JP2003118033A - Metal plate having hydrophilic lower layer coating film and coated metal plate - Google Patents
Metal plate having hydrophilic lower layer coating film and coated metal plateInfo
- Publication number
- JP2003118033A JP2003118033A JP2001319719A JP2001319719A JP2003118033A JP 2003118033 A JP2003118033 A JP 2003118033A JP 2001319719 A JP2001319719 A JP 2001319719A JP 2001319719 A JP2001319719 A JP 2001319719A JP 2003118033 A JP2003118033 A JP 2003118033A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- metal plate
- coating
- lower layer
- condensate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、優れた密着性で上層塗
膜が形成されるように下層塗膜を改良した金属板及び塗
装金属板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal plate and a coated metal plate in which a lower layer coating film is improved so that an upper layer coating film can be formed with excellent adhesion.
【０００２】[0002]
【従来の技術】外装建材に金属板を使用する場合、耐食
性、耐久性、意匠性等を改善するために一般的に塗装が
施されており、耐久性に優れた種々の塗料が開発され汎
用されている。プレコート金属板としては下塗り塗膜及
び上塗り塗膜の２コートタイプが主流である。場合によ
っては、中塗りを設けることもある。下塗り塗膜は、下
地金属板を隠蔽すると共に、防錆顔料等の添加によって
塗装金属板の耐食性を改善する作用を持つ。上塗り塗膜
には、塗装金属板の意匠性を高めるために必要とする色
調に応じた着色顔料やメタリック顔料が添加され、或い
は耐摩耗性、耐汚れ付着性、耐キズ付き性等の性能を改
善するために樹脂ビーズ、無機粉末、ＴｉＯ2等の光触
媒、骨材等が添加されることもある。2. Description of the Related Art When a metal plate is used as an exterior building material, it is generally painted to improve its corrosion resistance, durability, design, etc. Has been done. As the pre-coated metal plate, a two-coat type of an undercoat coating film and a top coating film is mainly used. In some cases, an intermediate coating may be provided. The undercoating film has a function of concealing the base metal plate and improving the corrosion resistance of the coated metal plate by adding a rust preventive pigment or the like. The top coating film is added with a color pigment or metallic pigment according to the color tone required to enhance the design of the coated metal plate, or wear resistance, stain resistance, scratch resistance, etc. To improve, resin beads, inorganic powder, photocatalyst such as TiO 2 , aggregate, etc. may be added.
【０００３】下塗り塗膜と上塗り塗膜の間の親和性が十
分でないと、塗装金属板を加工する場合等で下塗り塗膜
／上塗り塗膜の界面で層間剥離したり、建材として使用
される間に塗膜膨れや剥離が生じることがある。そのた
めに、上塗り塗料の種類に応じて下塗り塗料を選択する
必要があった。更に、プレコート金属板の上塗り塗膜の
上層にインライン又はポストコートで上層塗膜が形成さ
れる場合もある。If the affinity between the undercoating film and the topcoating film is not sufficient, delamination may occur at the interface of the undercoating film / topcoating film during processing of a coated metal plate, or during use as a building material. The coating may swell or peel off. Therefore, it is necessary to select the undercoat paint depending on the type of the topcoat paint. Further, the upper coating film may be formed in-line or by post coating on the upper coating film of the precoated metal plate.
【０００４】[0004]
【発明が解決しようとする課題】一般的にプレコート金
属板は２コート又は３コートの塗膜層を有する。それぞ
れの下層塗膜を形成するための塗料は、その上層塗膜用
塗料の塗れ性および上層塗膜との密着性を確保できる性
能を有するものが選択され、使用できるものは限定され
たものとなっている。更に、プレコート金属板の上塗り
塗膜の上層にインライン又はポストコートで上層塗膜が
形成される場合もある。しかし、プレコート金属板用上
塗り塗膜は、通常、焼付け型塗料であるため塗膜の架橋
密度が高く緻密な表面であったり、フッ素塗膜などのよ
うに表面張力が低いものであるために、その上層に塗装
すると、濡れ性が悪く塗料をはじいたり、塗れたとして
も層間密着性が不十分である場合が多くある。本発明
は、上記のプレコート金属板の各塗膜層間密着性の向上
及びプレコート金属板の上塗り塗膜上へのインライン又
はポストコートで塗装したオーバーコートの密着性付与
の何れの場合にも適用できるものである。Generally, a precoated metal sheet has a coating layer of 2 coats or 3 coats. As the coating material for forming each lower layer coating film, those having the ability to secure the wettability of the coating material for the upper layer coating film and the adhesiveness with the upper layer coating film are selected, and those that can be used are limited. Has become. Further, the upper coating film may be formed in-line or by post coating on the upper coating film of the precoated metal plate. However, the precoat metal plate top coating film is usually a baking-type coating material, so that the coating film has a high cross-linking density and a dense surface, or because the surface tension is low such as a fluorine coating film, When it is applied to the upper layer, the wettability is poor and the paint is repelled, and even if it is applied, the interlayer adhesion is often insufficient. INDUSTRIAL APPLICABILITY The present invention can be applied to any of the cases of improving the adhesion between the coating layers of the above-mentioned precoated metal sheet and imparting the adhesion of an overcoat applied by in-line or post-coating on the top coating film of the precoated metal sheet. It is a thing.
【０００５】[0005]
【課題を解決するための手段】ところで、本出願人は、
オルガノアルコキシシラン又はその縮合物を配合した塗
料を用いて塗膜を作製すると、耐汚れ付着性に優れた塗
膜表面が得られることを見出し、特開平８−３１８２１
６号公報、特開平１０−１２８２３２号公報で紹介し
た。その優れた耐汚れ性はオルガノアルコキシシランの
縮合物によって塗膜表面に親水性が付与され、疎水性の
汚染物質が雨水等で洗い流されることによるものであ
る。親水性が付与された塗膜表面について調査研究した
結果、塗膜の親水性は、耐汚れ付着性の向上だけでな
く、さらにその上層に塗装を施した場合、その上層塗膜
との層間密着性が向上することを見出した。その特性
は、上層塗膜がプレコート用熱硬化塗料、プレコート用
熱可塑性塗料、溶剤系常温乾燥塗料、水系常温乾燥塗
料、熱融着樹脂等通常使用されるほとんどの塗料種にお
いて発現することが分かった。[Means for Solving the Problems] By the way, the present applicant
It has been found that when a coating film is prepared using a coating material containing an organoalkoxysilane or a condensate thereof, a coating film surface excellent in stain resistance can be obtained.
No. 6 and Japanese Patent Laid-Open No. 10-128232. The excellent stain resistance is due to the fact that the organoalkoxysilane condensate imparts hydrophilicity to the surface of the coating film, and hydrophobic contaminants are washed away with rainwater or the like. As a result of investigating and researching the surface of the coating film to which hydrophilicity has been imparted, the hydrophilicity of the coating film is not only improved in stain resistance but also when the coating is applied to the upper layer, the interlayer adhesion with the upper layer coating It was found that the property is improved. It has been found that the characteristics of the upper coating film are exhibited in most commonly used paint types such as thermosetting paints for precoats, thermoplastic paints for precoats, solvent-based room temperature dry paints, water-based room temperature dry paints, and heat fusion resins. It was
【０００６】本発明は、このような知見をベースに完成
されたものであり、オルガノアルコキシシラン又はオル
ガノアルコキシシランの縮合物が表層に濃化した塗膜を
下層塗膜に利用することによって、上層塗膜の選択自由
度を拡大し、上層塗膜／下層塗膜間の層間剥離がなく、
塗膜密着性に優れた塗装金属板を提供することを目的と
する。本発明の塗装金属板は、その目的を達成するため
に上層塗膜の下地に用いられる下層塗膜の表層にオルガ
ノアルコキシシラン又はオルガノアルコキシシランの縮
合物を濃化させ、アルコキシル基の加水分解で生成した
水酸基が塗膜表面に配向するときに対水接触角が小さく
親水性に富む塗膜表面が得られる。The present invention has been completed on the basis of such findings, and an organoalkoxysilane or a condensate of an organoalkoxysilane is concentrated on the surface layer to form a coating film for the lower layer. Enhancing the degree of freedom in selecting coating films, eliminating delamination between upper layer coating / lower layer coating,
It is an object to provide a coated metal plate having excellent coating film adhesion. The coated metal plate of the present invention, in order to achieve the object, to concentrate the organoalkoxysilane or a condensate of organoalkoxysilane in the surface layer of the lower layer coating used as the underlayer of the upper layer coating, by hydrolysis of the alkoxyl group. When the generated hydroxyl groups are oriented on the surface of the coating film, the contact angle with water is small and the coating surface is highly hydrophilic.
【０００７】親水性に富む下層塗膜は、塗料樹脂１００
質量部に対して一般式Ｒ1 4-nＳｉ（ＯＲ2）n［ただし、
Ｒ1：アルキル基又はアルコキシル基、Ｒ2：アルキル
基、ｎ：３又は４］で表されるオルガノアルコキシシラ
ン又はその縮合物を１〜２０質量部の割合で配合した塗
料から形成される。オルガノアルコキシシラン又はその
縮合物に代えてオルガノアルコキシシラン又はその縮合
物をキレート化したキレート誘導体も使用できる。オル
ガノアルコキシシラン又はその縮合物を配合した塗料で
は、塗料中の水分とオルガノアルコキシシラン又はその
縮合物との反応により、塗料粘度の上昇を生じ、それが
進行すると塗料がゲル化する。塗料中の水分を除去する
為にオルト蟻酸トリアルキル、オルト酢酸トリアルキ
ル、オルト硼酸トリアルキル等の脱水剤を添加すること
が好ましい。顔料を添加する場合、水素イオンや水酸化
物イオンの発生源とならない中性顔料の使用が好まし
い。The lower layer coating film which is highly hydrophilic is a coating resin 100.
General formula R 1 4-n Si (OR 2 ) n [where
R 1 : alkyl group or alkoxyl group, R 2 : alkyl group, n: 3 or 4] or an organoalkoxysilane represented by the formula or a condensate thereof in a proportion of 1 to 20 parts by mass. A chelate derivative obtained by chelating an organoalkoxysilane or a condensate thereof may be used instead of the organoalkoxysilane or a condensate thereof. In a coating material containing an organoalkoxysilane or a condensate thereof, the reaction between water in the coating material and the organoalkoxysilane or a condensate thereof causes an increase in the viscosity of the coating material. In order to remove water in the paint, it is preferable to add a dehydrating agent such as trialkyl orthoformate, trialkyl orthoacetate, or trialkyl orthoborate. When a pigment is added, it is preferable to use a neutral pigment that does not generate hydrogen ions or hydroxide ions.
【０００８】[0008]
【作用】上層塗膜の下地に用いられる下層塗膜の表面に
オルガノアルコキシシラン又はオルガノアルコキシシラ
ンの縮合物を濃化させ、アルコキシル基の加水分解で生
成した水酸基を塗膜表面に配向させることによって、親
水性に富む塗膜表面を得ることができる。下層塗膜の表
面に水酸基を配向させることにより、下層塗膜の表面張
力が高くなり上層塗膜用塗料の濡れ性が良くなり、ハジ
キなどの欠陥のない良好な上層塗膜を形成することがで
きる。更に、下層塗膜表面のアルコキシル基又は水酸基
は、上層塗膜中に含まれる水酸基、メトキシ基、エトキ
シ基、カルボキシル基、カルボニル基、アミノ基、エポ
キシ基、エステル基、エーテル基等の官能基と水素結合
や一次結合を形成するために上層塗膜との密着性が向上
する。[Function] By concentrating an organoalkoxysilane or a condensate of organoalkoxysilane on the surface of a lower coating film used as a base of an upper coating film, and by orienting hydroxyl groups formed by hydrolysis of an alkoxyl group on the coating surface. It is possible to obtain a coating film surface having high hydrophilicity. By orienting hydroxyl groups on the surface of the lower coating film, the surface tension of the lower coating film becomes high and the wettability of the coating material for the upper coating film improves, so that a good upper coating film without defects such as cissing can be formed. it can. Further, the alkoxyl group or hydroxyl group on the lower layer coating surface is a functional group such as a hydroxyl group, a methoxy group, an ethoxy group, a carboxyl group, a carbonyl group, an amino group, an epoxy group, an ester group or an ether group contained in the upper layer coating film. Adhesion with the upper coating film is improved because hydrogen bonds and primary bonds are formed.
【０００９】下層塗膜用塗料に配合されたオルガノアル
コキシシラン又はその縮合物は、塗料の焼き付け時に表
面張力の小さいアルコキシル基が空気面すなわち塗膜表
面に配向する。塗膜表面のアルコキシル基は、空気中の
水分により加水分解され水酸基を生成する。加水分解の
速度は、アルコキシル基の種類や気温、湿度により異な
るが、アルコキシル基の一部が水酸基に変化しているだ
けで、上層塗膜の密着性を高めることができる。アルコ
キシル基を積極的に加水分解させるために酸やアルカリ
水溶液で処理することもできる。In the organoalkoxysilane or its condensate compounded in the coating material for the lower layer coating, the alkoxyl group having a small surface tension is oriented to the air surface, that is, the coating surface when the coating material is baked. The alkoxyl group on the surface of the coating film is hydrolyzed by moisture in the air to form a hydroxyl group. The rate of hydrolysis varies depending on the type of alkoxyl group, temperature and humidity, but the adhesiveness of the upper coating film can be improved by only changing a part of the alkoxyl group to a hydroxyl group. It is also possible to treat with an acid or alkaline aqueous solution in order to actively hydrolyze the alkoxyl group.
【００１０】[0010]
【実施の形態】親水性に富む塗膜表面は、一般式Ｒ1 4-n
Ｓｉ（ＯＲ2）n［ただし、Ｒ1：アルキル基又はアルコ
キシル基、Ｒ2：アルキル基、ｎ：３又は４］で表され
るオルガノアルコキシシラン又はその縮合物を配合した
塗料を塗装原板に塗布し焼成することにより形成され
る。焼成時にオルガノアルコキシシラン又はその縮合物
が下層塗膜の塗膜表面に濃化し、アルキル基又はその加
水分解で生じた水酸基が塗膜表面に配向して塗膜の親水
性を向上させる。BEST MODE FOR CARRYING OUT THE INVENTION The surface of a coating film rich in hydrophilicity is represented by the general formula R 1 4-n
Si (OR 2 ) n [wherein R 1 is an alkyl group or an alkoxyl group, R 2 is an alkyl group, n: 3 or 4] is coated with a coating material containing an organoalkoxysilane or a condensate thereof. Then, it is formed by firing. During the baking, the organoalkoxysilane or its condensate is concentrated on the coating film surface of the lower coating film, and the alkyl group or the hydroxyl group generated by the hydrolysis thereof is oriented on the coating film surface to improve the hydrophilicity of the coating film.
【００１１】塗料のベース樹脂は、特に樹脂種に制約を
受けるものではなく、プレコート金属板用に使用される
ポリフッ化ビニリデンとアクリル樹脂の混合樹脂、溶剤
可溶型フッ素樹脂、ポリエステル樹脂、シリコーン樹
脂、シリコーンポリエステル樹脂、ウレタン樹脂、アク
リル樹脂、塩化ビニル樹脂、エポキシ樹脂等が使用され
る。これらの樹脂の中で、特にフッ素系樹脂やシリコー
ン系樹脂からなる塗膜表面は不活性で表面張力が低いた
め、上塗り塗料として適用できるものが限定されるのが
現状であり、こうした表面張力の低い樹脂を下層塗膜と
した場合に本発明の効果がより顕著である。The base resin of the paint is not particularly limited by the resin type, and is a mixed resin of polyvinylidene fluoride and acrylic resin used for precoated metal plates, solvent-soluble fluororesin, polyester resin, silicone resin. , Silicone polyester resin, urethane resin, acrylic resin, vinyl chloride resin, epoxy resin and the like are used. Among these resins, the coating film surface made of fluorine resin or silicone resin is inactive and has a low surface tension. Therefore, at present, what can be applied as a topcoat paint is limited. The effect of the present invention is more remarkable when a low resin is used as the lower coating film.
【００１２】オルガノアルコキシシラン又はその縮合物
は、塗料樹脂１００質量部に対して１質量部以上の割合
で配合されるとき、塗膜表面を親水化する作用が顕著に
なる。しかし、２０質量部を超える過剰量のオルガノア
ルコキシシラン又はその縮合物が配合されると、塗膜の
加工性が低下し、塗膜割れが生じやすくなる。オルガノ
アルコキシシラン又はその縮合物は、塗料に混入してい
る水分、水酸基、アミノ基、カルボキシル基、エポキシ
基、アルコキシ基、フェニル基等の官能基を持つ塗料樹
脂、硬化剤、顔料とも反応し貯蔵安定性を低下させる傾
向がある。この種の反応は、オルガノアルコキシシラン
又はその縮合物をキレート誘導体とすることによって抑
制され、塗料の貯蔵安定性が向上する。When the organoalkoxysilane or its condensate is blended in a proportion of 1 part by mass or more relative to 100 parts by mass of the coating resin, the effect of hydrophilizing the coating film surface becomes remarkable. However, when an excessive amount of organoalkoxysilane or its condensate exceeding 20 parts by mass is blended, the workability of the coating film is deteriorated and the coating film cracks easily occur. Organoalkoxysilane or its condensate reacts with water, hydroxyl group, amino group, carboxyl group, epoxy group, alkoxy group, functional group such as phenyl group, etc. which are mixed in the coating resin, curing agent, and pigment to react and store. Tends to reduce stability. This type of reaction is suppressed by using organoalkoxysilane or a condensate thereof as a chelate derivative, and the storage stability of the paint is improved.
【００１３】キレート化剤としては、アセチルアセトン
等のβジケトン、アセト酢酸エチル等のβケト酸エステ
ル、２，３−ブタンジオール、１，３プロパンジオー
ル、エチレングリコール、２−メチル−２，４−ペンタ
ンジオール、ピナコール等の２価アルコール類、モノ−
エタノールアミン、ジ−エタノールアミン、トリ−エタ
ノールアミン、モノ−イソプロパノールアミン、Ｎ−メ
チルジエタノールアミン、Ｎ−エチルジエタノールアミ
ン等のエタノールアミン類を単独又は複数同時に使用で
きる。Examples of chelating agents include β-diketones such as acetylacetone, β-keto acid esters such as ethyl acetoacetate, 2,3-butanediol, 1,3 propanediol, ethylene glycol, 2-methyl-2,4-pentane. Dihydric alcohols such as diol and pinacol, mono-
Ethanolamines such as ethanolamine, di-ethanolamine, tri-ethanolamine, mono-isopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine can be used alone or in combination.
【００１４】キレート化剤の添加量は、特に制約される
ものではないが、テトラアルコキシシランの部分加水分
解縮合物に含まれるＳｉ原子のモル数に対して０．１〜
２当量の範囲に収まるように添加量を調整することが好
ましい。塗料に含まれている水分を除去することによっ
ても、オルガノアルコキシシラン又はその縮合物の反応
が抑制され、塗料の貯蔵安定性が向上する。脱水剤とし
ては、オルト蟻酸トリメチル、オルト蟻酸トリエチル、
オルト蟻酸トリブチル等のオルト蟻酸トリアルキル類、
オルト酢酸トリメチル、オルト酢酸トリエチル、オルト
酢酸トリブチル等のオルト酢酸トリアルキル類、オルト
硼酸トリメチル、オルト硼酸トリエチル、オルト硼酸ト
リブチル等のオルト硼酸トリアルキル類、メチルトリメ
トキシシラン、γ−メタクリロキシプロピルトリメトキ
シシラン、ビニルトリメトキシシラン、テトラメトキシ
シラン、テトラエトキシシラン等の加水分解性シラン化
合物等がある。The amount of the chelating agent added is not particularly limited, but it is 0.1 to the number of moles of Si atoms contained in the partially hydrolyzed condensate of tetraalkoxysilane.
It is preferable to adjust the addition amount so that it falls within the range of 2 equivalents. By removing the water contained in the paint, the reaction of the organoalkoxysilane or its condensate is also suppressed, and the storage stability of the paint is improved. As the dehydrating agent, trimethyl orthoformate, triethyl orthoformate,
Trialkyl orthoformates such as tributyl orthoformate,
Trialkyl orthoacetates such as trimethyl orthoacetate, triethyl orthoacetate and tributyl orthoacetate, trimethyl orthoborate, triethyl orthoborate, trialkyl orthoborates such as tributyl orthoborate, methyltrimethoxysilane, γ-methacryloxypropyltrimethoxy Examples include hydrolyzable silane compounds such as silane, vinyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane.
【００１５】脱水剤は、塗料樹脂１００質量部に対して
１質量部以上の割合で配合することにより脱水効果が顕
著となり、オルガノアルコキシシラン又はその縮合物と
水分との反応が効果的に抑制される。しかし、５０質量
部を超える過剰量の脱水剤を配合すると、塗料組成物の
粘度が低下し、塗装性に悪影響を及ぼす。塗料に着色顔
料、体質顔料を添加することもあるが、オルガノアルコ
キシシラン又はその縮合物が塗膜表層に濃化し易くする
ために、ＪＩＳ Ｋ５１０１の顔料試験方法（常温法）
で定められている方法で測定したｐＨ値が５．５〜８．
５の中性顔料を使用することが望ましい。酸性又はアル
カリ性顔料は、塗料中に存在する水分や雰囲気から塗料
中に吸収された水分に接すると、水素イオンや水酸化物
イオンの発生源になり、発生した水酸化物イオンがアル
コキシル基を水酸基に加水分解し、水素イオンが水酸基
の脱水縮合を促進させる。そのため、塗料組成物に含ま
れている水分とオルガノアルコキシシラン又はその縮合
架橋物との反応が促進され分子量が増大することによっ
て、塗膜表層への濃化が妨げられ、さらに縮合架橋が進
行すると塗料がゲル化する。When the dehydrating agent is blended in an amount of 1 part by mass or more with respect to 100 parts by mass of the coating resin, the dehydrating effect becomes remarkable, and the reaction between the organoalkoxysilane or its condensate and water is effectively suppressed. It However, if an excessive amount of dehydrating agent exceeding 50 parts by mass is blended, the viscosity of the coating composition is lowered, and the paintability is adversely affected. Color pigments and extender pigments may be added to the paint, but in order to make it easier for the organoalkoxysilane or its condensate to concentrate on the surface layer of the coating film, the pigment test method of JIS K5101 (normal temperature method)
The pH value measured by the method defined in 5.
It is desirable to use 5 neutral pigments. An acidic or alkaline pigment becomes a source of hydrogen ions or hydroxide ions when it comes into contact with water present in the paint or water absorbed in the paint from the atmosphere, and the generated hydroxide ions form an alkoxyl group into a hydroxyl group. Is hydrolyzed into hydrogen, and hydrogen ions accelerate the dehydration condensation of hydroxyl groups. Therefore, by increasing the molecular weight by promoting the reaction of water contained in the coating composition and the organoalkoxysilane or its condensation crosslinked product, the concentration to the coating surface layer is prevented, and further condensation crosslinking proceeds. The paint gels.
【００１６】さらに、塗装性、塗膜硬度、意匠性、耐食
性等を改善するため、必要に応じて防錆顔料、ガラスビ
ーズ、ガラスフレーク、鱗片状酸化鉄粉等の骨材、マイ
カ、鱗片状金属粉、金属被覆鱗片状粉末等の光輝性顔
料、ＰＡＮビーズ、アクリルビーズ、ナイロンビーズ、
ポリテトラフルオロエチレン等の有機粒子、つや消し
剤、レベリング剤、紫外線吸収剤、光安定剤等の各種添
加剤を添加しても良い。これらの添加剤としても、顔料
と同様に水素イオンや水酸化物イオンの発生源とならな
いように、中性の添加剤を使用することが望ましい。Further, in order to improve paintability, coating film hardness, designability, corrosion resistance, etc., if necessary, rust-preventive pigments, glass beads, glass flakes, aggregates such as scale-like iron oxide powder, mica, scale-like. Bright pigments such as metal powder, metal-coated scale-like powder, PAN beads, acrylic beads, nylon beads,
Various additives such as organic particles such as polytetrafluoroethylene, a matting agent, a leveling agent, an ultraviolet absorber and a light stabilizer may be added. As these additives, it is desirable to use neutral additives so that they do not become a source of generation of hydrogen ions or hydroxide ions like the pigments.
【００１７】所定組成に調製された塗料組成物をロール
コート、カーテンコート、スプレーコート、ダイコード
等で下地処理した塗装原板に塗布し、焼成することによ
って親水性に富んだ下層塗膜が形成される。塗布された
塗料組成物は、使用する塗料の標準的条件、具体的には
１５０〜３００℃、２０〜１２０秒の加熱で焼成され
る。また、塗装原版との密着性や耐食性を高めるため
に、必要に応じて塗装原版にプライマー層を設けた後に
下層塗膜を形成してもよい。プライマーに使用する樹脂
は、エポキシ樹脂、フェノキシ樹脂、ポリエステル樹
脂、ウレタン樹脂、アクリル樹脂などが好ましい。プラ
イマーには、必要に応じて防錆顔料、体質顔料、骨材な
どを添加してもよい。塗装原板には、冷延鋼板、亜鉛め
っき鋼板、Ｚｎ−Ａｌ合金めっき鋼板、Ｚｎ−Ａｌ−Ｍ
ｇ合金めっき鋼板、アルミニウムめっき鋼板、ステンレ
ス鋼板、アルミニウム合金板、銅板等が使用される。塗
装原板は、必要に応じて脱脂、酸洗、クロメート処理、
クロムフリー処理、リン酸塩処理等の塗装前処理が施さ
れる。A coating composition prepared to have a predetermined composition is applied to a coating base plate which has been pretreated with a roll coat, a curtain coat, a spray coat, a die code, etc., and baked to form a hydrophilic lower layer coating film. It The applied coating composition is baked under standard conditions of the coating used, specifically, 150 to 300 ° C. and 20 to 120 seconds of heating. Further, in order to improve the adhesion to the coating original plate and the corrosion resistance, a lower layer coating film may be formed after providing a primer layer on the coating original plate, if necessary. The resin used for the primer is preferably epoxy resin, phenoxy resin, polyester resin, urethane resin, acrylic resin or the like. If necessary, a rust preventive pigment, an extender pigment, an aggregate and the like may be added to the primer. As the original coating plate, cold rolled steel plate, zinc plated steel plate, Zn-Al alloy plated steel plate, Zn-Al-M
A g-alloy plated steel plate, an aluminum-plated steel plate, a stainless steel plate, an aluminum alloy plate, a copper plate or the like is used. If necessary, the original coating plate may be degreased, pickled, chromated,
Pre-painting treatment such as chromium-free treatment and phosphate treatment is applied.
【００１８】下層塗膜は親水性に富み、表面張力が大き
いために、各種従来塗料を用いて上層塗膜を形成して
も、塗料との濡れ性が良好で、十分な層間密着性が得ら
れ、下層塗膜／上層塗膜間の層間剥離を起こさない。上
層塗膜用塗料の種類には、特に制約は無く、アクリル樹
脂、シリコーン樹脂、シリコーンアクリル樹脂、ウレタ
ン樹脂、ポリエステル樹脂、シリコーンポリエステル樹
脂、ポリオレフィン系樹脂、ポリフッ化ビニリデンとア
クリル樹脂の混合樹脂、溶剤可溶型フッ素樹脂、塩化ビ
ニル樹脂、エポキシ樹脂等が使用される。Since the lower coating film is rich in hydrophilicity and has a large surface tension, even if the upper coating film is formed by using various conventional coating materials, the wettability with the coating material is good and sufficient interlayer adhesion is obtained. Therefore, delamination between the lower layer coating / upper layer coating does not occur. There is no particular limitation on the type of coating material for the upper coating film, and acrylic resin, silicone resin, silicone acrylic resin, urethane resin, polyester resin, silicone polyester resin, polyolefin resin, mixed resin of polyvinylidene fluoride and acrylic resin, solvent Soluble fluororesin, vinyl chloride resin, epoxy resin and the like are used.
【００１９】それら上層塗膜用塗料は、溶剤系、水系、
粉体のいずれでも良く、その硬化タイプによって常温乾
燥もしくは加熱乾燥が選択される。加熱乾燥タイプの場
合は、塗料種によって異なるが、一般的には、４０℃〜
３００℃、２０秒〜６０分の範囲で乾燥あるいは焼付け
硬化条件が選定される。上層塗膜用塗料はクリアータイ
プでも着色顔料を配合したエナメルタイプでもよい。必
要とする塗膜性能に応じてメタリック顔料、樹脂ビー
ズ、ガラスビーズ、シリカなどの艶消し剤、光触媒粒
子、紫外線吸収剤、光安定剤等が添加される。These upper layer coating materials are solvent-based, water-based,
Either powder may be used, and room temperature drying or heat drying is selected depending on the curing type. In the case of heat-drying type, it varies depending on the type of paint, but generally 40 ℃ ~
Drying or bake hardening conditions are selected in the range of 300 ° C. for 20 seconds to 60 minutes. The coating material for the upper coating film may be a clear type or an enamel type containing a color pigment. Metallic pigments, resin beads, glass beads, matting agents such as silica, photocatalyst particles, ultraviolet absorbers, and light stabilizers are added depending on the required coating film performance.
【００２０】[0020]
【実施例１】５５％アルミ亜鉛合金めっき鋼板に化成処
理を施し、熱硬化型エポキシ樹脂プライマー塗料を乾燥
膜厚が５μｍとなるように塗装し、２００℃、３０秒間
加熱硬化させた後、ポリフッ化ビニリデン樹脂（ＰＶｄ
Ｆ）にアクリル樹脂をブレンドした塗料（品名：大日本
インキ化学工業製、ディックフローＣ）にテトラメトキ
シキシシランの縮合物を塗料樹脂１００質量部に対して
５質量部添加した塗料を乾燥膜厚が２０μｍとなるよう
塗装し２５０℃、６０秒間加熱乾燥させた。その塗膜
を、下層塗膜とし、更に上層塗膜として溶剤系ポリエス
テルクリアー塗料を乾燥膜厚が２０μｍとなるよう塗装
し、２２０℃、４０秒で焼成させた。Example 1 A 55% aluminum-zinc alloy-plated steel sheet was subjected to chemical conversion treatment, a thermosetting epoxy resin primer coating was applied so that the dry film thickness was 5 μm, and the coating was cured by heating at 200 ° C. for 30 seconds. Vinylidene chloride resin (PVd
F) A blend of acrylic resin blended (product name: Dainippon Ink and Chemicals, Dickflow C) with 5 parts by weight of a condensate of tetramethoxyoxysilane added to 100 parts by weight of the coating resin. Of 20 μm, and dried by heating at 250 ° C. for 60 seconds. The coating film was used as a lower layer coating film, and a solvent-based polyester clear coating material was further coated as an upper layer coating film so that the dry film thickness was 20 μm, and baked at 220 ° C. for 40 seconds.
【実施例２】実施例１と同様に下層塗膜を形成した上に
水系アクリルクリアー塗料を乾燥膜厚が３０μｍとなる
よう塗装し、８０℃、６０秒間乾燥した。Example 2 Similar to Example 1, a lower layer coating film was formed and a water-based acrylic clear coating material was applied so that the dry film thickness was 30 μm, and dried at 80 ° C. for 60 seconds.
【実施例３】実施例１と同様に下層塗膜を形成した上に
常温乾燥型ウレタン塗料を乾燥膜厚が３０μｍとなるよ
う塗装し、３日間常温乾燥（２５℃）させた。Example 3 A lower layer coating film was formed in the same manner as in Example 1 and then a room temperature dry type urethane coating material was applied so as to have a dry film thickness of 30 μm and dried at room temperature (25 ° C.) for 3 days.
【００２１】[0021]
【比較例１】実施例１と同様に熱硬化型エポキシのプラ
イマー塗料を塗装した後、ポリフッ化ビニリデン樹脂
（ＰＶｄＦ）にアクリル樹脂をブレンドした塗料（品
名：大日本インキ化学工業製、ディックフローＣ）の従
来品を塗装し２５０℃、６０秒間加熱乾燥させた。その
塗膜を下層塗膜とし、更に上層塗膜として溶剤系ポリエ
ステルクリアー塗料を塗装し、２２０℃、４０秒で焼成
させた。Comparative Example 1 A paint prepared by coating a thermosetting epoxy primer paint in the same manner as in Example 1 and then blending an acrylic resin with polyvinylidene fluoride resin (PVdF) (product name: Dainippon Ink and Chemicals, Dickflow C The conventional product of 1) was coated and heated and dried at 250 ° C. for 60 seconds. The coating film was used as a lower layer coating film, and a solvent-based polyester clear coating material was further applied as an upper layer coating film, followed by baking at 220 ° C. for 40 seconds.
【比較例２】比較例１と同様に下層塗膜を形成した上に
水系アクリルクリアー塗料を塗装し、８０℃、６０秒間
乾燥した。[Comparative Example 2] As in Comparative Example 1, a lower layer coating film was formed, a water-based acrylic clear paint was applied thereto, and the coating was dried at 80 ° C for 60 seconds.
【比較例３】比較例１と同様に下層塗膜を形成した上に
常温乾燥型ウレタン塗料を塗装し、３日間常温乾燥（２
５℃）させた。[Comparative Example 3] A lower layer coating film was formed in the same manner as in Comparative Example 1, and then a room temperature dry type urethane paint was applied and dried at room temperature for 3 days (2
5 ° C.).
【００２２】試験片の評価
（１）下層塗膜の親水性の評価下層塗膜の親水性は、対
水接触角により評価した。テトラメトキシシラン縮合物
を配合した実施例では、低い接触角を示し親水性表面で
あることが確認できた。このことから塗膜表面に水酸基
が配向していることが推察できた。一方、テトラメトキ
シシラン縮合物を配合しない従来塗膜の場合は、接触角
が高く、疎水性の表面であることが確認できた。
（２）塗膜密着性の評価塗膜密着性は、ＪＩＳ Ｋ５４
００に規定される碁盤目テープ法により評価した。すき
ま間隔１ｍｍで碁盤目状に切り傷を付け、１００個の桝
目を作製し、セロハン粘着テープを貼り付けて、引き剥
がした後の桝目内の塗膜の残存数を評価した。比較例で
は、いずれも８０％以上の桝目で塗膜が剥離したのに対
し、実施例では塗膜剥離が全くなく、良好な塗膜密着性
を示した。Evaluation of test pieces (1) Evaluation of hydrophilicity of lower coating film The hydrophilicity of the lower coating film was evaluated by the contact angle with water. In the example in which the tetramethoxysilane condensate was blended, a low contact angle was exhibited and it was confirmed that the surface was hydrophilic. From this, it was inferred that the hydroxyl groups were oriented on the surface of the coating film. On the other hand, it was confirmed that the conventional coating film containing no tetramethoxysilane condensate had a high contact angle and had a hydrophobic surface. (2) Evaluation of coating film adhesion The coating film adhesion is measured according to JIS K54.
It was evaluated by the cross-cut tape method specified in 00. Cuts were made in a grid pattern with a clearance interval of 1 mm, 100 grids were prepared, cellophane adhesive tape was attached, and the number of coating films remaining in the grids after peeling off was evaluated. In each of the comparative examples, the coating film peeled off at 80% or more meshes, whereas in the examples, there was no coating film peeling and good coating film adhesion was exhibited.
【００２３】 [0023]
【００２４】[0024]
【発明の効果】以上に説明したように、本発明において
は、親水性に富む下層塗膜を塗装原板に形成しているた
め、下層塗膜を介して設けられる上層塗膜の密着性が高
く、しかも使用可能な上層塗膜用塗料の選択自由度が向
上し、目標性能を備えた上層塗膜を優れた密着性で形成
できる。そのため、下塗り塗膜を設けた金属板は、種々
の用途で後塗装して利用できる。得られた塗装金属板
は、優れた密着性及び加工性を活用し、現場塗装が不要
なプレコート鋼板として広範な分野で使用される。As described above, in the present invention, since the lower coating film having a high hydrophilicity is formed on the coating original plate, the upper coating film provided through the lower coating film has high adhesion. In addition, the degree of freedom in selecting the usable coating material for the upper coating film is improved, and the upper coating film having the target performance can be formed with excellent adhesion. Therefore, the metal plate provided with the undercoat coating film can be post-coated and used for various purposes. The obtained coated metal sheet is used in a wide range of fields as a pre-coated steel sheet which does not require on-site coating by utilizing excellent adhesion and workability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 201/00 Ｃ０９Ｄ 201/00 (72)発明者 圓谷 浩 千葉県市川市高谷新町７番１号 日新製鋼 株式会社技術研究所内 Ｆターム(参考） 4D075 AE03 AE08 BB91Y CA13 CA37 DA06 DB02 DB04 DB05 DB06 DB07 DC02 EA06 EB15 EB16 EB17 EB22 EB33 EB35 EB38 EB42 4F100 AB01C AB03 AH06B AK19 AK25 AK41 AK52 AK53 AL05 AL05B BA03 BA07 BA10A BA10C BA44 CC00A CC00B EH46 EH462 EJ08 EJ082 EJ42 EJ422 EJ68 EJ681 EJ86 EJ862 GB08 JB04B JB13 JL11 YY00B 4J038 CD021 CD111 CG001 DB001 DD001 DG001 DL031 NA12 PB05 PC02 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09D 201/00 C09D 201/00 (72) Inventor Hiroshi Enya 7-1 Takatani Shinmachi, Ichikawa, Chiba Nisshin Steelmaking Co., Ltd. Technical Research Institute F-term (Reference) 4D075 AE03 AE08 BB91Y CA13 CA37 DA06 DB02 DB04 DB05 DB06 DB07 DC02 EA06 EB15 EB16 EB17 EB22 EB33 EB35 EB38 EB42 4F100 AB01C AB03 BA03 BA05 BA10A05 BA53A05 BA05A07 BA05 AL05 AK41 BA05 AL05 AK41 BA05 AL05 AK41 AL02 CC00B EH46 EH462 EJ08 EJ082 EJ42 EJ422 EJ68 EJ681 EJ86 EJ862 GB08 JB04B JB13 JL11 YY00B 4J038 CD021 CD111 CG001 DB001 DD001 DG001 DL031 NA12 PB05 PC02
Claims (4)
れ、該下層塗膜の対水接触角が６０度以下であることを
特徴とする親水性に富む下層塗膜を設けた金属板。1. A metal plate provided with a lower coating film having a high hydrophilicity, wherein a lower coating film is provided as a base of the upper coating film, and the lower coating film has a contact angle with water of 60 degrees or less. .
シラン又はその縮合物が濃化し、アルコキシル基又はそ
の加水分解で生成した水酸基が塗膜表面に配向している
請求項１記載の金属板。2. The metal plate according to claim 1, wherein the organoalkoxysilane or a condensate thereof is concentrated in the surface layer of the lower coating film, and an alkoxyl group or a hydroxyl group produced by hydrolysis thereof is oriented on the coating surface.
1 4-nＳｉ（ＯＲ2）n［ただし、Ｒ1：アルキル基又はア
ルコキシル基、Ｒ2：アルキル基、ｎ：３又は４］で表
されるオルガノアルコキシシラン又はその縮合物を１〜
２０質量部の割合で配合した塗料から下層塗膜が形成さ
れている請求項１または２記載の金属板。3. The general formula R with respect to 100 parts by mass of the coating resin.
1 4-n Si (OR 2 ) n [wherein R 1 is an alkyl group or an alkoxyl group, R 2 is an alkyl group, n: 3 or 4] is an organoalkoxysilane or a condensate thereof.
The metal plate according to claim 1 or 2, wherein the lower layer coating film is formed from a coating material mixed in a proportion of 20 parts by mass.
上に上層塗膜が形成されている塗装金属板。4. A coated metal plate having an upper coating film formed on the lower coating film according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001319719A JP2003118033A (en) | 2001-10-17 | 2001-10-17 | Metal plate having hydrophilic lower layer coating film and coated metal plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001319719A JP2003118033A (en) | 2001-10-17 | 2001-10-17 | Metal plate having hydrophilic lower layer coating film and coated metal plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003118033A true JP2003118033A (en) | 2003-04-23 |
Family
ID=19137231
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|---|---|---|---|
| JP2001319719A Withdrawn JP2003118033A (en) | 2001-10-17 | 2001-10-17 | Metal plate having hydrophilic lower layer coating film and coated metal plate |
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| Country | Link |
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| JP (1) | JP2003118033A (en) |
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| JP2017071848A (en) * | 2015-08-21 | 2017-04-13 | ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー | Heat treatment method for black plate covered with conversion coating |
| WO2019225765A1 (en) * | 2018-05-25 | 2019-11-28 | 日本製鉄株式会社 | Surface-treated steel plate |
| CN111155051A (en) * | 2019-12-23 | 2020-05-15 | 浙江万合邦新材料科技有限公司 | Stainless steel, stainless steel surface treatment process and application of stainless steel surface treatment process in preparation of water tank |
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2001
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006035011A (en) * | 2004-07-22 | 2006-02-09 | Mazda Motor Corp | Coating film structure and method of forming coating film structure |
| JP4513444B2 (en) * | 2004-07-22 | 2010-07-28 | マツダ株式会社 | Method for forming coating film structure |
| JP2014172930A (en) * | 2013-03-06 | 2014-09-22 | Nippon Steel & Sumikin Coated Sheet Corp | Coating material for coated metal plate and coated metal plate |
| JP2017071848A (en) * | 2015-08-21 | 2017-04-13 | ティッセンクルップ ラッセルシュタイン ゲー エム ベー ハー | Heat treatment method for black plate covered with conversion coating |
| WO2019225765A1 (en) * | 2018-05-25 | 2019-11-28 | 日本製鉄株式会社 | Surface-treated steel plate |
| JP6680412B1 (en) * | 2018-05-25 | 2020-04-15 | 日本製鉄株式会社 | Surface treated steel plate |
| CN111683811A (en) * | 2018-05-25 | 2020-09-18 | 日本制铁株式会社 | Surface-treated steel sheet |
| CN111683811B (en) * | 2018-05-25 | 2022-06-14 | 日本制铁株式会社 | Surface-treated steel sheet |
| CN111155051A (en) * | 2019-12-23 | 2020-05-15 | 浙江万合邦新材料科技有限公司 | Stainless steel, stainless steel surface treatment process and application of stainless steel surface treatment process in preparation of water tank |
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