発明では、最表層塗膜と下層塗膜の塗料の表面張力を制御することによっても柚子肌を形成することが可能である。柚子肌を形成するには、最表層塗膜の塗料の表面張力δaと下層塗膜の塗料の表面張力δbの差の絶対値が、0.1mN/m≦｜δa-δb｜≦5.0mN/mの範囲内にあることが重要である。表面張力差が0.1mN/m未満では、塗膜内で対流現象が発生しても塗膜表面の表面張力の不均一が起こりにくく、柚子肌が形成され難い。一方、5.0mN/mを超えると、上下層の大きい表面張力差によって最表層塗膜と下層塗膜の界面が逆に安定化し、上下層を通じた対流が抑制され、柚子肌が発生しにくい。 In the present invention, the insulator skin can be formed also by controlling the surface tension of the paint of the outermost layer coating film and the lower layer coating film. In order to form cocoon skin, the absolute value of the difference between the surface tension δa of the outermost layer paint and the surface tension δb of the lower layer paint is 0.1 mN / m ≦ | δa-δb | ≦ 5.0 mN / m It is important to be within the range. When the difference in surface tension is less than 0.1 mN / m, even if a convection phenomenon occurs in the coating film, the surface tension of the coating film surface is unlikely to be uneven, and cocoon skin is difficult to form. On the other hand, when it exceeds 5.0 mN / m, the interface between the outermost layer coating and the lower layer coating is stabilized due to a large difference in surface tension between the upper and lower layers, convection through the upper and lower layers is suppressed, and insulator skin is hardly generated.
本発明においては、塗膜の加熱乾燥による塗料樹脂の硬化中に上層(最表層塗膜)とその下層の塗料の一部が適度に再配置されて対流が生じ、上下層の境界面が波状構造を形成して、良好な柚子肌外観を得ることができる。このような機構により柚子肌を形成するためには、上下層の表面張力の差を前記の範囲内に維持する必要がある。 In the present invention, during curing of the coating resin by heat drying of the coating film, the upper layer (outermost layer coating film) and a part of the lower layer coating are appropriately rearranged to cause convection, and the boundary surface between the upper and lower layers is wavy. A good cocoon skin appearance can be obtained by forming a structure. In order to form cocoon skin by such a mechanism, it is necessary to maintain the difference in surface tension between the upper and lower layers within the above range.
上記の範囲に塗料の表面張力を調整する方法としては、塗料の添加剤(例えばレベラー、界面活性剤等)の種類を変更したりその添加量を調整する方法、溶剤の種類と量を変える方法などが可能である。例えば、塗料中の界面活性剤を添加して表面張力を調整する場合には、塗料中の界面活性剤濃度は、上述のように0.4mass%以下であるのが好ましい。 As a method of adjusting the surface tension of the paint within the above range, a method of changing the kind of paint additive (e.g., leveler, surfactant, etc.) or a method for adjusting the amount thereof, a method of changing the kind and amount of the solvent Etc. are possible. For example, when the surface tension is adjusted by adding a surfactant in the paint, the surfactant concentration in the paint is preferably 0.4 mass% or less as described above.
上下層の塗料は、それらの粘度が低いほど流動の障壁がなくなるため、柚子肌が発生し易くなる。塗料の粘度は0.2〜1.0Pa・sの範囲に調整し、望ましくは0.5〜1.0Pa・sの範囲とする。塗料の粘度の調整は、塗料中の溶剤量や溶剤種類の変更によって行うことができる。また、増粘剤などの添加剤によって粘度を調整することも可能であり、公知の方法によればよい。 Since the upper and lower layer coating materials have lower flow barriers as their viscosities are lower, insulator skin is more likely to occur. The viscosity of the paint is adjusted in the range of 0.2 to 1.0 Pa · s, preferably in the range of 0.5 to 1.0 Pa · s. The viscosity of the paint can be adjusted by changing the amount of solvent or the kind of solvent in the paint. Moreover, it is also possible to adjust a viscosity with additives, such as a thickener, and what is necessary is just to follow a well-known method.
上述の塗料条件の調整に加え、柚子肌形成のもう一つの重要なファクターが塗膜の加熱乾燥条件である。 In addition to the above-described adjustment of the paint conditions, another important factor for the formation of cocoon skin is the heat drying condition of the coating film.
本発明では、加熱方法については、特に限定されない。赤外線輻射、熱風、超音波加熱、誘導加熱など、製品に応じて適宜選択すればよい。 In the present invention, the heating method is not particularly limited. What is necessary is just to select suitably according to products, such as infrared radiation, a hot air, ultrasonic heating, induction heating.
とは言え、塗膜中の塗料の対流現象を起すには、基板側から加熱するほうが生産効率を高くするのに有利である。塗膜表面から加熱しても対流現象を発生させることはできるが、加熱速度は基板側から加熱するほど高くできない。この観点から、金属を基板とする場合は、誘導加熱、通電加熱、超音波加熱など塗膜内面(基板側)から加熱乾燥する手段を採用するのが好適であり、基板側からの急速加熱によって柚子肌を発生させ易くなる。 However, in order to cause the convection phenomenon of the paint in the coating film, heating from the substrate side is advantageous for increasing the production efficiency. Although the convection phenomenon can be generated even when heated from the surface of the coating film, the heating rate cannot be so high as it is heated from the substrate side. From this point of view, when a metal is used as a substrate, it is preferable to adopt a means for heating and drying from the coating film inner surface (substrate side) such as induction heating, electric heating, ultrasonic heating, etc., by rapid heating from the substrate side. It becomes easy to generate cocoon skin.
金属基板の加熱速度は特に限定されないが、一般に1〜20℃/秒の範囲とするのが好適である。1℃/秒より小さいと生産性が落ちるので好ましくなく、20℃/秒より大きいとわきの問題が発生する。 The heating rate of the metal substrate is not particularly limited, but is generally preferably in the range of 1 to 20 ° C./second. If it is less than 1 ° C / second, the productivity is lowered, which is not preferable, and if it is higher than 20 ° C / second, a side problem occurs.
次に、実施例により本発明を更に説明する。とは言え、本発明が以下の実施例に限定されるものでないことは言うまでもない。 Next, the present invention will be further described with reference to examples. However, it goes without saying that the present invention is not limited to the following examples.
亜鉛を60g/m2めっきした鋼板に塗装下地処理としてノンクロメート処理(日本パーカライジング社製CTE236)を施して基板を作製した。 Non-chromate treatment (CTE236 manufactured by Nihon Parkerizing Co., Ltd.) was applied to a steel plate coated with 60 g / m 2 of zinc as a coating base treatment to produce a substrate.
この基板上に、表1、表2に示す本発明による塗膜A-1〜A-21(これらのうち、塗膜A-11〜A-14は参考例である)を形成した。これらの塗膜は、乾燥平均膜厚10μmの最表層(上層)塗膜層と乾燥平均膜厚12μmの下層塗膜層から構成され、上層塗膜層はポリエステル系樹脂FLC7000(日本ファインコーティング社製、ベージュ色)を主樹脂とする塗料を用い、下層塗膜層はポリエステル系樹脂(日本ファインコーティング社製、ベージュ色、樹脂のガラス転移点12℃)を主樹脂とする塗料を用いて、カーテンコーターを使用するウェットオンウェット法又はスライドホッパー型カーテン塗布装置を使用する同時多層塗布法により形成した。なお、結果はいずれの塗装方法によっても同一であった。 On this substrate, coating films A-1 to A-21 according to the present invention shown in Tables 1 and 2 (among these, coating films A-11 to A-14 are reference examples) were formed. These coatings consist of an outermost layer (upper layer) coating layer having a dry average film thickness of 10 μm and a lower layer coating layer having a dry average film thickness of 12 μm. The upper coating layer is a polyester resin FLC7000 (manufactured by Nippon Fine Coating Co., Ltd.). , Beige color), and the lower coating layer is made of a polyester resin (made by Nippon Fine Coating, beige color, glass transition point of resin 12 ° C). It was formed by a wet-on-wet method using a coater or a simultaneous multilayer coating method using a slide hopper type curtain coating apparatus. In addition, the result was the same with any coating method.
上下層の塗料に各種添加剤を配合してその表面張力を変化させた。使用した添加剤は次のとおりである。
・ポリフロ-S:楠本化成社製界面活性剤
・非Si系レベラー(S):楠本化成社製界面活性剤
・BYK-141:BYK社製Si系消泡剤
・BYK-080:BYK社製Si系消泡剤
・BYK-065:BYK社製Si系消泡剤
・BYK-057:BYK社製非Si系消泡剤
・BYK-055:BYK社製非Si系消泡剤
・BYK-053:BYK社製非Si系消泡剤
・BYK-077:BYK社製非Si系消泡剤
・Si系レベラー:BYK社製Si系レベラー
上層塗膜には、特に指示しない限り0.2mass%のポリフロ-Sを添加し、下層塗膜には表1、表2に示した量の添加剤を添加した。
Various additives were blended in the upper and lower coating layers to change the surface tension. The additives used are as follows.
・ Polyflo-S: Surfactant manufactured by Enomoto Kasei Co., Ltd. ・ Non-Si leveler (S): Surfactant manufactured by Enomoto Kasei Co., Ltd. ・ BYK-141: Si-based antifoaming agent manufactured by BYK ・ BYK-080: Si manufactured by BYK BYK-065: BYK Si-based antifoam agent BYK-057: BYK Non-Si-based antifoam agent BYK-055: BYK Non-Si-based antifoam agent BYK-053: BYK non-Si defoamer ・ BYK-077: BYK non-Si defoamer ・ Si leveler: BYK Si leveler Unless otherwise specified, 0.2 mass% polyflow S was added, and the amount of additives shown in Tables 1 and 2 was added to the lower coating film.
各上層用塗料及び各下層用塗料の樹脂、架橋剤、顔料成分は同じとし、特に指示しない限り溶剤としてキシレン/ソルベッソ150(1/1質量比)を用いた。A-13〜A-16の下層塗膜では、添加剤を添加せずに溶剤の種類を変更することにより表面張力を変化させた。塗膜の加熱乾燥条件は、熱風炉で最高到達板温230℃、乾燥時間70秒、とした。 The resin, the cross-linking agent, and the pigment component of each upper layer paint and each lower layer paint were the same, and xylene / solvesso 150 (1/1 mass ratio) was used as a solvent unless otherwise specified. In the lower coating films A-13 to A-16, the surface tension was changed by changing the type of the solvent without adding the additive. The coating film was heated and dried under the conditions of a hot air oven with a maximum plate temperature of 230 ° C. and a drying time of 70 seconds.
各塗料の表面張力、上層及び下層塗料の表面張力の差の絶対値を、加熱乾燥後の塗膜の柚子肌形成の有無(柚子肌形成は○、柚子肌形成なしは×)とともに表1、表2に示す。 Table 1, the absolute value of the surface tension of each paint, the difference in surface tension between the upper and lower paints, along with the presence or absence of cocoon skin formation of the coating after heat drying (○ for cocoon skin formation, x for cocoon skin formation) Table 2 shows.
上層及び下層塗料の表面張力差の絶対値｜δa-δb｜を制御することによって、柚子肌の形成が可能なことが分かる。｜δa-δb｜が5.0mN/mを超える(参考例の塗膜A-11〜A-14)と、塗膜層間の境界面が安定するため柚子肌は部分的にしか出現しない。また、δaとδbに差が無い場合(A-21)にも柚子肌は形成されないか不明瞭なものとなった。 By controlling the absolute value | δa−δb | of the surface tension difference between the upper layer and the lower layer paint, it can be seen that the cocoon skin can be formed. When | δa−δb | exceeds 5.0 mN / m (coating films A-11 to A-14 in the reference example), the boundary surface between the coating film layers becomes stable, and the insulator skin appears only partially. In addition, even when there is no difference between δa and δb (A-21), cocoon skin was not formed or became unclear.
実施例1で作製した亜鉛めっき鋼板に、実施例１で説明した塗膜A-1〜A-10を形成した試験片と、次に示す比較例の塗膜B-1〜B-5を形成した試験片を用意した。 On the galvanized steel sheet prepared in Example 1, the test pieces on which the coating films A-1 to A-10 described in Example 1 were formed and the coating films B-1 to B-5 of the following comparative examples were formed. A prepared test piece was prepared.
(1) 塗膜B-1
基板上にポリエステル系プライマー樹脂の下層塗膜5μmを形成(焼付)し、その上層にガラス転移点12℃のポリエステル樹脂とブチル化メラミン樹脂を85/15(質量比)の比率で配合した樹脂にポリエステル樹脂ビーズ(粒径40μm)を10%含有させた塗料を塗布し、そして高周波誘導加熱炉を用いて最高到達板温230℃で焼付けた。樹脂ビーズを含む上層の乾燥膜厚は15μmであった。
(2) 塗膜B-2
ポリエステル樹脂のガラス転移点を35℃にした以外はB-1と同じ。
(3) 塗膜B-3
ポリエステル樹脂ビーズを含有しない以外はB-1と同じ。
(4) 塗膜B-4
樹脂ビーズの平均粒径を10μm、樹脂ビーズの添加量を12%とした以外はB-1と同じ。
(5) 塗膜B-5
樹脂ビーズの添加量を2%とした以外はB-1と同じ。
(1) Coating B-1
A 5 μm lower layer coating of polyester primer resin is formed (baked) on the substrate. A paint containing 10% polyester resin beads (particle size 40 μm) was applied and baked at a maximum plate temperature of 230 ° C. using a high-frequency induction heating furnace. The dry film thickness of the upper layer containing the resin beads was 15 μm.
(2) Coating B-2
Same as B-1, except that the glass transition point of the polyester resin is 35 ° C.
(3) Coating B-3
Same as B-1, except it does not contain polyester resin beads.
(4) Coating B-4
Same as B-1, except that the average particle size of the resin beads is 10 μm and the addition amount of the resin beads is 12%.
(5) Coating B-5
Same as B-1, except that the amount of resin beads added is 2%.
各塗膜のWca、Wc-smの測定を、東洋精密社製の表面粗度測定機Surfcomを用い、測定長さ25mm、カットオフ80μm、測定速度0.5mm/sで行った。 Wca and Wc-sm of each coating film were measured using a surface roughness measuring machine Surfcom manufactured by Toyo Seimitsu Co., Ltd., with a measurement length of 25 mm, a cutoff of 80 μm, and a measurement speed of 0.5 mm / s.
耐傷付性は、はがきを指で塗膜表面に荷重約5kgで押し当てて、塗膜表面上を30回往復させて擦った後の、塗膜表面の傷付き具合を目視で判定した。傷が目立つ場合は×、傷がほとんど見えない場合を〇、若干の傷が見える場合を△と評価した。 The scratch resistance was determined by visual observation of the degree of scratching on the coating film surface after the postcard was pressed against the coating film surface with a finger at a load of about 5 kg and rubbed by reciprocating 30 times on the coating film surface. The case where the scratches were conspicuous was evaluated as x, the case where the scratches were hardly visible was evaluated as ◯, and the case where some scratches were visible was evaluated as Δ.
加工性の評価は、20℃でT折り曲げ試験を行い、折り曲げ加工部の塗膜に10倍ルーペで観察して亀裂が入らない限界のＴを求めることにより行った。例えば、2T曲げで亀裂が認められ3T曲げで亀裂が認められなかった場合は、評点は3Tとなる。 The workability was evaluated by performing a T-bending test at 20 ° C. and observing the coating film of the bent portion with a 10-fold loupe to obtain the limit T at which cracks do not occur. For example, if a crack is observed in 2T bending and no crack is observed in 3T bending, the score is 3T.
光沢の評価には、塗膜表面の60度鏡面反射率(%)を採用した。 For the evaluation of gloss, the 60-degree specular reflectance (%) of the coating film surface was adopted.
得られた結果を、塗膜断面の上下層塗膜界面の大波間距離及び目視による外観とともに、表3に示す。 The obtained results are shown in Table 3 together with the distance between the waves at the upper and lower coating film interfaces of the coating film cross section and the visual appearance.
ビーズを混入した比較例の塗膜B-1、B-2、B-4、B-5では、加工性又は耐傷付性の何れかが劣る。ビーズ混入のない塗膜B-3では、柚子肌ができない。 In the coating films B-1, B-2, B-4, and B-5 of Comparative Examples in which beads are mixed, either processability or scratch resistance is inferior. In coating film B-3 without bead contamination, cocoon skin is not possible.
実施例1で作製した亜鉛めっき鋼板に、実施例1で説明した塗膜A-3、A-9の塗料を、スライド式のカーテンコーターを用いて下層10μm、上層12μmとなるように塗布し、誘導加熱炉及び熱風加熱炉を用いて、加熱条件を変えて焼き付けた。加熱条件は、常温(約20℃)から最高到達板温である230℃まで加熱し、その際の加熱速度(230℃に到達するまでの平均速度)を、
A: 1.0℃/秒
B: 2.5℃/秒
C: 4.0℃/秒
D: 5.5℃/秒
E: 20℃/秒
とした。
To the galvanized steel sheet produced in Example 1, the coatings A-3 and A-9 described in Example 1 were applied using a slide curtain coater so that the lower layer was 10 μm and the upper layer was 12 μm. Using an induction heating furnace and a hot-air heating furnace, baking was performed under different heating conditions. Heating conditions are from normal temperature (about 20 ° C) to the maximum temperature of 230 ° C, and the heating rate at that time (average rate until reaching 230 ° C)
A: 1.0 ℃ / sec
B: 2.5 ℃ / sec
C: 4.0 ℃ / sec
D: 5.5 ℃ / sec
E: 20 ° C./second.
加熱処理後の塗膜表面を観察して、柚子肌がうまくできている場合を○、できていない場合を×と評価した。結果を表4に示す。 The surface of the coating film after the heat treatment was observed, and the case where the cocoon skin was successfully made was evaluated as ◯, and the case where it was not formed was evaluated as ×. The results are shown in Table 4.
表4の結果から、誘導加熱を用いるとラインスピードを速くでき、制御性よく柚子肌を形成できることが分かる。誘導加熱を用いたいずれの事例でも、溶剤が塗膜中からうまく抜けないために発生するワキ欠陥は認められなかった。 From the results in Table 4, it can be seen that if induction heating is used, the line speed can be increased and the insulator skin can be formed with good controllability. In any case where induction heating was used, no cracking defect occurred because the solvent did not escape well from the coating film.
実施例1で作製した亜鉛めっき鋼板に、表5に示す本発明による塗膜A-22〜A-24(これらのうち、塗膜A-24は参考例である)を形成した。これらの塗膜は、表5に示した添加剤を除いて、実施例1と同一の条件とした。塗料の調整に際しては、塗料に所定の添加剤を添加してから、高速ディスパ装置(東洋精機社製ペイントシェイカーモデルSCD）にて2000rpmで15分間強攪拌した。 Coating films A-22 to A-24 according to the present invention shown in Table 5 (of these, coating film A-24 is a reference example) were formed on the galvanized steel sheet produced in Example 1. These coating films had the same conditions as in Example 1 except for the additives shown in Table 5. In preparing the paint, a predetermined additive was added to the paint, and then vigorously stirred at 2000 rpm for 15 minutes with a high-speed dispa device (Paint Shaker Model SCD manufactured by Toyo Seiki Co., Ltd.).
上層の塗料調整直後の表面張力測定は、強攪拌後20分間静置してから行った。また、1日放置後、1ヶ月放置後の塗料の表面張力測定は、高速ディスパ装置にて2000rpmで5分間強攪拌し、20分間静置してから行った。なお、塗料の表面張力測定には、BYK社製のダイノメーターを用い、20℃における白金リング引き上げ法による静的表面張力の値を測定した。 The surface tension measurement immediately after adjustment of the upper layer paint was carried out after standing for 20 minutes after vigorous stirring. In addition, the surface tension of the paint after standing for 1 day and after standing for 1 month was measured after vigorously stirring at 2000 rpm for 5 minutes with a high-speed disperser and allowing to stand for 20 minutes. The surface tension of the paint was measured using a BYK dynometer and the static surface tension measured by the platinum ring pulling method at 20 ° C.
一般的な塗料の表面張力を5回測定した場合、通常その最大値と最小値の差(ばらつき)は、大きくても0.05mN/mの範囲内に収まるのが普通であるが、本発明に用いる塗料(A-22)では2.8mN/mとなっている。上層と下層の表面張力差が無いので、通常であれば柚子肌の形成は起こらないが、上層の表面張力のばらつきが2mN/m以上となっているため、柚子肌外観が得られている。 When the surface tension of a general paint is measured five times, the difference between the maximum and minimum values (variation) is usually within 0.05 mN / m at the most. The paint used (A-22) has a value of 2.8 mN / m. Since there is no difference in surface tension between the upper layer and the lower layer, the formation of cocoon skin does not usually occur, but since the variation in the surface tension of the upper layer is 2 mN / m or more, the cocoon skin appearance is obtained.
この塗料を保管しておくと、表面張力のばらつきは徐々に小さくなっていく。1日保管後(A-23)では、未だ表面張力のばらつきが2.1mN/mであるため、柚子肌外観が発現している。しかしながら、1ヶ月保管後(A-24)には、表面張力のばらつきが1.5mN/mとなり、柚子肌外観は見られなくなっている。 When this paint is stored, the variation in surface tension gradually decreases. After storage for 1 day (A-23), since the variation in surface tension is still 2.1 mN / m, the cocoon skin appearance is still manifesting. However, after storage for 1 month (A-24), the surface tension variation is 1.5 mN / m, and the cocoon skin appearance is not seen.
本発明による塗装板は、美的表面外観と意匠性が要求される建材、家電、日用雑貨、自動車などの分野で広く使用される可能性がある。特に、本発明の塗装板は塗装後に成形加工処理を受けても塗膜が損傷せずに柚子肌状の美観を保つので、プレコート金属板への応用が期待される。
更に、柚子肌状の意匠は紛体塗装や静電塗装法により形成される場合が多いので、この分野の代替技術として本発明の製造方法が利用される可能性が高い。
The coated plate according to the present invention may be widely used in the fields of building materials, home appliances, daily goods, automobiles and the like that require aesthetic surface appearance and design. In particular, the coated plate of the present invention is expected to be applied to a pre-coated metal plate because the coating film is not damaged even if it is subjected to a molding treatment after coating, and the aesthetic appearance of a cocoon skin is maintained.
Furthermore, since the insulator-like design is often formed by powder coating or electrostatic coating, the manufacturing method of the present invention is likely to be used as an alternative technique in this field.
1 基板
3 下層塗膜
5 最表層塗膜
10 塗装板
1 Board
3 Underlayer coating
5 outermost layer coating
10 Paint board
Claims (15)
(1) 塗膜最外表面と境界面の波形曲線との距離をA、最表層塗膜の平均膜厚をBとして、A≦0.8Bの領域を持つとして定義される大波を含むこと、
(2) 大波間の平均距離が750μm以下であること、
という条件を満足することを特徴とする加工性、耐傷付性に優れた塗装板。 The outermost surface of the coating has a wavy centerline average (Wca) of 0.35 μm ≦ Wca ≦ 1.25 μm, and the average waviness of the waviness of the waviness (Wc-sm) is 2800 μm ≦ Wc-sm ≦ 12500 μm. boundary surface coating and the underlying coating film have a corrugated structure, the curve of the waveforms appearing when observing the interface between the outermost layer coating film and the underlying coating in the coating thickness direction cross-section,
(1) The distance between the outermost surface of the coating film and the waveform curve of the boundary surface is A, the average film thickness of the outermost layer coating film is B, and includes a large wave defined as having an area of A ≦ 0.8B,
(2) The average distance between large waves is 750 μm or less,
A paint plate with excellent workability and scratch resistance, characterized by satisfying the above conditions .
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| JP2005250971A JP4837337B2 (en) | 2004-08-31 | 2005-08-31 | Painted plate excellent in processability and scratch resistance and method for producing the same |
| KR1020087004937A KR101006245B1 (en) | 2005-08-31 | 2006-03-10 | Painted plate excellent in workability and scratch resistance, and method for producing the same |
| KR1020107019326A KR20100112186A (en) | 2005-08-31 | 2006-03-10 | Painted plate excellent in workability and scratch resistance, and method for producing the same |
| PCT/JP2006/305299 WO2007026442A1 (en) | 2005-08-31 | 2006-03-10 | Painted plate excellent in workability and scratch resistance, and method for producing the same |
| CN2006800321203A CN101253001B (en) | 2005-08-31 | 2006-03-10 | Coated plate excellent in workability and scratch resistance and manufacturing method for the same |
| US11/990,828 US20090246472A1 (en) | 2005-08-31 | 2006-03-10 | Precoated sheet having good workability and scratch resistance and method for production thereof |
| SG201006293-3A SG165323A1 (en) | 2005-08-31 | 2006-03-10 | Precoated sheet having good workability and scratch resistance and method for production thereof |
| EP06715693A EP1930088A4 (en) | 2005-08-31 | 2006-03-10 | Painted plate excellent in workability and scratch resistance, and method for producing the same |
| RU2008112172/12A RU2388552C2 (en) | 2005-08-31 | 2006-03-10 | Sheet with applied coat that has high mohs' hardness and good machinability |
| TW095108413A TWI291918B (en) | 2005-08-31 | 2006-03-13 | Precated sheet having good workability and scratch resistance and method for production thereof |
| MYPI20061632 MY152913A (en) | 2005-08-31 | 2006-04-10 | Precoated sheet having good workability and scratch resistance and method for producing thereof |
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| JPH04370164A (en) * | 1991-06-18 | 1992-12-22 | Nippon Paint Co Ltd | Coating composition |
| JPH06190336A (en) * | 1992-12-24 | 1994-07-12 | Nippon Steel Corp | Preparation of pattern-coated metal sheet |
| JP3143316B2 (en) * | 1994-04-04 | 2001-03-07 | 住友金属建材株式会社 | Painted metal plate with yuzu skin appearance |
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| JP3686513B2 (en) * | 1998-01-20 | 2005-08-24 | 新日本製鐵株式会社 | Manufacturing method of coated metal plate with smooth uneven appearance |
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