JP4603435B2 - Organic resin coated steel sheet - Google Patents
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- JP4603435B2 JP4603435B2 JP2005203107A JP2005203107A JP4603435B2 JP 4603435 B2 JP4603435 B2 JP 4603435B2 JP 2005203107 A JP2005203107 A JP 2005203107A JP 2005203107 A JP2005203107 A JP 2005203107A JP 4603435 B2 JP4603435 B2 JP 4603435B2
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本発明は、導電性，耐食性，意匠性，密着性に優れた有機樹脂被覆鋼板に関する。 The present invention relates to an organic resin-coated steel sheet excellent in conductivity, corrosion resistance, designability, and adhesion.
普通鋼板，めっき鋼板等の原板を有機樹脂で被覆すると、耐食性，耐指紋性の良好な有機樹脂被覆鋼板が得られる。必要な色調を有機樹脂被覆鋼板に付与する場合、着色顔料を有機樹脂皮膜に分散させている。着色顔料で色調を付与した有機樹脂被覆鋼板では、着色顔料の配合量が多くなると耐食性，加工性等が劣化する傾向を示すので、有機樹脂皮膜を厚膜化することにより必要な色調を得ている。しかし、厚膜の有機樹脂皮膜は、有機樹脂被覆鋼板にプレス成形，曲げ等の加工を施す際、有機樹脂皮膜に亀裂，剥離等が生じやすい。 When an original plate such as a normal steel plate or a plated steel plate is coated with an organic resin, an organic resin-coated steel plate having good corrosion resistance and fingerprint resistance can be obtained. When a required color tone is imparted to the organic resin-coated steel sheet, the color pigment is dispersed in the organic resin film. Organic resin-coated steel sheets to which color tones are imparted with colored pigments tend to deteriorate the corrosion resistance, workability, etc., as the amount of the colored pigment increases, so the necessary color tone can be obtained by increasing the thickness of the organic resin film. Yes. However, a thick organic resin film tends to cause cracking, peeling, etc. in the organic resin film when the organic resin-coated steel sheet is subjected to processing such as press molding and bending.
樹脂自体で必要な色調が得られると、着色顔料の配合を必要とせず、有機樹脂皮膜の薄膜化が可能になる。有色樹脂として共役二重結合を有するπ共役高分子が知られており、ドーパントの共存下でπ共役高分子が導電性を示すことを活用し、OA機器のケーシング材としての利用も検討されている。たとえば、アニリン，チオフェン，ピロール等の酸化重合体を含む塗料から成膜された導電性高分子皮膜(特許文献１)，ポリアニリン系化合物を含む塗料から成膜された防食皮膜(特許文献２)，ドーパントの配合により導電性を付与したポリアニリン皮膜(特許文献３)等がある。
しかし、ポリアニリンに代表されるπ共役高分子は、下地鋼に対する密着に必要な水素結合を有する官能基が少なく、水素結合力も弱いため皮膜密着性に乏しい。そのため、π共役高分子を含む有機樹脂皮膜を設けた鋼板にプレス成形，曲げ等の加工を施すと、皮膜に剥離や亀裂が生じ目標とする性能が損なわれる。そこで、本発明者等は、アミノ系シランカップリング剤を微量添加すると導電性高分子の弱点であった密着性が比較的に改善されることを解明し、導電性，耐食性，意匠性，密着性の何れにおいても優れた有機樹脂被覆鋼板を提案した(特許文献４)。
アミノ系シランカップリング剤の配合によって有機樹脂皮膜の密着性は向上するが、シランカップリング剤の種類によっては有機樹脂皮膜の導電性低下が散見される。そこで、シランカップリング剤と有機樹脂皮膜の導電性との関係を調査・検討したところ、π共役高分子とπ結合する有機官能基を有するシランカップリング剤を使用すると、導電性の低下なく皮膜密着性を改善した有機樹脂被覆鋼板が得られることを見出した。
本発明は、かかる知見をベースに完成されたものであり、特定のシランカップリング剤を配合して密着性向上に有効な界面層を形成し、導電性高分子本来の特性を活用した有機樹脂被覆鋼板を提供することを目的とする。
Although the adhesion of the organic resin film is improved by the incorporation of the amino silane coupling agent, the conductivity of the organic resin film is sometimes lowered depending on the type of the silane coupling agent. Therefore, the relationship between the conductivity of the silane coupling agent and the organic resin film was investigated and examined. When a silane coupling agent having an organic functional group that is π-bonded to a π-conjugated polymer is used, the film does not deteriorate in conductivity. It has been found that an organic resin-coated steel sheet with improved adhesion can be obtained.
The present invention has been completed on the basis of such knowledge, and an organic resin that incorporates a specific silane coupling agent to form an interface layer effective for improving adhesion and utilizes the original characteristics of a conductive polymer. It aims at providing a coated steel plate.
本発明の有機樹脂被覆鋼板は、中性又は酸性の有機官能基とするシランカップリング剤からなる界面層を介し、複素環式共役系又はヘテロ原子含有共役系のπ共役高分子を主成分とし、ドーパントの添加によって導電性が付与された有機樹脂皮膜が設けられていることを特徴とする。シランカップリング剤の有機官能基には、シクロアルカン，π結合を有する原子団から選ばれた一種又は二種以上がある。
ドーパントとしては、ＳＯ4，Ｃｌ，Ｆ，ＰＯ4，これらの原子団を有する無機又は有機化合物から選ばれた一種又は二種以上が使用される。π共役高分子に含まれるヘテロ原子としては、窒素，硫黄がある。
The organic resin-coated steel sheet of the present invention is mainly composed of a heterocyclic conjugated system or a heteroatom-containing conjugated π-conjugated polymer via an interface layer made of a silane coupling agent having a neutral or acidic organic functional group. An organic resin film provided with conductivity by the addition of a dopant is provided. The organic functional group of the silane coupling agent includes one or more selected from a cycloalkane and an atomic group having a π bond.
As the dopant, SO 4 , Cl, F, PO 4 , or one or more selected from inorganic or organic compounds having these atomic groups are used. Heteroatoms contained in the π-conjugated polymer include nitrogen and sulfur.
π共役高分子が導電性を呈する状態は、プロトン酸，ハロゲン等のドーパントＸがイオン結合してヘテロ原子Ｎがプラスに帯電した状態である。
ところが、アミノ基を有するシランカップリング剤を配合した有機樹脂皮膜では、アミノ基Ｒが導電性高分子のヘテロ原子Ｎに結合するため、自由電子の個数が少なくなる。ドーパント(アニオン)とシランカップリング剤のアミノ基(カチオン)との反応による塗料のゲル化も懸念される。
これに対し、π共役高分子のヘテロ原子Ｎと反応しやすい塩基性基を含まず、ベンゼン環(π結合部)と結合する有機官能基を有するシランカップリング剤を使用すると、自由電子の個数減少もなく、ドーパントとの反応もない(図１)。その結果、π共役高分子本来の導電性が維持され、有機樹脂皮膜の密着性も改善される。しかも、塗料のゲル化も防止される。導電性の向上は、ドープ状態にあるπ共役高分子のベンゼン環にシランカップリング剤の有機官能基が作用することでベンゼン環中の電子が誘起され、電子が非局在化することも一因と考えられる。なかでも、π共役高分子のベンゼン環(π結合部)とシランカップリング剤のシクロアルカン，π結合を有する有機官能基がπ-π相互作用する誘起効果を受けると一層の導電性向上が図られる。
However, in an organic resin film containing a silane coupling agent having an amino group, the number of free electrons is reduced because the amino group R is bonded to the heteroatom N of the conductive polymer. There is also concern about the gelation of the paint due to the reaction between the dopant (anion) and the amino group (cation) of the silane coupling agent.
In contrast, when a silane coupling agent that does not contain a basic group that easily reacts with the hetero atom N of the π-conjugated polymer and has an organic functional group that binds to the benzene ring (π bond portion), the number of free electrons There is no reduction and no reaction with the dopant (Figure 1). As a result, the original conductivity of the π-conjugated polymer is maintained, and the adhesion of the organic resin film is also improved. Moreover, the gelation of the paint is also prevented. The improvement in conductivity is due to the fact that electrons in the benzene ring are induced by the action of the organic functional group of the silane coupling agent on the benzene ring of the π-conjugated polymer in the doped state, and the electrons are delocalized. It is thought to be the cause. In particular, when the benzene ring (π bond part) of the π-conjugated polymer, the cycloalkane of the silane coupling agent, and the organic functional group having a π bond are subjected to the induction effect of π-π interaction, the conductivity is further improved. It is done.
更に、π共役高分子を含む有機樹脂皮膜は、有機樹脂被覆鋼板の防食にも有効である。防食能は、貴金属的性質を有するπ共役高分子によって下地鋼が酸化され、緻密な不動態皮膜が下地表面に生成することに起因すると考えられる。しかも、下地に対する有機樹脂皮膜の密着性が高くなっているので環境遮断能が高く、ピンホール，皮膜疵付き等の欠陥が発生しても欠陥部を起点とする腐食の進行が抑制される。 Furthermore, the organic resin film containing a π-conjugated polymer is effective for preventing corrosion of the organic resin-coated steel sheet. The anticorrosive ability is considered to be caused by the fact that the base steel is oxidized by the π-conjugated polymer having noble metal properties, and a dense passive film is formed on the base surface. In addition, since the adhesion of the organic resin film to the base is high, the environmental barrier ability is high, and even if a defect such as a pinhole or film flaw occurs, the progress of corrosion starting from the defective portion is suppressed.
有機樹脂皮膜が設けられる塗装原板は、材質に特段の制約を受けるものではないが、普通鋼板，めっき鋼板，低合金鋼，ステンレス鋼板等、種々の鋼板を使用できる。必要に応じて適宜の前処理が施された塗装原板にπ共役高分子，シランカップリング剤を含む塗料を塗布し焼き付けることにより、密着性，耐食性に優れた有機樹脂皮膜が形成される。ドーパントを含む塗料の使用、或いは皮膜形成後にドーパント溶液を用いた接触処理の何れによっても有機樹脂皮膜に導電性を付与できる。 Although the coating original plate on which the organic resin film is provided is not particularly restricted by the material, various steel plates such as a normal steel plate, a plated steel plate, a low alloy steel, and a stainless steel plate can be used. An organic resin film having excellent adhesion and corrosion resistance is formed by applying and baking a coating containing a π-conjugated polymer and a silane coupling agent on a coating original plate that has been subjected to appropriate pretreatment as necessary. Conductivity can be imparted to the organic resin film by using either a paint containing a dopant or a contact treatment using a dopant solution after the film is formed.
有機樹脂皮膜の主成分であるπ共役高分子は、複素環式共役系又はヘテロ原子含有共役系があり、具体的には以下の化合物が使用される。
複素環式共役系：ポリピロール，ポリフラン，ポリチオフェン，ポリセレノフェン
ヘテロ原子含有共役系：ポリ(パラフェニレンスルフィド)，ポリ(パラフェニレンオキシド)，ポリアニリン
特に、ヘテロ原子Ｓを有するポリ(パラフェニレンスルフィド)やＮを有するポリアニリンをπ共役高分子に使用する場合、有機樹脂皮膜の密着性が一層向上する。
The π-conjugated polymer that is the main component of the organic resin film has a heterocyclic conjugated system or a heteroatom-containing conjugated system, and specifically, the following compounds are used.
Heterocyclic conjugated system: polypyrrole, polyfuran, polythiophene, polyselenophene heteroatom-containing conjugated system: poly (paraphenylene sulfide), poly (paraphenylene oxide), polyaniline When polyaniline having N is used for the π-conjugated polymer, the adhesion of the organic resin film is further improved.
シランカップリング剤としては、π共役高分子のヘテロ原子でなくベンゼン環(π結合部)に結合する有機官能基を有する必要があり、特にシクロアルカン及び／又はπ結合を有する原子団を有機官能基とするシランカップリング剤が好ましい。シランカップリング剤は、下地表面にある金属酸化物，金属水酸化物にシラノール基で強く結合し、有機樹脂皮膜のπ共役高分子に有機官能基で強く結合する。 As a silane coupling agent, it is necessary to have an organic functional group that binds to a benzene ring (π bond portion) rather than a hetero atom of a π-conjugated polymer, and in particular, an atomic group having a cycloalkane and / or a π bond is an organic functional group. Silane coupling agents based on them are preferred. The silane coupling agent is strongly bonded to the metal oxide or metal hydroxide on the base surface with a silanol group and strongly bonded to the π-conjugated polymer of the organic resin film with an organic functional group.
具体的には、3-アニリノプロピルトリメトキシシラン，シクロヘキシルメチルジメトキシシラン，フェニルトリメトキシシラン，ジフェニルジメトキシシラン2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン，3-メタクリロキシプロピルトリメトキシシラン，3-アクリロキシプロピルトリメトキシシラン，ビニルトリアセトキシシラン，ビニルトリメトキシシラン，ビニルトリエトキシシラン，メタクリロキシオキシプロピルトリエトキシシラン等がある。 Specifically, 3-anilinopropyltrimethoxysilane, cyclohexylmethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-acryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxyoxypropyltriethoxysilane, and the like.
π共役高分子，シランカップリング剤を含む塗料から成膜された有機樹脂皮膜にドーパントを含ませることにより、導電性が付与される。ドーパントは、塗料成分として有機樹脂皮膜に含ませる一段処理、或いは成膜後にドーパント溶液と接触させる二段処理で有機樹脂皮膜に含ませることができる。
ドーパントには、無機酸，有機酸，ハロゲン，ルイス酸等が使用される。具体的には、塩酸，過塩素酸，過塩素酸テトラメチルアンモニウム，テトラフルオロホウ酸，リン酸，ヘキサフルオロリン酸等の無機酸、ベンゼンスルホン酸，トルエンスルホン酸，ナフタレンスルホン酸等の有機酸、塩素，臭素，フッ素等のハロゲン、五フッ化リン，三フッ化ホウ素等のルイス酸がある。なかでも、ＳＯ4，ＣｌＦ，ＰＯ4又はこれらの原子団を有する無機又は有機化合物をドーパントに使用すると、シランカップリング剤との相性が良く、優れた導電性が有機樹脂皮膜に付与される。
Conductivity is imparted by adding a dopant to an organic resin film formed from a paint containing a π-conjugated polymer and a silane coupling agent. The dopant can be contained in the organic resin film by a one-step treatment to be included in the organic resin film as a coating component, or a two-stage treatment in which the dopant is brought into contact with the dopant solution after the film formation.
As the dopant, an inorganic acid, an organic acid, a halogen, a Lewis acid, or the like is used. Specifically, inorganic acids such as hydrochloric acid, perchloric acid, tetramethylammonium perchlorate, tetrafluoroboric acid, phosphoric acid and hexafluorophosphoric acid, and organic acids such as benzenesulfonic acid, toluenesulfonic acid and naphthalenesulfonic acid And halogens such as chlorine, bromine and fluorine, and Lewis acids such as phosphorus pentafluoride and boron trifluoride. Among these, when an inorganic or organic compound having SO 4 , ClF, PO 4 or an atomic group thereof is used as a dopant, the compatibility with the silane coupling agent is good, and excellent conductivity is imparted to the organic resin film.
シランカップリング剤，π共役高分子を溶媒に溶解することにより、有機樹脂皮膜形成用の塗料が調製される。使用可能な溶媒は、シランカップリング剤，π共役高分子を安定に溶解させる限り特に種類が制約されるものではなく、水，メタノール等のアルコール類，メチルエチルケトン，キシレン，アセトン，アセトニトリル，N-メチル-2-ピロリドン等の有機溶媒がある。
π共役高分子は、１〜３０質量％で配合することが好ましい。π共役高分子の配合量が１質量％未満では、塗料中のπ共役高分子が不足し、均一な有機樹脂皮膜を形成させ難い。逆に、３０質量％を超える過剰量では、塗料の安定性が悪くなり、塗料の更新時期を早めることにもなる。
A paint for forming an organic resin film is prepared by dissolving a silane coupling agent and a π-conjugated polymer in a solvent. Solvents that can be used are not particularly limited as long as silane coupling agents and π-conjugated polymers are stably dissolved. Water, alcohols such as methanol, methyl ethyl ketone, xylene, acetone, acetonitrile, N-methyl There are organic solvents such as -2-pyrrolidone.
The π-conjugated polymer is preferably blended at 1 to 30% by mass. When the amount of the π-conjugated polymer is less than 1% by mass, the π-conjugated polymer in the coating is insufficient, and it is difficult to form a uniform organic resin film. On the other hand, when the amount exceeds 30% by mass, the stability of the paint is deteriorated and the renewal time of the paint is also advanced.
シランカップリング剤は、π共役高分子に対して０.１〜３０質量％の割合で添加することが好ましい。０.１質量％未満の添加量では十分な密着性向上効果が得られず、逆に３０質量％を超える過剰量ではπ共役高分子による特性付与に悪影響を及ぼしやすい。
一段処理では、π共役高分子を形成しているモノマーに対するモル濃度比：０.０１〜１.０でドーパントを塗料に配合することが好ましい。０.０１未満の濃度比では十分な導電性が得られず、逆に１.０を超える濃度比では過剰なドーパントに起因する塗料の不安定化，有機樹脂皮膜の特性劣化が懸念される。
The silane coupling agent is preferably added at a ratio of 0.1 to 30% by mass with respect to the π-conjugated polymer. If the addition amount is less than 0.1% by mass, a sufficient adhesion improving effect cannot be obtained. Conversely, if the addition amount exceeds 30% by mass, the property imparting by the π-conjugated polymer tends to be adversely affected.
In the one-step treatment, it is preferable to add the dopant to the paint at a molar concentration ratio of 0.01 to 1.0 with respect to the monomer forming the π-conjugated polymer. If the concentration ratio is less than 0.01, sufficient conductivity cannot be obtained. Conversely, if the concentration ratio exceeds 1.0, there is a concern that the coating may become unstable and the characteristics of the organic resin film may deteriorate due to excessive dopant.
ロールコート，スプレー，浸漬法等で原板に塗料を塗布し、焼付け・乾燥により目標の有機樹脂皮膜が形成される。焼付け・乾燥は、π共役高分子の分解を防止しながら溶媒を揮発させる限り温度条件に特段の制約が加わるものではないが、工業的な観点から焼付け・乾燥温度を５０〜３００℃の範囲で選定することが好ましい。５０℃に達しない温度では長時間の焼付け・乾燥を必要とし、３００℃を超える温度ではπ共役高分子の分解に起因する品質低下が懸念される。 A coating material is applied to the original plate by roll coating, spraying, dipping, etc., and a target organic resin film is formed by baking and drying. Baking / drying does not impose any particular restrictions on the temperature conditions as long as the solvent is volatilized while preventing decomposition of the π-conjugated polymer, but the baking / drying temperature is in the range of 50 to 300 ° C. from an industrial viewpoint. It is preferable to select. If the temperature does not reach 50 ° C., baking and drying for a long time is required, and if the temperature exceeds 300 ° C., there is a concern that the quality may be deteriorated due to decomposition of the π-conjugated polymer.
有機樹脂皮膜は、塗装後耐食性に優れており、下塗り塗膜，表層塗膜の何れにも使用でき、好ましくは乾燥膜厚：０.１〜１０μｍに調整される。０.１μｍ未満の薄膜では、十分な耐食性が確保されない。有機樹脂皮膜が厚膜になるほど耐食性等の品質が向上するものの、１０μｍを超えて厚膜化しても更なる品質向上効果が得られず経済的に不利となる。下塗り塗膜として使用する場合も同様である。 The organic resin film is excellent in corrosion resistance after coating, and can be used for both the undercoat film and the surface film, and is preferably adjusted to a dry film thickness of 0.1 to 10 μm. With a thin film of less than 0.1 μm, sufficient corrosion resistance is not ensured. The thicker the organic resin film, the better the quality such as corrosion resistance. However, even if the film thickness exceeds 10 μm, a further quality improvement effect cannot be obtained, which is economically disadvantageous. The same applies to the case where it is used as an undercoat coating film.
有機樹脂皮膜が形成された鋼板表層の深さ方向に沿った元素分布状態を測定すると、下地鋼と有機樹脂皮膜との界面にシランカップリング剤からなる界面層が検出される。シランカップリング剤由来の界面層は、ESCA，AES等の解析結果からシランカップリング剤のＳｉを読み取ることにより確認できる。
シランカップリング剤からなる界面層は、シランカップリング剤を配合した塗料の使用に代え、シランカップリング剤含有液を用いた原板を塗装前処理によっても形成できる。この場合にも、有機樹脂皮膜の密着性向上に寄与する。
When the element distribution state along the depth direction of the steel sheet surface layer on which the organic resin film is formed is measured, an interface layer made of a silane coupling agent is detected at the interface between the base steel and the organic resin film. The interface layer derived from the silane coupling agent can be confirmed by reading Si of the silane coupling agent from the analysis results such as ESCA and AES.
The interface layer made of a silane coupling agent can be formed by pre-coating a base plate using a silane coupling agent-containing liquid instead of using a paint containing the silane coupling agent. This also contributes to improving the adhesion of the organic resin film.
板厚：０.８ｍｍ，片面当りめっき付着量：２０ｇ／ｍ2の電気亜鉛めっき鋼板を塗装原板に用い、π共役高分子を含む有機樹脂皮膜を形成した実施例で本発明を具体的に説明する。しかし、電気亜鉛めっき鋼板が塗装原板に限られるものではなく、熱延鋼板，冷延鋼板，他の電気めっき鋼板，溶融めっき鋼板，化成処理鋼板，ステンレス鋼板等を使用した場合でも、密着性，導電性，意匠性の良好な有機樹脂被覆鋼板が同様に得られることは勿論である。 The present invention will be described in detail with reference to an example in which an electrogalvanized steel sheet having a plate thickness of 0.8 mm and a coating amount per side of 20 g / m 2 is used as a coating base plate and an organic resin film containing a π-conjugated polymer is formed. To do. However, the electrogalvanized steel sheet is not limited to the coated raw sheet, even when hot rolled steel sheet, cold rolled steel sheet, other electroplated steel sheet, hot dip plated steel sheet, chemical conversion treated steel sheet, stainless steel sheet, etc. are used. Of course, an organic resin-coated steel sheet having good conductivity and design can be obtained in the same manner.
有機樹脂皮膜形成用の塗料は、次の手順で調製した。
アニリン：４２ｇに水：６００ｇ，濃塩酸：４０ｇを加えた溶液に、濃硫酸：４０ｇを水：１５０ｇに溶解させた水溶液を混合し、モノマー溶液を調製した。モノマー溶液を０℃以下の温度に保持しながら、水：２２０ｇに過硫酸アンモニウム：１３０ｇを溶解した酸化剤溶液をモノマー溶液に滴下した。滴下後、５時間攪拌しながら重合反応させることによりポリアニリンを合成した。次いで、濃アンモニア水で脱ドープ処理し、水洗，メタノール洗浄を繰り返した後、真空乾燥により脱ドープ状態のポリアニリン粉末を得た。
ポリアニリン粉末をメチルピロリドンに１：１０の質量比で溶し込み、更に表１に掲げたシランカップリング剤を０.１質量％，３.０質量％、ドーパントとしてp-トルエンスルホン酸を０.１モル／ｌの割合で配合することにより塗料を調製した。
The paint for forming the organic resin film was prepared by the following procedure.
An aqueous solution in which 40 g of concentrated sulfuric acid was dissolved in 150 g of water was mixed with a solution obtained by adding 600 g of water and 40 g of concentrated hydrochloric acid to 42 g of aniline to prepare a monomer solution. While maintaining the monomer solution at a temperature of 0 ° C. or lower, an oxidant solution in which 130 g of ammonium persulfate was dissolved in 220 g of water was added dropwise to the monomer solution. After dropping, polyaniline was synthesized by carrying out a polymerization reaction with stirring for 5 hours. Next, after dedoping with concentrated ammonia water, water washing and methanol washing were repeated, a polyaniline powder in a dedope state was obtained by vacuum drying.
Polyaniline powder was dissolved in methylpyrrolidone at a mass ratio of 1:10, 0.1% by mass and 3.0% by mass of the silane coupling agents listed in Table 1, and 0.0% of p-toluenesulfonic acid as a dopant. A paint was prepared by blending at a ratio of 1 mol / l.
脱脂・洗浄した原板に塗料をバーコーター塗布し、到達板温：１５０℃で加熱・乾燥し、乾燥膜厚：２μｍの有機樹脂皮膜を形成した。
得られた有機樹脂被覆鋼板は、有機樹脂皮膜が薄膜であるにも拘わらず、ポリアニリンに由来する鮮明度の高い淡緑色の色調を呈していた。
有機樹脂被覆鋼板から試験片を切り出し、１８０度密着曲げ試験(２ｔ)に供した。曲げ試験後、曲げ部外側に粘着テープを貼り付け瞬時に引き剥がすテープ剥離試験で有機樹脂皮膜の剥離状態を観察し、剥離の程度から加工密着性を評価した。
A paint was applied to the degreased and washed original plate with a bar coater, heated and dried at an ultimate plate temperature of 150 ° C., and an organic resin film having a dry film thickness of 2 μm was formed.
The obtained organic resin-coated steel sheet exhibited a light green color tone with high definition derived from polyaniline even though the organic resin film was a thin film.
A test piece was cut out from the organic resin-coated steel sheet and subjected to a 180 ° adhesion bending test (2t). After the bending test, the peeled state of the organic resin film was observed by a tape peeling test in which an adhesive tape was applied to the outside of the bent portion and peeled off instantaneously, and the work adhesion was evaluated from the degree of peeling.
また、シランカップリング剤No.１をポリアニリンに添加した塗料を電気亜鉛めっき鋼板に塗布した後、鋼板表面から深さ方向に沿って元素分布状態をAESで分析した。図２の分析結果にみられるように、塗料に添加したシランカップリング剤が原板側に濃化し、界面層を形成していることを確認できる。図中、Ｎはポリアニリンを、Ｓｉはシランカップリング剤を示す元素である。シランカップリング剤や原板の種類を変更した場合でも、同様に原板側に濃化したシランカップリング剤が検出された。 Moreover, after applying the coating material which added silane coupling agent No. 1 to polyaniline to the electrogalvanized steel sheet, the element distribution state was analyzed by AES along the depth direction from the steel sheet surface. As can be seen from the analysis result of FIG. 2, it can be confirmed that the silane coupling agent added to the coating is concentrated on the original plate side to form an interface layer. In the figure, N is an element indicating polyaniline, and Si is an element indicating a silane coupling agent. Even when the type of the silane coupling agent or the original plate was changed, the concentrated silane coupling agent was detected on the original plate side.
〔比較例１-１〕
実施例１で合成したポリアニリン粉末をメチルピロリドンに質量比１：１０で溶し込み、表２のシランカップリング剤を０.１質量％，３.０質量％、ドーパントとしてp-トルエンスルホン酸を０.１モル／ｌの割合で配合することにより調製した塗料を用い、実施例１と同じ方法で形成した有機樹脂皮膜の加工密着性を調査した。
The polyaniline powder synthesized in Example 1 was dissolved in methylpyrrolidone at a mass ratio of 1:10, 0.1% by mass and 3.0% by mass of the silane coupling agent shown in Table 2, and p-toluenesulfonic acid as a dopant. Using the paint prepared by blending at a ratio of 0.1 mol / l, the processing adhesion of the organic resin film formed by the same method as in Example 1 was investigated.
〔比較例１-２〕
実施例１で合成したポリアニリン粉末をメチルピロリドンに質量比１：１０で溶かし込み、更にドーパントとしてp-トルエンスルホン酸を０.１モル／ｌの割合で配合した塗料を、クロメート処理(Ｃｒ付着量：５０ｍｇ／ｍ2)した板厚：０.８ｍｍ，片面当りめっき付着量：２０ｇ/ｍ2の電気亜鉛めっき鋼板に実施例１と同様に塗布し、加工密着性を調査した。
〔比較例１-３〕
実施例１で合成したポリアニリン粉末をメチルピロリドンに質量比１：１０で溶し込み、更にエポキシ樹脂を１０質量％，ドーパントとしてp-トルエンスルホン酸を０.１モル／ｌの割合で配合した塗料を用い、実施例１と同じ方法で形成した有機樹脂皮膜の加工密着性を調査した。
[Comparative Example 1-2]
The polyaniline powder synthesized in Example 1 was dissolved in methylpyrrolidone at a mass ratio of 1:10, and a paint containing p-toluenesulfonic acid as a dopant at a ratio of 0.1 mol / l was chromated (Cr adhesion amount). : 50 mg / m 2 ) Plate thickness: 0.8 mm, coated amount per side: 20 g / m 2 of electrogalvanized steel sheet was applied in the same manner as in Example 1 and the work adhesion was investigated.
[Comparative Example 1-3]
A paint in which the polyaniline powder synthesized in Example 1 is dissolved in methylpyrrolidone at a mass ratio of 1:10, and further 10% by mass of an epoxy resin and 0.1 mol / l of p-toluenesulfonic acid as a dopant. The working adhesion of the organic resin film formed by the same method as in Example 1 was investigated.
表３の調査結果にみられるように、有機官能基にシクロアルカン，π結合を有するシランカップリング剤No.１〜３を配合した塗料から成膜された有機樹脂皮膜は、曲げ試験前とほぼ同じ状態で下地鋼に付着しており、シランカップリング剤無添加，クロメート処理，エポキシ樹脂との混合系と比較すると加工密着性の大幅な改善を確認できた。
アミノ基を有するシランカップリング剤No.４を配合した場合、塗料がゲル化した。この例では、シランカップリング剤のアミノ基とドーパントが相互作用して塗料がゲル化したものと考えられる。
As can be seen from the results of the investigation in Table 3, the organic resin film formed from the paint containing the silane coupling agent No. 1 to 3 having cycloalkane and π bond in the organic functional group is almost the same as before the bending test. Adhering to the base steel in the same state, it was confirmed that the work adhesion was greatly improved compared to the mixed system with no addition of silane coupling agent, chromate treatment, and epoxy resin.
When silane coupling agent No. 4 having an amino group was blended, the paint gelled. In this example, it can be considered that the amino group of the silane coupling agent and the dopant interacted to gel the paint.
実施例１で合成したポリアニリン粉末をメチルピロリドンに質量比１：１０で溶し込み、表１のシランカップリング剤No.１を３.０質量％配合した塗料を用いて製造された実施例１の有機樹脂被覆鋼板にドーパント溶液を塗布量：５ｍｌ／ｍ2でバーコート塗布し、到達板温：１５０℃で加熱・乾燥することにより有機樹脂皮膜を改質した。ドーパント溶液としては、各種ドーパントを溶解した０.１モル／ｌ水溶液(表４)を使用した。
改質された有機樹脂皮膜について、実施例１と同様に加工密着性を調査すると共に、四端子法で表面抵抗を測定することにより導電性を調査した。
Example 1 produced using a paint in which the polyaniline powder synthesized in Example 1 was dissolved in methylpyrrolidone at a mass ratio of 1:10 and 3.0% by mass of silane coupling agent No. 1 shown in Table 1 was blended. The organic resin-coated steel sheet was coated with a dopant solution at a coating amount of 5 ml / m 2 , and the organic resin film was modified by heating and drying at an ultimate plate temperature of 150 ° C. As the dopant solution, a 0.1 mol / l aqueous solution (Table 4) in which various dopants were dissolved was used.
The modified organic resin film was examined for process adhesion in the same manner as in Example 1, and the conductivity was investigated by measuring the surface resistance by the four-terminal method.
〔比較例２-１〕
実施例１で合成したポリアニリン粉末をメチルピロリドンに質量比１：１０で溶し込み、表２のシランカップリング剤No.４を３.０質量％配合した塗料を用いて製造された実施例１の有機樹脂被覆鋼板に実施例２と同様の方法でドープ処理し、導電性，加工密着性を調査した。
〔比較例２-２〕
ウレタン樹脂(スーパーフレックス110：第一工業製薬製)を主成分とする塗料を用いてウレタン樹脂被覆鋼板を作製し、導電性を調査した。
[Comparative Example 2-1]
Example 1 produced using a paint in which the polyaniline powder synthesized in Example 1 was dissolved in methylpyrrolidone at a mass ratio of 1:10 and 3.0% by mass of silane coupling agent No. 4 in Table 2 was blended. The organic resin-coated steel sheet was doped by the same method as in Example 2, and the conductivity and work adhesion were investigated.
[Comparative Example 2-2]
A urethane resin-coated steel sheet was prepared using a paint mainly composed of a urethane resin (Superflex 110: manufactured by Daiichi Kogyo Seiyaku), and the conductivity was investigated.
表４の調査結果にみられるように、ドープ状態の有機樹脂被覆鋼板は、ドーパント種に応じて異なる色調を呈したが、色調に及ぼすシランカップリング剤の影響は見られなかった。何れの有機樹脂被覆鋼板も、ドーピングによる加工密着性の低下は生じなかった。
有機官能基としてシクロアルカン，π結合を有するシランカップリング剤No.１を用いた有機樹脂皮膜では、ドーピング前に比較して導電率が大幅に向上しており、なかでもp-トルエンスルホン酸をドープした有機樹脂皮膜で高い導電率が得られた。
表４の結果は、ドーピングにより導電性を付与した有機樹脂被覆鋼板は、家電機器，OA機器のケーシング材として使用したときに十分な帯電防止能，電磁波シールド性をもつことを示している。
As seen in the investigation results of Table 4, the organic resin-coated steel sheet in the doped state exhibited a different color tone depending on the dopant species, but no influence of the silane coupling agent on the color tone was observed. None of the organic resin-coated steel sheets caused a decrease in work adhesion due to doping.
In the organic resin film using the silane coupling agent No. 1 having cycloalkane and π bond as the organic functional group, the conductivity is greatly improved as compared with that before doping, and in particular, p-toluenesulfonic acid is used. High conductivity was obtained with the doped organic resin film.
The results in Table 4 indicate that the organic resin-coated steel sheet imparted with conductivity by doping has sufficient antistatic ability and electromagnetic wave shielding properties when used as a casing material for home appliances and OA equipment.
原板として、フェライト系ステンレス鋼板，オーステナイト系ステンレス鋼板，電気亜鉛めっき鋼板，溶融Ｚｎ-６質量％Ａｌ-３質量％Ｍｇ合金めっき鋼板，溶融Ａｌ-９質量％Ｓｉ合金めっき鋼板，溶融Ｚｎ-５５質量％Ａｌ合金めっき鋼板，電気銅めっき鋼板，冷延鋼板を用意した。
シランカップリング剤No.１を３.０質量％配合した塗料を用い、実施例２と同じ条件下で膜厚：２μｍの有機樹脂皮膜を各原板に形成した後、０.１モル／ｌのp-トルエンスルホン酸，ポリリン酸をドーパント溶液として用い実施例２と同じ条件で有機樹脂被覆鋼板に塗布した。
Ferrous stainless steel plate, austenitic stainless steel plate, electrogalvanized steel plate, molten Zn-6 mass% Al-3 mass% Mg alloy plated steel plate, molten Al-9 mass% Si alloy plated steel plate, molten Zn-55 mass % Al alloy-plated steel sheet, electrolytic copper-plated steel sheet, and cold-rolled steel sheet were prepared.
An organic resin film having a film thickness of 2 μm was formed on each original plate under the same conditions as in Example 2 using a paint in which 3.0% by mass of silane coupling agent No. 1 was blended, and then 0.1 mol / l. p-Toluenesulfonic acid and polyphosphoric acid were applied as a dopant solution to the organic resin-coated steel sheet under the same conditions as in Example 2.
ドーピング後の有機樹脂被覆鋼板から試験片を切り出し、腐食試験，加工試験に供した。
腐食試験では、JIS Z2371に準拠して３５℃の５％ＮａＣｌ水溶液を端面をシールした試験片に噴霧した。２４０時間の塩水噴霧後、電気亜鉛めっき鋼板，溶融Ｚｎ-Ａｌ-Ｍｇ合金めっき鋼板，溶融Ａｌ-Ｓｉ合金めっき鋼板，溶融Ｚｎ-５５％Ａｌ合金めっき鋼板については試験片表面に発生した白錆を、フェライト系ステンレス鋼板，オーステナイト系ステンレス鋼板，冷延鋼板については試験片表面に発生した赤錆を、電気銅めっき鋼板については試験片表面に発生した緑錆を観察した。そして、試験片表面に占める各錆の面積率が５％未満を◎，５〜１０％を○，１０〜３０％を△，３０〜５０％を▲，５０％以上を×として平坦部の耐食性を評価した。
A test piece was cut out from the organic resin-coated steel sheet after doping and subjected to a corrosion test and a processing test.
In the corrosion test, a 5% NaCl aqueous solution at 35 ° C. was sprayed on the test piece whose end face was sealed in accordance with JIS Z2371. After spraying salt water for 240 hours, electrogalvanized steel sheet, hot-dip Zn-Al-Mg alloy-plated steel sheet, hot-melted Al-Si alloy-plated steel sheet, hot-dip Zn-55% Al alloy-plated steel sheet For the ferritic stainless steel plate, austenitic stainless steel plate and cold rolled steel plate, red rust generated on the surface of the test piece was observed, and for the electrolytic copper plated steel plate, green rust generated on the surface of the test piece was observed. And the area ratio of each rust occupying the surface of the test piece is less than 5%, 5-10% is ◯, 10-30% is △, 30-50% is ▲, 50% or more is x, and the corrosion resistance of the flat part. Evaluated.
表５の調査結果にみられるように、鋼板の種類に拘わらず、有機樹脂皮膜の形成によって耐食性が向上していることが判る。また、ドーパントの種類による耐食性の有意差は検出されなかった。 As can be seen from the investigation results in Table 5, it can be seen that the corrosion resistance is improved by the formation of the organic resin film regardless of the type of the steel sheet. In addition, no significant difference in corrosion resistance depending on the type of dopant was detected.
加工試験では、曲げ部内側に同じ厚みの板材を複数枚介在させて１８０度曲げ試験した。曲げ試験後、曲げ部外側に粘着テープを貼り付け瞬時に引き剥がすテープ剥離試験で有機樹脂皮膜の剥離状態を観察し、実施例１と同じ基準で加工密着性を評価した。
表６の調査結果にみられるように、有機樹脂皮膜にシランカップリング剤を含ませることにより加工密着性が向上していることがわかる。シランカップリング剤配合による加工密着性向上効果は、なかでもステンレス鋼板，電気銅めっき鋼板，Ａｌ系めっき鋼板で顕著であった。
In the processing test, a 180-degree bending test was performed with a plurality of plate materials having the same thickness interposed inside the bent portion. After the bending test, the peeled state of the organic resin film was observed by a tape peeling test in which an adhesive tape was applied to the outside of the bent portion and peeled off instantaneously, and the work adhesion was evaluated according to the same criteria as in Example 1.
As seen in the investigation results in Table 6, it can be seen that the work adhesion is improved by including a silane coupling agent in the organic resin film. The effect of improving the work adhesion by blending the silane coupling agent was particularly remarkable in stainless steel plates, electrolytic copper plated steel plates, and Al-based plated steel plates.
以上に説明したように、本発明の有機樹脂被覆鋼板は、複素環式共役系又はヘテロ原子含有共役系のπ共役高分子に有機官能基としてシクロアルカン，π結合を有するシランカップリング剤を配合した塗料から成膜された有機樹脂皮膜にドープ処理で導電性を付与すると、従来の塗装鋼板からは予想できない高導電性の有機樹脂被覆鋼板が得られる。この有機樹脂被覆鋼板は、高い導電率の他に加工密着性，耐食性にも優れているので内装材，外装材，表装材，電磁シールド材等として広汎な分野で使用される。 As described above, the organic resin-coated steel sheet of the present invention is compounded with a heterocyclic conjugated system or a heteroatom-containing conjugated π-conjugated polymer with a cycloalkane or silane coupling agent having a π bond as an organic functional group. When conductivity is imparted to the organic resin film formed from the coated paint by doping, a highly conductive organic resin-coated steel sheet that cannot be predicted from a conventional coated steel sheet is obtained. This organic resin-coated steel sheet is used in a wide range of fields as an interior material, an exterior material, a cover material, an electromagnetic shield material, and the like because it has excellent work adhesion and corrosion resistance in addition to high conductivity.
Claims (3)
前記シランカップリング剤の量は、前記π共役高分子の質量に対して０．１〜３０質量％であることを特徴とする有機樹脂被覆鋼板。 Containing a heterocyclic conjugated system or heteroatom on the surface of the base steel via an interface layer made of a silane coupling agent having one or more organic functional groups selected from cycloalkane and π-bonded atomic groups An organic resin-coated steel sheet provided with an organic resin film containing a conjugated π-conjugated polymer as a main component and a dopant imparting conductivity to the π-conjugated polymer ,
The amount of the silane coupling agent is 0.1 to 30% by mass with respect to the mass of the π-conjugated polymer .
The organic resin-coated steel sheet according to claim 1 or 2, wherein the hetero atom contained in the π-conjugated polymer is nitrogen and / or sulfur.
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| CN201160163Y (en) * | 2007-12-29 | 2008-12-03 | 富士康(昆山)电脑接插件有限公司 | Electric Connector |
| JP5605011B2 (en) * | 2010-06-25 | 2014-10-15 | Ｊｆｅスチール株式会社 | Resin-coated metal plate for containers |
| CA2819340C (en) * | 2012-08-31 | 2019-04-30 | The Boeing Company | Chromium-free conversion coating |
| JP6051784B2 (en) * | 2012-11-02 | 2016-12-27 | Ｊｆｅスチール株式会社 | Resin-coated metal plate for containers |
| JP6862316B2 (en) * | 2016-09-08 | 2021-04-21 | Ｊｆｅスチール株式会社 | High-strength steel sheet with excellent delayed fracture resistance and its manufacturing method |
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