JP2001316629A - Anticorrosive coating material composition and steel stock having anticorrosive covering - Google Patents
Anticorrosive coating material composition and steel stock having anticorrosive coveringInfo
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- JP2001316629A JP2001316629A JP2000133542A JP2000133542A JP2001316629A JP 2001316629 A JP2001316629 A JP 2001316629A JP 2000133542 A JP2000133542 A JP 2000133542A JP 2000133542 A JP2000133542 A JP 2000133542A JP 2001316629 A JP2001316629 A JP 2001316629A
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- Prior art keywords
- coating
- anticorrosive
- mass
- anticorrosion
- steel material
- Prior art date
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- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気防食を施した鋼構
造物等に塗装し、陰極剥離を低減するために有効な防食
塗料組成物および防食被覆鋼材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anticorrosion paint composition and an anticorrosion-coated steel material which are applied to a steel structure or the like which has been subjected to cathodic protection to reduce cathodic peeling.
【０００２】[0002]
【従来の技術】海中や土中環境下における鋼材の腐食を
防止する手段の一つに電気防食がある。2. Description of the Related Art Electrolytic protection is one of the means for preventing the corrosion of steel materials under the sea or soil environment.
【０００３】電気防食は、鋼材を鋼材の安定電位に分極
することにより腐食を防止する方法であるが、鉄部分が
大面積になると電力や犠牲陽極の消費が増加するため、
通常は鋼材をそのまま電気防食することはなく、塗装や
ライニングのような有機被膜による防食手段と併せてお
こなうことが多い。[0003] Cathodic protection is a method of preventing corrosion by polarizing a steel material to a stable potential of the steel material. However, when the iron part has a large area, consumption of power and sacrificial anode increases.
Normally, steel materials are not directly subjected to electrolytic protection, but are often used in combination with anticorrosion measures using an organic coating such as painting or lining.
【０００４】つまりこの複合防食は、鋼材の大部分が有
機被膜により防食し、該有機被膜に発生する傷、ピンホ
ール等の欠陥部分は電気防食で補うことで効果的な防食
を行うようにした方法である。[0004] In other words, in this composite corrosion protection, most of the steel material is protected by the organic coating, and defects such as scratches and pinholes generated in the organic coating are compensated for by the electrolytic protection to provide effective corrosion protection. Is the way.
【０００５】一般に、陰極に分極された金属表面では金
属イオンが還元されて溶解されなくなるため、溶解しよ
うとする金属イオンに見合うだけの電力を与えて電気防
食すれば十分な効果が得られる。しかし、土中などの防
食では、欠陥部分の表面積を知ることは極めて困難であ
るため、過剰な電気防食を施すのが通例とされている。In general, metal ions are reduced and no longer dissolved on the surface of the metal polarized on the cathode, so that a sufficient effect can be obtained by applying an electric power corresponding to the metal ions to be dissolved and performing cathodic protection. However, since it is extremely difficult to know the surface area of a defective portion in the protection of soil or the like, it is customary to apply excessive electrolytic protection.
【０００６】とは言え、過剰な分極化は陰極における水
の電気分解により水酸イオンを発生させる関係で、有機
被膜の傷部が陰極となり、常にアルカリ雰囲気に曝され
ることになり、鋼材−有機被膜の界面ないしは有機被膜
間のいずれかの界面、とくに耐アルカリ性の弱い部位で
被膜の劣化や接着点の切断が起こり、陰極剥離現象が発
生することも避け難い。[0006] However, excessive polarization causes hydroxyl ions to be generated by electrolysis of water at the cathode, so that the damaged portion of the organic film becomes a cathode and is always exposed to an alkaline atmosphere. It is also unavoidable that the deterioration of the coating and the breaking of the adhesion point occur at the interface between the organic coatings or at any interface between the organic coatings, particularly at the site having weak alkali resistance, and the cathode peeling phenomenon occurs.
【０００７】このような陰極剥離現象を抑制するための
手段として、クロメート処理や特定の熱硬化性エポキシ
樹脂を施す方法〔特開昭59−222275号公報〕やエポキシ
樹脂中に防錆顔料を含有させる方法〔特開平07-178871
号公報〕などが提案されている。しかし、これらの技術
は、耐陰極剥離性の要求に対しては不十分である。As a means for suppressing such a cathode peeling phenomenon, a method of applying a chromate treatment or a specific thermosetting epoxy resin (Japanese Patent Application Laid-Open No. 59-222275), or a method of containing a rust-preventive pigment in the epoxy resin. Method (JP-A-07-178871
Gazette] has been proposed. However, these techniques are insufficient for the demand for cathodic peel resistance.
【０００８】[0008]
【発明が解決しようとする課題】本発明者は、電気防食
時における形成塗膜の陰極剥離を防止する機構ならびに
有効成分について多角的に研究を進めた結果、二価およ
び／または三価のマンガン塩と熱硬化性樹脂からなる組
成物が耐陰極剥離性の塗料として優れた防止機能を発揮
することを解明した。SUMMARY OF THE INVENTION The present inventor has conducted various studies on a mechanism for preventing cathodic peeling of a formed coating film during cathodic protection and an active ingredient. As a result, the present inventors have found that divalent and / or trivalent manganese can be obtained. It has been elucidated that a composition comprising a salt and a thermosetting resin exerts an excellent prevention function as a cathode peeling-resistant paint.
【０００９】本発明は、前記の知見に基づいて開発され
たもので、その目的は、電気防食時における防食塗膜の
陰極剥離を効果的に防止することができる防食塗料組成
物を提供し、またかかる防食塗料組成物を用いて形成す
ることができる耐陰極剥離性に優れた防食被覆鋼材を提
供することにある。The present invention has been developed on the basis of the above findings, and has as its object to provide an anticorrosion paint composition which can effectively prevent cathodic peeling of an anticorrosion coating film during cathodic protection. Another object of the present invention is to provide an anticorrosion-coated steel material which can be formed using such an anticorrosion coating composition and has excellent cathode peeling resistance.
【００１０】[0010]
【課題を解決するための手段】上記の目的を達成するた
めの本発明による防食塗料組成物は、（１）熱硬化性樹
脂固形分100 質量％に対して二価および／または三価の
マンガン塩固形分5 〜300 質量％を含有することを特徴
とするものである。In order to achieve the above object, the anticorrosion coating composition of the present invention comprises (1) a divalent and / or trivalent manganese based on 100% by mass of a thermosetting resin solid content. It is characterized by containing a salt solid content of 5 to 300% by mass.
【００１１】また本発明は、上記の防食塗料組成物を使
用して、（２）鋼材表面に、同防食塗料組成物を積層
し、その上に厚さ１ｍｍ以上の防食被覆を積層したこと
を特徴とする防食被覆鋼材を提供するものである。Further, the present invention provides (2) using the above anticorrosion coating composition, laminating the anticorrosion coating composition on the surface of a steel material, and laminating an anticorrosion coating having a thickness of 1 mm or more thereon. The present invention provides a corrosion-resistant coated steel material.
【００１２】さらにより優れた防食被覆鋼材として、
（３）鋼材表面に化成被膜が積層され、その上に上記
（１）の防食塗料組成物からなる防食塗料組成物を積層
し、さらにその上に厚さ１ｍｍ以上の防食被覆を積層し
たことを特徴とする防食被覆鋼材を提供するものであ
る。As an even more excellent anticorrosion coated steel material,
(3) A conversion coating is laminated on the surface of a steel material, an anticorrosion coating composition comprising the anticorrosion coating composition of (1) is laminated thereon, and an anticorrosion coating having a thickness of 1 mm or more is further laminated thereon. The present invention provides a corrosion-resistant coated steel material.
【００１３】[0013]
【発明の実施の形態】本発明に用いられる熱硬化性樹脂
は、基本的に鋼材、ブラストクリーニング等の機械的処
理を施した鋼材あるいはクロメート、リン酸亜鉛等の化
成処理を施した鋼材に強固に密着し得るものであればよ
い。対象樹脂としては、エポキシ樹脂とエポキシ樹脂硬
化剤、ポリオール樹脂とイソシアネート類、アクリル変
性エポキシ樹脂と重合開始剤、アルキッド樹脂、湿気硬
化型ウレタン樹脂等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin used in the present invention is basically a steel material, a steel material subjected to a mechanical treatment such as blast cleaning or a steel material subjected to a chemical conversion treatment such as chromate or zinc phosphate. Any material can be used as long as it can be adhered to. Examples of the target resin include an epoxy resin and an epoxy resin curing agent, a polyol resin and an isocyanate, an acryl-modified epoxy resin and a polymerization initiator, an alkyd resin, and a moisture-curable urethane resin.
【００１４】このうち本発明の目的に最も好適な樹脂
は、エポキシ樹脂とウレタン樹脂である。この理由は、
エポキシ樹脂およびウレタン樹脂は耐水性が優れてお
り、しかも鋼材に対する密着性が良好であるためであ
る。なお、これ以外の樹脂を用いた場合にも耐陰極剥離
性に対して効果があることは言うまでもない。Among these, the most preferred resins for the purpose of the present invention are epoxy resins and urethane resins. The reason for this is
This is because epoxy resins and urethane resins have excellent water resistance and good adhesion to steel materials. Needless to say, the use of other resins is also effective for the cathode peeling resistance.
【００１５】一方、本発明の防食塗料組成物を構成する
二価のマンガン塩としては、炭酸マンガン［MnCO3 ］、
硼酸マンガン［MnH2(BO3)2］または塩基性リン酸マンガ
ン［Mn(H2PO4)2・4H20］、酸化マンガン（II）［MnO ］
が挙げられ、三価のマンガン塩としては酸化マンガン
（III）［Ｍｎ2Ｏ3］などが挙げられ、これらの1 種も
しくは２種以上の混合物が適用できるが、炭酸マンガン
が最も好ましい。On the other hand, the divalent manganese salt constituting the anticorrosion coating composition of the present invention includes manganese carbonate [MnCO 3 ],
Borate Manganese [MnH 2 (BO 3) 2 ] or a basic manganese phosphate [Mn (H 2 PO 4) 2 · 4H 2 0], manganese oxide (II) [MnO]
Examples of the trivalent manganese salt include manganese oxide (III) [Mn 2 O 3 ]. One or a mixture of two or more of these can be used, but manganese carbonate is most preferred.
【００１６】熱硬化性樹脂と二価および／または三価の
マンガン塩との配合割合は、熱硬化性樹脂固形分100 質
量％に対して二価および／または三価のマンガン塩固形
分5〜300 質量％の範囲、好ましくは10〜200 質量％、
より好ましくは10〜100 質量％に設定する。二価および
／または三価のマンガン塩固形分が5 質量％未満では陰
極剥離現象に対する抑制効果が発現せず、300 質量％を
越えると耐陰極剥離効果は発揮されるものの、塗膜が脆
弱となって実用することが不可能となる。The mixing ratio of the thermosetting resin to the divalent and / or trivalent manganese salt is such that the divalent and / or trivalent manganese salt solid content is 5 to 100% by mass of the thermosetting resin solid content. In the range of 300% by weight, preferably 10-200% by weight,
More preferably, it is set to 10 to 100% by mass. When the divalent and / or trivalent manganese salt solids content is less than 5% by mass, the effect of suppressing the cathodic peeling phenomenon is not exhibited, and when the content exceeds 300% by mass, the cathodic peeling effect is exhibited, but the coating film is fragile. It becomes impossible to put it into practical use.
【００１７】熱硬化性樹脂と二価および／または三価の
マンガン塩組成成分のほか、必要に応じて有機溶剤、着
色顔料、表面調整剤等の成分を添加することができる。
本発明の塗料組成物中の固形分濃度は10〜100 質量％で
使用することができる。[0017] In addition to the thermosetting resin and the divalent and / or trivalent manganese salt composition components, components such as an organic solvent, a coloring pigment, and a surface conditioner can be added as necessary.
The solid content in the coating composition of the present invention can be used at 10 to 100% by mass.
【００１８】上記の組成からなる防食塗料は、通常の塗
料製造と同一の方法で製造することができる。すなわ
ち、液状無溶剤型塗料の場合には、熱硬化性樹脂に所定
量の二価および／または三価のマンガン塩を加え、ロー
ルミル、ディゾルバー等で分散処理し、有機溶剤型塗料
の場合にはロールミル、ディゾルバー、SGミル、ポット
ミル等で分散処理する。粉体塗料にする場合には、熱硬
化性樹脂に二価および／または三価のマンガン塩の所定
量を加え、予備混合したのち加熱混練し、冷却後に粉
砕、分級すればよい。結晶水を持つリン酸マンガン塩の
様な場合には、予め１５０℃程度に加熱して、結晶水を
取り除いておくのが好ましい。The anticorrosion paint having the above-mentioned composition can be produced by the same method as the usual paint production. That is, in the case of a liquid non-solvent type paint, a predetermined amount of a divalent and / or trivalent manganese salt is added to a thermosetting resin, and a dispersion treatment is performed with a roll mill, a dissolver or the like. Dispersion treatment is performed with a roll mill, dissolver, SG mill, pot mill, or the like. In the case of a powder coating, a predetermined amount of a divalent and / or trivalent manganese salt may be added to the thermosetting resin, premixed, heated and kneaded, cooled and then pulverized and classified. In the case of a manganese phosphate salt having water of crystallization, it is preferable to remove the water of crystallization by heating to about 150 ° C. in advance.
【００１９】本発明による防食塗料組成物を塗布するに
は、刷毛、ローラー、エアレススプレー、エアスプレ
ー、粉体塗装機などを塗料の形態に合わせて選定し、常
法に従って塗装される。To apply the anticorrosion coating composition according to the present invention, a brush, a roller, an airless spray, an air spray, a powder coating machine and the like are selected according to the form of the coating, and the coating is applied according to a conventional method.
【００２０】本発明の被覆鋼材は、ショットブラストや
サンドブラストなどの機械的清浄処理または酸洗などに
よる表面清浄の後に、そのまま、またはクロメートを塗
布した後、本発明の防食塗料組成物を塗装することで得
られる。クロメートとしてはクロム酸クロムにシリカコ
ロイドあるいはリン酸が添加されても良い。The coated steel material of the present invention is obtained by applying the anticorrosion coating composition of the present invention as it is or after applying a chromate after mechanical cleaning treatment such as shot blasting or sand blasting or surface cleaning by pickling. Is obtained. As the chromate, silica colloid or phosphoric acid may be added to chromium chromate.
【００２１】本発明の防食組成物は、被覆鋼材の上に塗
布し硬化される。The anticorrosion composition of the present invention is applied on a coated steel material and cured.
【００２２】この防食塗料組成物として用いられるエポ
キシ樹脂は、常温あるいは加熱硬化させた後、ポリエチ
レン接着剤、ポリエチレンを積層する事で、耐陰極剥離
性に優れたポリエチレン被覆鋼材が得られる。また、ポ
リオールとイソシアネートあるいは湿気硬化型ウレタン
からなる防食塗料組成物を塗装した後、ポリオールとイ
ソシアネートの反応によって得られるウレタン塗装を、
好ましくは１ｍｍ以上の厚みとなるように実施すること
によって対陰極剥離性に優れたポリウレタン被覆鋼材が
得られる。１ｍｍ以下では、長期の防食性が不十分とな
り、電気防食時の塗膜膨れが顕著となる。一方、１ｍｍ
以上であれば厚みに制限は無い。望ましくは、経済上か
ら２〜３ｍｍが好ましい。本発明の塗装後の塗膜面に
は、エポキシ樹脂塗料などの重防食塗膜や着色、美装の
ための上塗り層を形成しても差し支えない。The epoxy resin used as the anticorrosion coating composition is cured at room temperature or by heating and then laminated with a polyethylene adhesive and polyethylene, whereby a polyethylene-coated steel material having excellent cathodic peeling resistance can be obtained. Further, after coating the anticorrosion coating composition comprising a polyol and isocyanate or moisture-curable urethane, urethane coating obtained by the reaction of the polyol and isocyanate,
Preferably, the thickness is 1 mm or more to obtain a polyurethane-coated steel excellent in anti-cathode peelability. When the thickness is 1 mm or less, the long-term corrosion resistance becomes insufficient, and the coating film swells during electrolytic protection. On the other hand, 1 mm
There is no limitation on the thickness as long as it is above. Desirably, it is 2-3 mm from the viewpoint of economy. On the coated film surface after the coating according to the present invention, a heavy-duty anticorrosive coating film such as an epoxy resin paint or an overcoating layer for coloring and appearance may be formed.
【００２３】本発明に係る防食塗料組成物が優れた耐陰
極剥離性を発揮する機構については詳しく解明するに至
っていないが、二価および／または三価のマンガン塩が
強アルカリ発生のもととなる酸素還元の抑制に対して有
効であると推測される。Although the mechanism by which the anticorrosion coating composition of the present invention exhibits excellent cathodic peel resistance has not been elucidated in detail, divalent and / or trivalent manganese salts may cause strong alkali generation. It is presumed to be effective for suppressing oxygen reduction.
【００２４】すなわち、陰極剥離の現象は次のような機
構によるものと推測される。 （1 ）欠陥部周囲の鋼材面が陰極となり、そこで塗膜を
通ってきた酸素の還元が起こる。 （2 ）酸素の還元により生じた水酸イオンにより強アル
カリとなる。 （3 ）水酸イオンにより鋼−塗膜間の接着点が破壊され
る。That is, the phenomenon of cathode separation is presumed to be due to the following mechanism. (1) The steel surface around the defect becomes the cathode, where oxygen that has passed through the coating is reduced. (2) It becomes a strong alkali by the hydroxyl ions generated by the reduction of oxygen. (3) The adhesion point between the steel and the coating film is destroyed by hydroxyl ions.
【００２５】したがって、陰極剥離を防止するためには
アルカリとなる水酸イオンの生成すなわち酸素の還元を
抑制することが有効である。かつアルカリを中和するこ
とが有効な手段となる。本発明の組成成分となる二価お
よび／または三価のマンガン酸塩は、酸素の補足に有効
であり、酸素還元量を減少させるのに有効に機能する。
また、炭酸マンガンや硼酸マンガン、リン酸マンガンの
陰イオン成分は、アルカリに対するpH緩衝作用があり、
この作用が水の拡散に伴って拡散する水酸イオンを中和
し、界面の破壊に対して保護作用を発現する。Therefore, in order to prevent cathode peeling, it is effective to suppress the generation of alkali hydroxide ions, that is, the reduction of oxygen. In addition, neutralizing the alkali is an effective means. The divalent and / or trivalent manganate which is a component of the present invention is effective for capturing oxygen, and functions effectively for reducing the amount of oxygen reduction.
In addition, the anionic components of manganese carbonate, manganese borate, and manganese phosphate have a pH buffering effect on alkali,
This action neutralizes the hydroxyl ions that diffuse with the diffusion of water, and exerts a protective action against destruction of the interface.
【００２６】このような作用が総合的に機能して電気防
食における形成皮膜の陰極剥離を効果的に防止すること
が可能となる。[0026] Such an operation functions comprehensively, and it is possible to effectively prevent cathodic peeling of the formed film in cathodic protection.
【００２７】[0027]
【実施例】以下、本発明の実施例を比較例と対比して詳
細に説明する。EXAMPLES Examples of the present invention will be described in detail below in comparison with comparative examples.
【００２８】実施例1 〜6 、比較例1 〜3 エポキシ樹脂〔「エピコート807 」油化シェルエポキシ
（株）製、液状〕 100質量％に対して、表１に示す組成
で炭酸マンガン塩を配合し、ロールミル１Passで分散処
理して液状無溶剤型のエポキシ樹脂塗料を調製した。こ
の塗料液100 質量％に複素環式ジアミン変性物系エポキ
シ硬化剤〔「エポメートB002」油化シェルエポキシ
（株）製〕23質量％を加えて撹伴混合した。Examples 1 to 6, Comparative Examples 1 to 3 Epoxy resin ("Epicoat 807" manufactured by Yuka Shell Epoxy Co., Ltd., liquid) 100% by mass of manganese carbonate with the composition shown in Table 1 Then, dispersion treatment was carried out with a roll mill 1 Pass to prepare a liquid solvent-free epoxy resin paint. To 100% by mass of the coating solution, 23% by mass of a heterocyclic diamine modified epoxy curing agent [“Epomate B002” manufactured by Yuka Shell Epoxy Co., Ltd.] was added and mixed with stirring.
【００２９】炭酸マンガン混合のエポキシ樹脂と硬化剤
の混合液をバーコーターにより膜厚30〜40μm になるよ
うにサンドブラストした鋼材（SS４００）に塗布し、3
日間自然放置したのち、80℃の温度で30分間強制乾燥し
た。このようにして塗布した巾70mm、長さ150mm 、厚さ
9mm の試験片につき電防試験、１mm巾ゴバン目試験およ
び衝撃試験を、また巾70mm、長さ150mm 、厚さ0 ． 8mm
の試験片を用いて折り曲げ試験をおこなった。それらの
測定結果を表2に併せて示した。A mixed solution of a manganese carbonate-mixed epoxy resin and a curing agent is applied by a bar coater to a steel material (SS400) sandblasted to a thickness of 30 to 40 μm.
After allowing to stand naturally for days, it was forcibly dried at a temperature of 80 ° C. for 30 minutes. 70mm width, 150mm length, thickness applied in this way
A 9 mm test piece was subjected to an electrical protection test, a 1 mm width gouge test and an impact test, and a width of 70 mm, a length of 150 mm and a thickness of 0 mm. 8mm
A bending test was performed using the test pieces of Example 1. The measurement results are also shown in Table 2.
【００３０】なお、各試験の測定方法は下記によった。 （１）電気防食試験１ 試験片の被覆層に長さ7cm の素地に達する2 本のカット
を交差するように切り込み、側面および裏面をJISK5664
第1 種のタールエポキシ樹脂塗料で保護コートする。試
験片の1 つの角部をやすりで磨き、コードをスポット溶
接してアルミ犠牲陽極（ナカボーテック（株）製）と結
線する。カット部および犠牲陽極を食塩水に浸漬させた
状態で、20℃で30日間放置する。放置後、試験片のカソ
−ド部をナイフでこじ上げ、剥離した片側巾を測定す
る。 （２）電気防食試験2 ASTM G8 −90に準拠して、鋼材に−１．５Ｖ（飽和硫酸
銅電極基準）の電位を印可して60℃で15日間試験をおこ
ない、人工欠陥による穴の周りからの剥離巾を上記の電
気防食試験1 と同様にして測定する。 （３）１mm巾ゴバン目試験JIS K ５４００ ８．５に準
拠し、セロテープ剥離後のゴバン目残率を評価する。 （４）折り曲げ試験 JIS K5400 8.1 に準拠し、直径10mmのシリンダーに沿っ
て180ー折り曲げ、曲げ部分の塗膜状態を評価する。判定
は次の基準でおこなった。 異常なし：◎ 微細なクラック：○ クラックおよび剥
離発生：× （５）衝撃試験 JIS K5400 8 ． 3． 2に準拠し、 500g の分銅を50cm高
さから落下し、塗膜状態を評価する。判定は次の基準で
おこなった。 異常なし：◎ 微細なクラック：○ 剥離発生：×The measuring method in each test was as follows. (1) Cathodic protection test 1 Two cuts reaching the base material of 7cm length were cut into the coating layer of the test piece so as to cross, and the side and back sides were JISK5664.
Protective coating with first class tar epoxy resin paint. One corner of the test piece is sanded, and the cord is spot-welded and connected to an aluminum sacrificial anode (manufactured by Nakabo Tech Co., Ltd.). The cut portion and the sacrificial anode are immersed in a saline solution and left at 20 ° C. for 30 days. After standing, the cathodic part of the test piece was pryed up with a knife, and the peeled one side width was measured. (2) Cathodic protection test 2 In accordance with ASTM G8-90, apply a potential of -1.5 V (based on a saturated copper sulfate electrode) to steel and conduct a test at 60 ° C for 15 days. Is measured in the same manner as in the above-described cathodic protection test 1. (3) 1 mm Width Gobang Test In accordance with JIS K 5400 8.5, the gobang residual ratio after peeling off the cellophane tape is evaluated. (4) Bending test According to JIS K5400 8.1, bend 180-degree along a cylinder with a diameter of 10 mm, and evaluate the coating state of the bent portion. The judgment was made based on the following criteria. No abnormalities: ◎ Fine cracks: ○ Cracks and peeling: × (5) Impact test JIS K5400 8. 3． In accordance with 2, a 500 g weight is dropped from a height of 50 cm to evaluate the state of the coating film. The judgment was made based on the following criteria. No abnormalities: ◎ Fine cracks: ○ Peeling occurred: ×
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 表２から、エポキシ樹脂に所定量の二価および／または
三価のマンガン塩を配合した塗料組成物による実施例1
〜6 の試験片は良好な耐陰極剥離性ならびに塗膜性能を
示したが、二価および／または三価のマンガン塩を添加
しない比較例1および二価および／または三価のマンガ
ン塩の配合量が5 質量％を下廻る比較例2 ては電防試験
での剥離が大きく、また、二価および／または三価のマ
ンガン塩配合量が300 質量％を越える比較例3 では耐剥
離性は良好であるものの、 1ｍｍ巾ゴバン目、折り曲げ
および衝撃特性が劣化する結果を示した。[Table 2] From Table 2, it can be seen that the coating composition in which a predetermined amount of a divalent and / or trivalent manganese salt is blended with an epoxy resin according to Example 1
The test specimens Nos. 1 to 6 showed good cathodic peeling resistance and coating film performance, but Comparative Example 1 in which no divalent and / or trivalent manganese salt was added and the combination of divalent and / or trivalent manganese salt In Comparative Example 2 in which the amount was less than 5% by mass, the peeling was large in an electrical protection test, and in Comparative Example 3 in which the content of divalent and / or trivalent manganese salts exceeded 300% by mass, the peeling resistance was poor. Although good, the result was that the 1 mm-wide gouge, bending and impact characteristics were deteriorated.
【００３３】実施例7 〜16、比較例4 表３に示す組成の塗料液100 質量％に実施例1 と同じ硬
化剤を30．9 質量％加えて混合し、これを実施例1 と同
様にして塗装試験片を作製し、測定試験を行い結果を表
４に示した。Examples 7 to 16 and Comparative Example 4 30.9% by mass of the same curing agent as in Example 1 was added to 100% by mass of a coating liquid having the composition shown in Table 3 and mixed. Then, a coated test piece was prepared, a measurement test was performed, and the results are shown in Table 4.
【００３４】[0034]
【表３】 [Table 3]
【００３５】[0035]
【表４】 表３および表４を対比して判るように、二価の炭酸マン
ガン塩（MnCO3 ）に塩基性リン酸マンガン（Mn(H2PO4)2
・4H2O）または／および硼酸マンガンを混合使用した実
施例7 〜16は良好な電防性を示したが、硼酸バリウムを
用いた比較例4の塗料組成物では電防性効果が著しく劣
る結果であった。[Table 4] As can be seen by comparing Tables 3 and 4, divalent manganese carbonate (MnCO 3 ) was added to basic manganese phosphate (Mn (H 2 PO 4 ) 2).
4H 2 O) and / or Examples 7 to 16 in which manganese borate was mixed and used showed good anti-electrostatic properties, but the coating composition of Comparative Example 4 using barium borate was significantly inferior in anti-electrostatic properties. It was a result.
【００３６】実施例17-26 エポキシ樹脂〔「エピコート807 」油化シェルエポキシ
（株）製、液状〕 100質量％に対して、表4の実施例17
−26に示す組成で二価および／または三価のマンガン塩
を配合し、ロールミル１Passで分散処理して液状無溶剤
型のエポキシ樹脂塗料を調製した。この塗料液100 質量
％に複素環式ジアミン変性物系エポキシ硬化剤〔「エポ
メートB002」油化シェルエポキシ（株）製〕23質量％を
加えて撹伴混合し、鋼材（SS４００）面にバーコーター
＃50で膜厚30〜50μm になるように塗装し、200 ℃の雰
囲気下で30分間加熱硬化して試験片を得た。この試験片
をホットプレス上で180 ℃の温度に急昇温し、これに厚
さ300 μｍの接着性ポリエチレンフィルム〔「アドマー
NE060 」三井石油化学（株）製〕を積層し、さらに180
℃に加温した低密度ポリエチレンの成形板（厚さ3mm ）
を重ねてローラー圧着した。この状態に30秒放置したの
ち水冷して、三層構造によるポリエチレン被覆鋼材の試
験片を作製した。この試験片につき、電防試験および密
着力試験をおこなった。密着力試験は、被覆層に1cm ｍ
巾で鋼材に達するようなカットをカッターナイフで形成
し、 180ー の角度の引張り試験値を測定する方法によ
り、初期密着力、食塩水（60℃、3 ％）浸漬後の密着力
および沸騰水（95〜100 ℃）浸漬後の密着力をそれぞれ
測定した。それらの測定結果を表6 に示した。Examples 17-26 Epoxy resin ["Epicoat 807", manufactured by Yuka Shell Epoxy Co., Ltd., liquid] 100% by mass of Example 17 in Table 4
A divalent and / or trivalent manganese salt having the composition shown in -26 was blended, and dispersed by a roll mill 1 Pass to prepare a liquid solvent-free epoxy resin paint. To 100% by mass of this coating liquid, 23% by mass of a heterocyclic diamine-modified epoxy curing agent [“Epomate B002” manufactured by Yuka Shell Epoxy Co., Ltd.] was added and mixed by stirring, and a bar coater was applied to the steel material (SS400) surface. It was coated with # 50 so as to have a film thickness of 30 to 50 μm, and cured by heating at 200 ° C. for 30 minutes to obtain a test piece. The specimen was rapidly heated to 180 ° C. on a hot press, and a 300 μm-thick adhesive polyethylene film [Admer
NE060 "manufactured by Mitsui Petrochemical Co., Ltd.]
Molded plate of low density polyethylene heated to ℃ (thickness 3mm)
Were stacked and pressed with a roller. After being left in this state for 30 seconds, it was cooled with water to produce a test piece of a polyethylene-coated steel material having a three-layer structure. This test piece was subjected to an electrical protection test and an adhesion test. Adhesion test is 1 cm
The initial adhesion, adhesion after immersion in saline solution (60 ° C, 3%) and boiling water were measured by forming a cut reaching the steel material with a width using a cutter knife and measuring the tensile test value at an angle of 180 °. (95 to 100 ° C.) The adhesion after immersion was measured. Table 6 shows the measurement results.
【００３７】比較例5 エポキシ樹脂〔「エピコート1004」油化シェルエポキシ
（株）製、固形〕 100質量％に対し、ジシアンアミド
〔「エビキュアDICY15」油化シェルエホキシ（株）製〕
8 質量％および2 メチル4 エチルイミダゾール〔四国化
成（株）製〕 1質量％を加えてミキサーで混合粉砕し、
ついでニーダーにより70〜90℃で分散予備反応させた。
この反応物100 質量％に酸化珪素微粉末〔「アエロジル
300 」日本アエロジル（株）製〕3 質量％を添加して粉
砕分級し、平均粒径38μm の粉体塗料を調製した。実施
例１７と同―の鋼材を180 ℃に予熱し、前記組成の粉体
塗料を静電塗装したのち後焼きして塗膜200 〜250 μm
の試験片を得た。この試験片に対して実施例１７と同様
に3 層構造によるポリエチレン被覆鋼材の試験片を作製
した。この試験片につき実施例１と同様に試験をおこな
い、結果を表6 に併載した。Comparative Example 5 Epoxy resin ["Epicoat 1004", manufactured by Yuka Shell Epoxy Co., Ltd., solid] 100% by mass of dicyanamide ["Evicure DICY15" manufactured by Yuka Shell Epoxy Co., Ltd.]
8% by mass and 1% by mass of 2-methyl-4-ethylimidazole [manufactured by Shikoku Chemicals Co., Ltd.]
Then, the mixture was preliminarily dispersed by a kneader at 70 to 90 ° C.
100% by mass of this reactant was added to silicon oxide fine powder [“Aerosil
300 "(manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was pulverized and classified to prepare a powder coating having an average particle size of 38 μm. The same steel material as in Example 17 was preheated to 180 ° C., the powder coating having the above composition was electrostatically applied, and then baked to obtain a coating film of 200 to 250 μm.
Was obtained. A test piece of a polyethylene-coated steel material having a three-layer structure was prepared from this test piece in the same manner as in Example 17. This test piece was tested in the same manner as in Example 1, and the results are shown in Table 6.
【００３８】[0038]
【表５】 [Table 5]
【００３９】[0039]
【表６】 実施例２７ 湿気硬化型ポリイノシアネート〔「デスモジュールE116
0 」住友バイエル（株）製、NC05． 5％〕 100質量％に
対し150 ℃で3 時間乾燥したのちデシケータ中で放冷し
た二価の炭酸マンガン塩60質量％を加え、ディスパーで
20分間撹件処理して湿気硬化型ウレタン樹脂塗料を調製
した。この塗料組成物を用い、塗装処理をおこない、さ
らにウレタンエラストマー塗料〔「ハイボン500 」日本
ペイント（株）製〕を乾燥膜厚3mm になるように塗布
し、常温で1 週間乾燥させて重防食ポリウレタン被覆鋼
材の試験片を作製した。この試験片につき、電防試験と
密着力試験をおこなった。この場合の密着力試験は、直
径2cm のアルミニウム製ドーリーをエポキシ系接着剤で
取りつけ、ドーリーの周りに沿つて素材に達する切れ目
を入れた状態で試験片とドーリーを上下に引つ張った際
の荷重を測定する方法によった。それらの試験結果を表
7に併せて示した。[Table 6] Example 27 Moisture-curable polyinocyanate [Desmodur E116
0 ”Sumitomo Bayer Corporation, NC05. 5%] After drying at 150 ° C for 3 hours with respect to 100% by mass, add 60% by mass of divalent manganese carbonate cooled in a desiccator and add
The mixture was stirred for 20 minutes to prepare a moisture-curable urethane resin paint. Using this coating composition, a coating treatment is carried out, and a urethane elastomer coating (“Hybon 500” manufactured by Nippon Paint Co., Ltd.) is applied to a dry film thickness of 3 mm and dried at room temperature for 1 week to obtain a heavy duty anticorrosive polyurethane. Test pieces of coated steel were produced. The test piece was subjected to an electrical protection test and an adhesion test. The adhesion test in this case was performed by attaching an aluminum dolly with a diameter of 2 cm with an epoxy adhesive, and pulling the test piece and dolly up and down with a cut reaching the material around the dolly. According to the method of measuring the load. Table showing the test results
7 is also shown.
【００４０】比較例６ 二価および／または三価のマンガン塩を添加しないで実
施例27と同様に湿気硬化型ウレタン樹脂塗装を行った
後、実施例27と同様に重防食ポリウレタン被覆鋼材の試
験片を作製した。この試験片につき実施例27と同様に試
験し、結果を表７に併載した。COMPARATIVE EXAMPLE 6 After applying a moisture-curable urethane resin coating in the same manner as in Example 27 without adding divalent and / or trivalent manganese salts, a test was carried out on the heavy corrosion-resistant polyurethane-coated steel in the same manner as in Example 27. Pieces were made. This test piece was tested in the same manner as in Example 27, and the results are shown in Table 7.
【００４１】実施例28-29 鋼材にクロム酸クロム（クロム酸還元率４０％）とシリ
カからなるクロメートを、クロム付着量で５００ｍｇ／
ｍ2となるように塗布し、１５０℃で乾燥させた。これ
に、実施例17および実施例27の被覆構成の試験片を作製
し試験した結果を表７に併載した。Examples 28-29 Chromate composed of chromium chromate (chromic acid reduction ratio 40%) and silica was added to a steel material in an amount of 500 mg / chromium.
m 2, and dried at 150 ° C. Table 7 also shows the test results of the test pieces having the coating configurations of Example 17 and Example 27.
【００４２】比較例７-8 鋼材にクロム酸クロム（クロム酸還元率４０％）とシリ
カからなるクロメートを、クロム付着量で５００ｍｇ／
ｍ2となるように塗布し、１５０℃で乾燥させた。これ
に、比較例５および比較例６の被覆構成の試験片を作製
し、実施例２８−２９と同様に試験し、結果を表7 に併
載した。Comparative Example 7-8 Chromate composed of chromium chromate (chromate reduction ratio 40%) and silica was added to a steel material in an amount of 500 mg / chromium.
m 2, and dried at 150 ° C. Test pieces having the coating configuration of Comparative Examples 5 and 6 were prepared and tested in the same manner as in Examples 28 to 29. The results are also shown in Table 7.
【００４３】[0043]
【表７】 表7 の結果から、本発明の塗料組成物は塗布面にライニ
ングや有機被覆を施した場合にも二価および／または三
価のマンガン塩を含まない比較例に比べて優れた耐陰極
剥離性を発揮し、密着力も良好である。また、鋼材にク
ロメート処理を行うと効果が増大するのが解る。[Table 7] From the results shown in Table 7, the coating composition of the present invention has excellent cathodic peeling resistance even when the coating surface is coated with a lining or an organic coating as compared with the comparative example containing no divalent and / or trivalent manganese salt. And good adhesion. Further, it can be seen that the effect increases when the steel material is subjected to the chromate treatment.
【００４４】[0044]
【発明の効果】以上のとおり、本発明の防食塗料組成物
は熱硬化性樹脂に所定量の二価および／または三価のマ
ンガン塩を配合して構成されており、この組成によって
電気防食塗膜の耐陰極剥離性を大幅に改善することが可
能であり、耐陰極剥離性に優れた防食被覆鋼材も提供で
きる。したがつて、海洋構造物、埋設構造物あるいは船
舶などを対象とする鋼材の耐久性を効果的に向上させる
ことができる。As described above, the anticorrosion coating composition of the present invention comprises a thermosetting resin mixed with a predetermined amount of a divalent and / or trivalent manganese salt. It is possible to greatly improve the cathodic peeling resistance of the film, and it is also possible to provide an anticorrosion coated steel material having excellent cathodic peeling resistance. Therefore, the durability of steel materials intended for marine structures, buried structures, ships, and the like can be effectively improved.
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） Ｂ３２Ｂ 15/18 Ｂ３２Ｂ 15/18 Ｃ０９Ｄ 5/08 Ｃ０９Ｄ 5/08 // Ｃ２３Ｆ 13/00 Ｃ２３Ｆ 13/00 Ｆ Ｆターム(参考） 4D075 AE03 CA33 DA06 DB02 DC05 EA02 EA19 EB33 EB38 EC01 EC54 4F100 AA08H AA18A AA18H AB03B AH02H AH03H AK01A AK06 AK53 AK53H AK70 AL06H AR00D BA03 BA04 BA07 BA10B BA10C CA02 CA14A CB00C CC03A EJ68D GB07 GB31 GB90 JB02C JB13A JK06 JL00 YY00A YY00C YY00H 4J038 DB001 DD231 DG131 DG241 DG291 FA251 HA216 HA296 HA416 HA476 NA03 PA08 PA10 PC02 4K060 AA03 AA07 AA09 BA22 BA26 EB01 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (Reference) B32B 15/18 B32B 15/18 C09D 5/08 C09D 5/08 // C23F 13/00 C23F 13/00 F F term ( Reference) 4D075 AE03 CA33 DA06 DB02 DC05 EA02 EA19 EB33 EB38 EC01 EC54 4F100 AA08H AA18A AA18H AB03B AH02H AH03H AK01A AK06 AK53 AK53H AK70 AL06H AR00D BA03 BA04 BA07 BA10BBAJC13 CA02 J02 DD231 DG131 DG241 DG291 FA251 HA216 HA296 HA416 HA476 NA03 PA08 PA10 PC02 4K060 AA03 AA07 AA09 BA22 BA26 EB01
Claims (3)
二価および／または三価のマンガン塩固形分5 〜300 質
量％を含有することを特徴とする防食塗料組成物。1. A thermosetting resin having a solid content of 100% by mass,
An anticorrosion coating composition comprising a divalent and / or trivalent manganese salt solid content of 5 to 300% by mass.
量％に対し、二価および／または三価のマンガン塩固形
分5 〜300 質量％を含有する防食塗料組成物が積層さ
れ、その上に厚さ１ｍｍ以上の防食被覆が積層されてい
ることを特徴とする防食被覆鋼材。2. An anticorrosive coating composition containing 5-300% by weight of divalent and / or trivalent manganese salt solids based on 100% by weight of thermosetting resin solids on the surface of a steel material. An anticorrosion-coated steel material on which an anticorrosion coating having a thickness of 1 mm or more is laminated.
に熱硬化性樹脂固形分100 質量％に対し、二価および／
または三価のマンガン塩固形分5 〜300 質量％を含有す
る防食塗料組成物が積層され、さらにその上に厚さ１ｍ
ｍ以上の防食被覆が積層されていることを特徴とする防
食被覆鋼材。3. A chemical conversion coating is laminated on the surface of a steel material.
Alternatively, an anticorrosion coating composition containing 5 to 300% by mass of a trivalent manganese salt solid content is laminated, and a 1 m thick
An anticorrosion-coated steel material, wherein at least m or more anticorrosion coatings are laminated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000133542A JP2001316629A (en) | 2000-05-02 | 2000-05-02 | Anticorrosive coating material composition and steel stock having anticorrosive covering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000133542A JP2001316629A (en) | 2000-05-02 | 2000-05-02 | Anticorrosive coating material composition and steel stock having anticorrosive covering |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001316629A true JP2001316629A (en) | 2001-11-16 |
Family
ID=18642016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000133542A Withdrawn JP2001316629A (en) | 2000-05-02 | 2000-05-02 | Anticorrosive coating material composition and steel stock having anticorrosive covering |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001316629A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110793A (en) * | 2004-10-13 | 2006-04-27 | Jfe Steel Kk | Resin-coated heavy corrosion-proof steel material |
| JP2010530018A (en) * | 2007-06-13 | 2010-09-02 | ビーエーエスエフ ソシエタス・ヨーロピア | Catalyst for epoxide curing |
-
2000
- 2000-05-02 JP JP2000133542A patent/JP2001316629A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110793A (en) * | 2004-10-13 | 2006-04-27 | Jfe Steel Kk | Resin-coated heavy corrosion-proof steel material |
| JP2010530018A (en) * | 2007-06-13 | 2010-09-02 | ビーエーエスエフ ソシエタス・ヨーロピア | Catalyst for epoxide curing |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20070703 |