JP2009262397A - Coated metal sheet and its method for manufacturing - Google Patents
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Abstract
Description
本発明は、クリーンルーム用の建材などに用いられる塗装金属板及びその製造方法に関するものである。 The present invention relates to a coated metal plate used for a building material for a clean room and the manufacturing method thereof.
従来より、めっき鋼板等の金属板の必要な耐食性を確保するために、クロメートを含有する薬液を金属板の表面に塗布することが行われていたが、最近では、環境や人体への影響を考慮してクロメートを使用しないクロメートフリー化が要望されている（例えば、特許文献１〜３参照）。 Conventionally, in order to ensure the necessary corrosion resistance of metal plates such as plated steel plates, a chemical solution containing chromate has been applied to the surface of the metal plates. Recently, however, the effect on the environment and human body has been reduced. In view of this, there is a demand for a chromate-free solution that does not use chromate (for example, see Patent Documents 1 to 3).
しかし、クロメートフリーの薬液を金属板に塗布・乾燥して得られる塗装金属板からは、フタル酸エステル類や環状シロキサン類や２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール（以下、「ＢＨＴ」という）の少なくとも一つがアウトガスとして検出されており、クリーンルーム業界ではクリーンルームを構成する部材から発生するアウトガスが一部問題視されている。特に、半導体メーカー等では、内装部材から発生するフタル酸エステル類や環状シロキサン類やＢＨＴを含むアウトガスがシリコンウェハ等の基材を汚染し、悪影響を及ぼすことが問題となっていた。
本発明は上記の点に鑑みてなされたものであり、アウトガスの発生を少なくすることができる塗装金属板及びその製造方法を提供することを目的とするものである。 This invention is made | formed in view of said point, and it aims at providing the coating metal plate which can reduce generation | occurrence | production of outgas, and its manufacturing method.
本発明の請求項１に係る塗装金属板は、水系樹脂を主成分とし、クロメートを含有せず、フタル酸エステル類の含有量が５０ｐｐｍ以下、環状シロキサン類の含有量が２５ｐｐｍ以下、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールの含有量が１０ｐｐｍ以下である塗料からなる塗膜を金属板に設けて成ることを特徴とするものである。 The coated metal plate according to claim 1 of the present invention is mainly composed of a water-based resin, does not contain chromate, has a content of phthalates of 50 ppm or less, a content of cyclic siloxanes of 25 ppm or less, 2, 6 -A metal plate is provided with a coating film made of a paint having a content of di-tert-butyl-4-methylphenol of 10 ppm or less.
本発明の請求項２に係る塗装金属板は、請求項１において、上記塗膜の付着量が０．５〜２．０ｇ／ｍ２であることを特徴とするものである。 The coated metal plate according to a second aspect of the present invention is characterized in that, in the first aspect, the adhesion amount of the coating film is 0.5 to 2.0 g / m 2 .
本発明の請求項３に係る塗装金属板の製造方法は、水系樹脂を主成分とし、クロメートを含有せず、フタル酸エステル類の含有量が５０ｐｐｍ以下、環状シロキサン類の含有量が２５ｐｐｍ以下、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールの含有量が１０ｐｐｍ以下である塗料を金属板に塗布した後、焼き付けて塗膜を形成することを特徴とするものである。 The method for producing a coated metal plate according to claim 3 of the present invention is based on an aqueous resin, does not contain chromate, has a content of phthalates of 50 ppm or less, and a content of cyclic siloxanes of 25 ppm or less, A coating film having a 2,6-di-tert-butyl-4-methylphenol content of 10 ppm or less is applied to a metal plate and then baked to form a coating film.
請求項１、３の発明では、塗料がクロメートを含有しないため、環境や人体への悪影響を少なくすることができるものである。また、フタル酸エステル類の含有量が５０ｐｐｍ以下、環状シロキサン類の含有量が２５ｐｐｍ以下、ＢＨＴの含有量が１０ｐｐｍ以下であるため、これらのアウトガスを少なくすることができるものである。さらに、水系樹脂を含む塗膜で金属板が被覆されるため、耐食性を確保することができるものである。 In the first and third aspects of the invention, since the paint does not contain chromate, adverse effects on the environment and the human body can be reduced. Further, since the content of phthalates is 50 ppm or less, the content of cyclic siloxanes is 25 ppm or less, and the content of BHT is 10 ppm or less, these outgasses can be reduced. Furthermore, since a metal plate is coat | covered with the coating film containing water-system resin, corrosion resistance can be ensured.
請求項２の発明では、アウトガスをほとんど発生させないようにしながら耐食性を確保することができるものである。 In invention of Claim 2, corrosion resistance can be ensured, generating little outgas.
以下、本発明を実施するための最良の形態を説明する。 Hereinafter, the best mode for carrying out the present invention will be described.
本発明の塗装金属板は、母材である金属板の片面又は両面にクロメートフリーの塗膜を形成したものである。 The coated metal plate of the present invention is obtained by forming a chromate-free coating film on one side or both sides of a base metal plate.
本発明で用いる金属板としては耐食性の高いものを用いるのが好ましく、亜鉛系めっきやアルミニウム系めっきを施しためっき鋼板を用いることができるが、切断端面や加工部を含めて優れた耐食性を維持するため、例えば、５５％アルミニウム亜鉛合金めっき鋼板を用いるのが好ましい。さらに、耐食性向上のために、マグネシウムなどの他の合金成分を含有しためっきを施しても良い。めっき鋼板には塗料の塗装の前に、必要に応じて、アルカリ脱脂などの洗浄を行うことができる。 As the metal plate used in the present invention, it is preferable to use a metal plate having high corrosion resistance, and a plated steel plate subjected to zinc plating or aluminum plating can be used, but excellent corrosion resistance is maintained including the cut end face and the processed portion. Therefore, for example, it is preferable to use a 55% aluminum zinc alloy plated steel sheet. Furthermore, in order to improve corrosion resistance, plating containing other alloy components such as magnesium may be performed. If necessary, the plated steel sheet can be washed, such as alkaline degreasing, before painting.
本発明で用いる塗料は、水性アクリル系樹脂や水性ウレタン系樹脂などの水系樹脂を主成分とする水性塗料であって、クロメートを含有せず、フタル酸エステル類の含有量が５０ｐｐｍ以下、環状シロキサン類の含有量が２５ｐｐｍ以下、ＢＨＴの含有量が１０ｐｐｍ以下のものを用いる。ここで、上記塗料中のフタル酸エステル類と環状シロキサン類とＢＨＴの各含有量は１０ｐｐｍ以下であることが好ましい。 The paint used in the present invention is an aqueous paint mainly composed of a water-based resin such as a water-based acrylic resin or a water-based urethane resin, does not contain chromate, has a phthalate ester content of 50 ppm or less, and a cyclic siloxane. A material having a content of 25 ppm or less and a BHT content of 10 ppm or less is used. Here, each content of phthalates, cyclic siloxanes, and BHT in the coating is preferably 10 ppm or less.
水系樹脂は水を溶媒として用いることができるので、有機溶媒を使用する溶剤系樹脂に比べて、環境や人体への悪影響を少なくすることができて好ましい。また、クロメートを含有すると、環境や人体への悪影響を及ぼすおそれがあるので、好ましくない。また、フタル酸エステル類と環状シロキサン類とＢＨＴの各含有量が上記よりも多くなると、本発明の効果を奏することができなくなる。本発明ではフタル酸エステル類と環状シロキサン類とＢＨＴを全く含まないことが好ましいが、不可避的に含有されることはある。フタル酸エステル類は、プラスチックを軟らかくするために添加される可塑剤として主に使用されている。可塑剤としてのフタル酸エステル類は樹脂（プラスチック）に加工性を与え、樹脂合成段階で添加されるものである。環状シロキサン類は樹脂に添加することで耐薬品性を向上させることができる。ＢＨＴは酸化防止剤として使用されるものであり、樹脂や溶剤が酸化によって劣化されるのを防ぐ目的で添加されるものであり、ウレタン系の樹脂や造膜助剤の溶剤に使用されている。 Since water-based resins can use water as a solvent, they are preferable because adverse effects on the environment and the human body can be reduced compared to solvent-based resins using organic solvents. Further, the inclusion of chromate is not preferable because it may adversely affect the environment and the human body. Moreover, when each content of phthalic acid esters, cyclic siloxanes, and BHT is higher than the above, the effects of the present invention cannot be achieved. In the present invention, it is preferable that phthalic acid esters, cyclic siloxanes, and BHT are not contained at all, but they are inevitably contained. Phthalate esters are mainly used as plasticizers added to soften plastics. Phthalate esters as plasticizers give processability to the resin (plastic) and are added at the resin synthesis stage. Cyclic siloxanes can improve chemical resistance by adding to the resin. BHT is used as an antioxidant and is added for the purpose of preventing the resin and solvent from being deteriorated by oxidation, and is used as a solvent for urethane-based resins and film-forming aids. .
本発明の塗装金属板を以下のようにして製造することができる。まず、金属板の片面又は両面に上記塗料をスプレーやロールコータなどの公知の手段で塗布する。次に、塗料を塗布した金属板を板温度が８０℃以上になるように加熱して、焼付・乾燥を行う。乾燥塗膜の付着量は金属板の片面当たり０．５〜２．０ｇ／ｍ２とすることができる。一般的に、塗膜が薄すぎると耐食性や潤滑性が劣り、塗膜厚みが大きすぎると、加工性低下を招くばかりでなく、コストアップにもつながる。このようにして乾燥焼付塗膜で被覆された本発明の塗装金属板を形成することができる。この塗装金属板ではフタル酸エステル類と環状シロキサン類とＢＨＴの発生量が１．０ｎｇ／ｃｍ２未満に抑制することができ、クリーンルームの建材などに好適に用いることができる。特に、半導体業界やディスプレー業界から、上記三物質によるシリコンウェハーの汚染等の不具合を防止するために、上記三物質の発生量を１．０ｎｇ／ｃｍ２未満に抑制することが要求されているが、本発明ではこの要求を満たすことができる。 The coated metal plate of this invention can be manufactured as follows. First, the said coating material is apply | coated to a single side | surface or both surfaces of a metal plate by well-known means, such as a spray and a roll coater. Next, the metal plate coated with the paint is heated so that the plate temperature is 80 ° C. or higher, and is baked and dried. The adhesion amount of the dry coating film can be 0.5 to 2.0 g / m 2 per one side of the metal plate. Generally, if the coating film is too thin, the corrosion resistance and lubricity are inferior. If the coating film thickness is too large, not only the workability is reduced, but also the cost is increased. In this way, the coated metal plate of the present invention coated with the dry baking coating film can be formed. In this coated metal plate, the amount of phthalates, cyclic siloxanes, and BHT generated can be suppressed to less than 1.0 ng / cm 2 , and it can be suitably used as a building material for clean rooms. In particular, the semiconductor industry and the display industry are required to suppress the generation amount of the three substances to less than 1.0 ng / cm 2 in order to prevent problems such as contamination of the silicon wafer by the three substances. The present invention can satisfy this requirement.
以下本発明を実施例によって具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
＜アウトガスの測定＞
実施例１−３及び比較例１−５について、塗装金属板からのアウトガスの測定を行った。ここで、アウトガスは固体捕集法により捕集し、これをガスクロマトグラフィ質量分析法により測定した。結果を表１に示す。尚、「Ｎ．Ｄ．」は検出されなかったことを示す。
<Measurement of outgas>
About Example 1-3 and Comparative Example 1-5, the outgas from a coating metal plate was measured. Here, outgas was collected by the solid collection method, and this was measured by the gas chromatography mass spectrometry. The results are shown in Table 1. “ND” indicates that no detection was made.
［実施例１−３、比較例１−５］
金属板としては、５５％アルミニウム亜鉛めっき鋼板（日鉄住金鋼板（株）製のガルバリウム鋼板）を用いた。塗料としては、水性アクリル系樹脂であるアクアブリッド４１７０−Ａ２（ダイセルファインケム製のアクリル樹脂エマルション、無溶剤品、樹脂成分を２３．７５％含有、溶媒は水、クロメートを含まない）に、薬剤（アウトガス成分）としてジブチルフタレート（フタル酸エステル類）と、オクタメチルシクロテトラシロキサン（環状シロキサン類）と、ＢＨＴとを所定量配合したものを用いた。
[Example 1-3, Comparative Example 1-5]
As the metal plate, a 55% aluminum galvanized steel plate (galvanium steel plate manufactured by Nippon Steel & Sumikin Steel Co., Ltd.) was used. As paint, Aquabrid 4170-A2 which is a water-based acrylic resin (Acrylic resin emulsion made by Daicel Finechem, solvent-free product, containing 23.75% resin component, solvent does not contain water and chromate), As the outgas component, dibutyl phthalate (phthalic acid esters), octamethylcyclotetrasiloxane (cyclic siloxanes), and BHT in a predetermined amount were used.
そして、金属板の表面（めっき表面）に塗料を塗布した後、３０〜４０秒間で所定の板温度になるまで加熱し、塗料を乾燥及び焼き付けをして塗膜を形成した。乾燥塗膜の付着量は１．５〜２．０ｇ／ｍ２であった。 And after apply | coating a coating material to the surface (plating surface) of a metal plate, it heated until it became predetermined plate | board temperature for 30 to 40 seconds, the coating material was dried and baked, and the coating film was formed. The adhesion amount of the dried coating film was 1.5 to 2.0 g / m 2 .
表１から明らかなように、実施例１−３及び比較例１、２ではジブチルフタレートの測定値は、１．０ｎｇ／ｃｍ２未満となり、実施例１−３及び比較例１ではオクタメチルシクロテトラシロキサンの測定量が１．０ｎｇ／ｃｍ２未満となり、実施例１−３ではＢＨＴの測定量が１．０ｎｇ／ｃｍ２未満となり、各薬剤の発生を抑えることができた。一方、比較例３−５ではジブチルフタレート、オクタメチルシクロテトラシロキサン、ＢＨＴの添加量が所定量以上となっているので、塗装金属板からの各薬剤の発生量が１．０ｎｇ／ｃｍ２以上となり、好ましくない。 As is clear from Table 1, in Example 1-3 and Comparative Examples 1 and 2, the measured value of dibutyl phthalate was less than 1.0 ng / cm 2 , and in Example 1-3 and Comparative Example 1, octamethylcyclotetra The measured amount of siloxane was less than 1.0 ng / cm 2 , and in Example 1-3, the measured amount of BHT was less than 1.0 ng / cm 2, and generation of each drug could be suppressed. On the other hand, in Comparative Example 3-5, since the addition amount of dibutyl phthalate, octamethylcyclotetrasiloxane, and BHT is a predetermined amount or more, the amount of each chemical generated from the coated metal plate is 1.0 ng / cm 2 or more. It is not preferable.
＜耐食性評価試験＞
実施例４−９及び比較例６について、ＪＩＳ Ｚ ２３７１に準拠して塩水噴霧試験を行った。すなわち、３５℃に設定した試験槽に５％食塩水を噴霧し、実施例及び比較例の耐食性や腐食性を外観により評価した。評価方法は、実用上問題がないものに○を、実用上ほとんど問題がないものに△を、実用上問題があるものに×をそれぞれ付した。結果を表２に示す。
<Corrosion resistance evaluation test>
About Example 4-9 and Comparative Example 6, the salt spray test was done based on JISZ2371. That is, 5% saline was sprayed on a test tank set at 35 ° C., and the corrosion resistance and corrosivity of Examples and Comparative Examples were evaluated by appearance. The evaluation methods were marked with ◯ when there was no practical problem, △ when there was little practical problem, and x when there was practical problem. The results are shown in Table 2.
［実施例４−９、比較例６］
金属板としては、５５％アルミニウム亜鉛めっき鋼板（日鉄住金鋼板（株）製のガルバリウム鋼板）を用いた。塗料としては、水性アクリル系樹脂であるアクアブリッド４１７０−Ａ２（ダイセルファインケム製のアクリル樹脂エマルション、無溶剤品、樹脂成分を２３．７５％含有、溶媒は水、クロメートを含まない）を用いた。
[Example 4-9, Comparative Example 6]
As the metal plate, a 55% aluminum galvanized steel plate (galvanium steel plate manufactured by Nippon Steel & Sumikin Steel Co., Ltd.) was used. As a coating material, Aquabrid 4170-A2 (Acrylic resin emulsion manufactured by Daicel Finechem, solvent-free product, containing 23.75% resin component, solvent does not contain water and chromate), which is a water-based acrylic resin, was used.
そして、金属板の表面（めっき表面）に塗料を塗布した後、３０〜４０秒間で８０℃の板温度になるまで加熱し、塗料を乾燥及び焼き付けをして塗膜を形成した。乾燥塗膜の付着量は０．３〜２．５ｇ／ｍ２となるように段階的に塗布した。 And after apply | coating a coating material on the surface (plating surface) of a metal plate, it heated until it became 80 degreeC plate temperature in 30 to 40 second, and the coating material was dried and baked and the coating film was formed. It applied in steps so that the adhesion amount of a dry coating film might be 0.3-2.5 g / m < 2 >.
表２から明らかなように、膜厚が薄い実施例４では耐食性はやや劣るものの、実施例５−９では比較例６と比べて耐食性は遜色なかった。 As is clear from Table 2, the corrosion resistance was slightly inferior in Example 4 where the film thickness was thin, but the corrosion resistance was inferior to that in Comparative Example 6 in Example 5-9.
Claims (3)
Containing water-based resin as the main component, containing no chromate, phthalic acid ester content of 50 ppm or less, cyclic siloxane content of 25 ppm or less, 2,6-di-tert-butyl-4-methylphenol content A method for producing a coated metal plate, comprising: applying a paint having an amount of 10 ppm or less to a metal plate;
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013209749A (en) * | 2012-02-28 | 2013-10-10 | Nippon Steel & Sumikin Coated Sheet Corp | Surface-coated aluminum-containing galvanized steel sheet |
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