JPH05171491A - Double layer plated steel excellent in corrosion resistance after coating - Google Patents
Double layer plated steel excellent in corrosion resistance after coatingInfo
- Publication number
- JPH05171491A JPH05171491A JP34521991A JP34521991A JPH05171491A JP H05171491 A JPH05171491 A JP H05171491A JP 34521991 A JP34521991 A JP 34521991A JP 34521991 A JP34521991 A JP 34521991A JP H05171491 A JPH05171491 A JP H05171491A
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- Prior art keywords
- plating
- coating
- corrosion resistance
- layer
- plated steel
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Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、自動車、建材、家電な
どの分野に好適な塗膜密着性に優れた2層めっき鋼材に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-layer plated steel material having excellent coating film adhesion suitable for fields such as automobiles, building materials and home appliances.
【0002】[0002]
【従来の技術】Zn系めっき鋼材を基材とし、その上層に
Al系めっきを施した2層めっき鋼材は本発明者らにより
先に開発され、特許出願されている (特開昭61−119693
号および同61−261496号公報) 。これらの2層めっき鋼
材は、基材のZn系めっき鋼材よりさらに優れた耐食性を
有し、特に未塗装、無傷の状態での耐食性が非常に高
い。しかし、さらに詳細に検討した結果、この種の一部
の2層めっき鋼材においては、塗膜カット部でふくれが
生じ易いことが判明した。[Prior Art] Zn-based plated steel as a base material
The present inventors have previously developed a double-layered steel material plated with Al and applied for a patent (Japanese Patent Laid-Open No. 61-119693).
No. 61-261496). These two-layer plated steel materials have even better corrosion resistance than the Zn-based plated steel material of the base material, and particularly have very high corrosion resistance in the unpainted and intact state. However, as a result of a more detailed study, it was found that in some of the double-layer plated steel materials of this type, blistering is likely to occur at the coating film cut portion.
【0003】この塗膜ふくれは、塗膜と上層Al系めっき
との界面ではなく、Al系めっきとZn系めっきとの界面で
生じており、外観的には一般的な塗膜ふくれと類似の状
況となる。通常、めっき鋼材は塗装して使用されること
が多く、このような塗膜ふくれは好ましくない。This coating film swelling occurs not at the interface between the coating film and the upper Al-based plating but at the interface between the Al-based plating and the Zn-based plating, and is similar in appearance to a general coating film swelling. It becomes a situation. Usually, the plated steel material is often used by painting, and such a blister of the coating film is not preferable.
【0004】[0004]
【発明が解決しようとする課題】本発明の目的は、未塗
装の耐食性のみならず、塗膜密着性や塗装後耐食性にも
優れた2層めっき鋼材を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a two-layer plated steel material which is excellent not only in unpainted corrosion resistance but also in coating adhesion and corrosion resistance after painting.
【0005】[0005]
【課題を解決するための手段】本発明者らは、2層めっ
きにおける塗膜ふくれの原因について調査した結果、上
層Al系めっきの付着量が10 g/m2 以下で、かつ上層のめ
っき皮膜が多孔性であると、上述した塗膜ふくれが抑制
されることを見出し、本発明を完成させるに至った。As a result of investigating the cause of coating film blistering in two-layer plating, the present inventors found that the amount of upper Al-based plating adhered was 10 g / m 2 or less and the upper-layer plating film It was found that the above-mentioned swelling of the coating film was suppressed when it was porous, and the present invention was completed.
【0006】ここに、本発明は、下層めっきがZnまたは
Zn合金層、上層めっきが付着量 0.1〜10 g/m2 の多孔性
AlまたはAl合金層であることを特徴とする、塗装後耐食
性に優れた2層めっき鋼材を要旨とする。In the present invention, the lower layer plating is Zn or
Zn alloy layer, upper layer plating is 0.1-10 g / m 2 porosity
The gist is a two-layer plated steel material having excellent corrosion resistance after painting, which is an Al or Al alloy layer.
【0007】[0007]
【作用】本発明者らの調査によると、塗膜カット部での
ふくれは、上層Al系めっきの付着量が10 g/m2 を超える
か、あるいは上層Al系めっきの付着量が10 g/m2 以下で
あっても、めっき皮膜が緻密なほど生じ易いことが判明
した。これは、上層Al系めっきと下層Zn系めっきの溶出
速度の差に起因すると考えられる。上層Al系めっきの付
着量が10 g/m2 を超える場合や、めっき皮膜が緻密な場
合には、得られる2層めっきの腐食電位は単層Al系めっ
きとほぼ同じ電位を示し (−0.7 V,vs Ag/AgCl)、下層Z
n系めっきよりもかなり電位的に貴となる。そのため、
塗膜カット部においてAl系めっきよりもZn系めっきが優
先的に溶出し、前述の如く、Al系めっきとZn系めっきの
界面でふくれが生じる。これに対して、上層Al系めっき
の付着量が10 g/m2 以下で、かつ皮膜が多孔性である場
合には、2層めっきの腐食電位は下層Zn系めっきと同等
の卑な腐食電位 (−1.0 〜−1.1 V, vs Ag/AgCl)を示
し、下層Zn系めっきの優先的な溶出が抑制される。その
ため、上記のふくれが防止されると考えられる。According to the investigation by the present inventors, the blisters in the coating film cut portion have an adhesion amount of the upper Al-based plating of more than 10 g / m 2 , or an adhesion amount of the upper-layer Al-based plating of 10 g / m 2. It has been found that the denser the plating film, the more likely it is to generate even if it is m 2 or less. This is considered to be due to the difference in the elution rate between the upper Al-based plating and the lower Zn-based plating. When the adhesion amount of the upper Al-based plating exceeds 10 g / m 2 or when the plating film is dense, the corrosion potential of the obtained two-layer plating shows almost the same potential as the single-layer Al-based plating (−0.7 V, vs Ag / AgCl), lower layer Z
It is significantly more noble than n-type plating. for that reason,
Zn-based plating is preferentially eluted over Al-based plating in the coating cut portion, and as described above, blistering occurs at the interface between the Al-based plating and the Zn-based plating. On the other hand, when the adhesion amount of the upper Al-based plating is 10 g / m 2 or less and the coating is porous, the corrosion potential of the two-layer plating is as low as the lower Zn-based plating. (-1.0 to -1.1 V, vs Ag / AgCl), and preferential elution of the lower Zn-based plating is suppressed. Therefore, it is considered that the above-mentioned blistering is prevented.
【0008】本発明の2層めっき鋼材の母材は、代表的
には冷延鋼板であるが、鋼種および形状のいずれも特に
限定されるものではない。炭素鋼、各種合金鋼、ステン
レス鋼などを含む任意の鋼種からなる、板材、棒材、線
材、管材、型材などの任意の形状の鋼材を母材としう
る。The base material of the two-layer plated steel material of the present invention is typically a cold rolled steel sheet, but the steel type and shape are not particularly limited. A base material may be a steel material having an arbitrary shape such as a plate material, a bar material, a wire material, a pipe material, and a mold material, which is made of an arbitrary steel type including carbon steel, various alloy steels, and stainless steel.
【0009】下層はZn系めっき、即ち、Znめっきか、Zn
合金めっきである。Zn合金めっきは、鋼に対する犠牲防
食能を有するものが好ましい。その例としては、Zn−Fe
合金めっき (合金化溶融亜鉛めっきを含む) 、Zn−Ni合
金めっき、Zn−Co合金めっき、Zn−Mn合金めっき、Zn−
Mg合金めっき、Zn−Cr合金めっき、Zn−Al合金めっきな
どが例示されるが、これらに限定されるものではない。
Zn合金めっきには、追加の合金元素としてNi, Fe, Mo,
Cr, Co, Al, Mgなどの各種の元素を1種もしくは2種以
上さらに添加してもよい。また、下層ZnめっきまたはZn
合金めっき層は、めっき中にAl2O3 、SiO2、TiO2、Zr
O2、SnO2、Sb2O3 などの酸化物を共析させた複合めっき
としてもよい。The lower layer is Zn-based plating, that is, Zn plating or Zn
Alloy plating. The Zn alloy plating preferably has a sacrificial anticorrosive ability for steel. For example, Zn-Fe
Alloy plating (including galvannealing), Zn-Ni alloy plating, Zn-Co alloy plating, Zn-Mn alloy plating, Zn-
Examples include Mg alloy plating, Zn-Cr alloy plating, and Zn-Al alloy plating, but the invention is not limited to these.
For Zn alloy plating, additional alloying elements such as Ni, Fe, Mo,
One or more of various elements such as Cr, Co, Al and Mg may be further added. Also, the lower layer Zn plating or Zn
The alloy plating layer is made of Al 2 O 3 , SiO 2 , TiO 2 , Zr during plating.
A composite plating in which an oxide such as O 2 , SnO 2 or Sb 2 O 3 is codeposited may be used.
【0010】下層Zn系めっきの付着量は特に限定されな
いが、加工性、溶接性などを考慮すれば、有利には100
g/m2以下、特に20〜60g/m2が好ましい。また、Zn系めっ
きの形成方法についても特に制限はなく、電気めっき
法、溶融めっき法、真空蒸着法、イオンプレーティング
法等を用いることができる。The amount of the lower Zn-based plating applied is not particularly limited, but it is preferably 100 in consideration of workability and weldability.
g / m 2 or less, in particular 20 to 60 g / m 2 is preferred. The method for forming the Zn-based plating is also not particularly limited, and an electroplating method, a hot dip plating method, a vacuum deposition method, an ion plating method or the like can be used.
【0011】上層はAl系めっき、即ち、Alめっきか、Al
合金めっきであり、付着量が 0.1〜10 g/m2 の多孔性皮
膜とする。上層Al系めっき皮膜の付着量が0.1 g/m2未満
では、未塗装、無傷での耐食性に劣り、10g/m2を超える
と、たとえ多孔性皮膜であっても、十分な塗膜密着性、
塗装後耐食性は得られない。The upper layer is Al-based plating, that is, Al plating or Al
It is an alloy plating, and the coating amount is 0.1 to 10 g / m 2 porous film. If the coating amount of the upper Al-based plating film is less than 0.1 g / m 2 , the corrosion resistance is unpainted and intact, and if it exceeds 10 g / m 2 , sufficient coating film adhesion is achieved even with a porous film. ,
No corrosion resistance is obtained after painting.
【0012】上層の多孔性Al系めっき皮膜の多孔度は、
有孔率 (単位面積当たりの孔の面積率) で 0.2〜0.7 の
範囲内が最適である。有孔率や孔径は、SEM (走査型
電子顕微鏡) 観察などでの測定により直接決定すること
ができる。有孔率が0.2 未満であると、緻密な皮膜と同
様に、塗装後耐食性が低下し、塗膜カット部で塗膜ふく
れを生じ易くなる。有孔率が0.7 を超えると、未塗装、
無傷での耐食性が低下する。また、孔径が小さすぎる
と、腐食生成物が孔に詰まり、効果が十分に発揮されな
いので、孔径は0.01〜3.0 mm程度が好ましい。The porosity of the upper porous Al-based plating film is
The optimum porosity (area ratio of holes per unit area) is 0.2 to 0.7. The porosity and the pore diameter can be directly determined by the measurement such as SEM (scanning electron microscope) observation. If the porosity is less than 0.2, the corrosion resistance after coating is lowered, and the coating film swells at the coating film cut portion, as in the case of the dense coating film. If the porosity exceeds 0.7, unpainted,
Corrosion resistance is reduced without damage. On the other hand, if the pore size is too small, the corrosion product will be clogged in the pores, and the effect will not be sufficiently exhibited. Therefore, the pore size is preferably about 0.01 to 3.0 mm.
【0013】Al系めっきの種類としては、上記の条件を
満たす限り特に制限されないが、塗装後耐食性の向上効
果を最も効果的に発揮させるには、Al−Mn合金めっき、
Al−Cr合金めっき、Al−Mg合金めっきなどのAl合金めっ
きが好適である。The type of Al-based plating is not particularly limited as long as the above conditions are satisfied, but in order to most effectively exhibit the effect of improving the corrosion resistance after coating, Al-Mn alloy plating,
Al alloy plating such as Al-Cr alloy plating and Al-Mg alloy plating is suitable.
【0014】上層Al系めっきの形成方法は、溶融塩浴、
有機溶媒浴などによる電気めっき法、真空蒸着法、イオ
ンプレーティング法などのドライプロセス法、溶射法な
ど、従来より公知の各種の方法を利用できる。ただし、
多孔性皮膜を形成するために、例えば、電気めっき法で
は電流密度を高くする、めっき液の撹拌を行わないなど
の方法を用いる。また、ドライプロセスの場合には、密
着性が低下しない範囲で基板温度を低くしたり、造膜速
度を大きくするといった手段を採用する。有孔率は、こ
のようなめっき条件の制御によって調整することができ
る。The upper layer Al-based plating is formed by a molten salt bath,
Various conventionally known methods such as an electroplating method using an organic solvent bath, a vacuum deposition method, a dry process method such as an ion plating method, and a thermal spraying method can be used. However,
In order to form the porous film, for example, the electroplating method uses a method such as increasing the current density or not stirring the plating solution. Further, in the case of the dry process, a means of lowering the substrate temperature or increasing the film forming speed is adopted within a range where the adhesiveness does not decrease. The porosity can be adjusted by controlling such plating conditions.
【0015】本発明の2層めっき鋼材は、上述した2層
めっきを鋼材の少なくとも1面に有していればよい。上
記2層めっきを全面に施さない場合、残りの面は非めっ
き面でも、別のめっき層 (例、Zn系めっき単層) を施し
た面でもよい。The two-layer plated steel material of the present invention may have the above-mentioned two-layer plating on at least one surface of the steel material. When the above two-layer plating is not applied to the entire surface, the remaining surface may be a non-plated surface or a surface on which another plating layer (eg, Zn-based plating single layer) is applied.
【0016】本発明の2層めっき鋼板に塗装する場合、
塗装下地処理として、クロメート処理またはリン酸塩処
理などの化成処理を常法により施してもよく、それによ
り耐食性および/または密着性が一層向上する。When coating the double-layer plated steel sheet of the present invention,
As the coating base treatment, a chemical conversion treatment such as a chromate treatment or a phosphate treatment may be performed by a conventional method, whereby the corrosion resistance and / or the adhesion is further improved.
【0017】[0017]
(下層Zn系めっき)ZnSO4 、Na2SO4を主成分とするZnめっ
き浴を基本浴として、必要により合金元素成分を硫酸塩
として添加した硫酸塩型めっき浴を用いて、板厚0.8 mm
の冷延鋼板にZnまたはZn合金めっきを電気めっき法によ
り施して、各種Zn系めっき鋼板を得た。めっき電流密度
は20 A/dm2とし、付着量40 g/m2 のめっき皮膜が形成さ
れるように通電を行った。As a basic bath (lower Zn-based plating) ZnSO 4, Zn plating bath composed mainly of Na 2 SO 4, the alloying elements components using the added sulfate type plating bath as the sulphate if necessary, plate thickness 0.8 mm
Various cold-rolled steel sheets were plated with Zn or Zn alloy by electroplating to obtain various Zn-plated steel sheets. The plating current density was 20 A / dm 2, and the current was applied so that a plating film with an adhesion amount of 40 g / m 2 was formed.
【0018】(上層Al系めっき)上で得た各種Zn系めっき
鋼板を母材として、下記条件での溶融塩電解法または蒸
着めっき法によりAl系めっきを施し、各種有孔率および
付着量の上層Al系多孔性めっき皮膜を形成した。上層Al
系めっき皮膜の有孔率は、溶融塩電解の場合にはめっき
電流密度と液流速の制御によって、蒸着めっきの場合に
は基板温度の制御によって、調整した。(Upper layer Al-based plating) Using various Zn-based plated steel sheets obtained above as a base material, Al-based plating is performed by a molten salt electrolysis method or a vapor deposition plating method under the following conditions to obtain various porosity and adhesion amount. An upper Al-based porous plating film was formed. Upper layer Al
The porosity of the system plating film was adjusted by controlling the plating current density and the liquid flow rate in the case of molten salt electrolysis and by controlling the substrate temperature in the case of vapor deposition plating.
【0019】(1) 溶融塩電解めっき法 基本浴: AlCl3−NaCl−KCl三元系溶融塩。Al合金めっ
きの場合には、各合金元素の塩化物を必要量添加。(1) Molten salt electroplating method Basic bath: AlCl 3 —NaCl—KCl ternary molten salt. In the case of Al alloy plating, the required amount of chloride of each alloy element is added.
【0020】浴温: 150 〜270 ℃ めっき電流密度: 20〜60 A/dm2 (合金元素により変
動、例えば、純Alめっきでは20 A/dm2;Al−Mn、Al−Cr
合金めっきでは60 A/dm2) 極間液流速: 0.4〜0.7 m/sec (2) 蒸着めっき法 前処理: Arスパッター 真空度: 10-3〜10-4 Torr 基板温度:200 ℃以下 成膜速度:10μm/min 以下 蒸着めっきは、抵抗加熱法により、Alと合金化しようと
する金属を別々のルツボ内で溶融し、蒸発させて行っ
た。Bath temperature: 150 to 270 ° C. Plating current density: 20 to 60 A / dm 2 (Varies depending on alloying element, for example, 20 A / dm 2 for pure Al plating; Al-Mn, Al-Cr
For alloy plating, 60 A / dm 2 ) Electrode flow velocity: 0.4 to 0.7 m / sec (2) Vapor plating method Pretreatment: Ar sputter Vacuum degree: 10 -3 to 10 -4 Torr Substrate temperature: 200 ℃ or less Film formation Velocity: 10 μm / min or less The vapor deposition plating was performed by melting the metal to be alloyed with Al in separate crucibles and evaporating by a resistance heating method.
【0021】得られた2層めっき鋼板を使用して、下記
要領でクロメート処理後に電着塗装を行い、塗装後耐食
性について調べた。 (塗装後耐食性評価試験法) クロメート処理:日本パーカー製のアルクロム713 を使
用し、常温浸漬によりクロメート処理した後、水洗乾燥
を行った。Cr付着量は10 mg/m2とした。 電着塗装:日本ペイント製UD80を液温28℃に保持し、
電圧210 Vで通電した後、水洗、焼付 (175 ℃) を行っ
た。焼付後の膜厚は20μmであった。Using the obtained two-layer plated steel sheet, after the chromate treatment in the following manner, electrodeposition coating was carried out, and the corrosion resistance after coating was examined. (Test method for evaluating corrosion resistance after painting) Chromate treatment: Alchrome 713 manufactured by Nippon Parker was used, and after chromate treatment by immersion at room temperature, it was washed with water and dried. The amount of deposited Cr was 10 mg / m 2 . Electrodeposition coating: Hold UD80 made by Nippon Paint at a liquid temperature of 28 ° C,
After energizing at a voltage of 210 V, it was washed with water and baked (175 ° C). The film thickness after baking was 20 μm.
【0022】塗装後耐食性は、塗装サンプルに素地鋼に
達するカットを入れ、塩水噴霧 (35℃) →乾燥 (50℃)
→湿潤 (50℃) を1サイクル (1サイクル24時間) とす
る複合腐食試験により、100 サイクル経過後の腐食深さ
および塗膜のふくれ幅により評価した。Corrosion resistance after coating, the coating sample cut to reach the base steel, salt spray (35 ℃) → dry (50 ℃)
→ A complex corrosion test was conducted with wet (50 ° C) as one cycle (one cycle 24 hours), and the corrosion depth after 100 cycles and the blister width of the coating film were evaluated.
【0023】また、参考として未塗装耐食性をJIS に規
定された塩水噴霧試験での赤錆発生までの日数として測
定した。試験結果を、下層および上層のめっきの詳細と
共に、次の表1〜表2にまとめて示す。As a reference, the unpainted corrosion resistance was measured as the number of days until the occurrence of red rust in the salt spray test specified by JIS. The test results are summarized in the following Tables 1 and 2 together with the details of the plating of the lower layer and the upper layer.
【0024】[0024]
【表1】 [Table 1]
【0025】[0025]
【表2】 [Table 2]
【0026】[0026]
【発明の効果】実施例の結果からもわかるように、本発
明による下層Zn系めっき皮膜と上層Al系多孔性めっき皮
膜を有する2層めっき鋼材は、上層Al系めっきを付着量
0.1〜10 g/m2 の多孔性めっきとすることにより、塗装
後耐食性試験において、塗膜ふれ、腐食深さともに非常
に微小であり、良好な塗装後耐食性を有する。それによ
り、この種の2層めっき鋼材で問題であった、塗膜に傷
が付いたときの塗膜ふくれの現象を大幅に軽減すること
ができる。本発明の種類の2層めっき鋼材は、自動車、
建材、家電製品などの用途に塗装して使用されることが
多く、塗膜ふくれの軽減は製品品質、商品価値の著しい
向上につながる。As can be seen from the results of the examples, the two-layer plated steel material having the lower Zn-based plating film and the upper Al-based porous plating film according to the present invention has an upper Al-based plating amount applied.
By using 0.1 to 10 g / m 2 of porous plating, in the post-painting corrosion resistance test, both the coating run-out and the corrosion depth are very small, and the post-painting corrosion resistance is excellent. As a result, the phenomenon of coating film swelling when the coating film is scratched, which is a problem with this type of double-layer plated steel material, can be greatly reduced. The two-layer plated steel material of the type of the present invention is used for automobiles,
It is often used as a coating for building materials, home appliances, etc., and reducing the swelling of the coating film leads to a marked improvement in product quality and product value.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 内田 淳一 大阪市中央区北浜4丁目5番33号 住友金 属工業株式会社内 (72)発明者 福井 国博 大阪市中央区北浜4丁目5番33号 住友金 属工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junichi Uchida 4-533 Kitahama, Chuo-ku, Osaka City Sumitomo Metal Industries, Ltd. (72) Inventor Kunihiro Fukui 4-53-3 Kitahama, Chuo-ku, Osaka City Sumitomo Metal Industries Co., Ltd.
Claims (1)
っきが付着量 0.1〜10 g/m2 の多孔性AlまたはAl合金層
であることを特徴とする、塗装後耐食性に優れた2層め
っき鋼材。1. A two-layer structure excellent in corrosion resistance after painting, characterized in that the lower layer plating is a Zn or Zn alloy layer and the upper layer plating is a porous Al or Al alloy layer having an adhesion amount of 0.1 to 10 g / m 2. Plated steel material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34521991A JPH05171491A (en) | 1991-12-26 | 1991-12-26 | Double layer plated steel excellent in corrosion resistance after coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34521991A JPH05171491A (en) | 1991-12-26 | 1991-12-26 | Double layer plated steel excellent in corrosion resistance after coating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05171491A true JPH05171491A (en) | 1993-07-09 |
Family
ID=18375108
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP34521991A Pending JPH05171491A (en) | 1991-12-26 | 1991-12-26 | Double layer plated steel excellent in corrosion resistance after coating |
Country Status (1)
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JP (1) | JPH05171491A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007500285A (en) * | 2003-07-29 | 2007-01-11 | フェストアルピネ シュタール ゲーエムベーハー | Method for manufacturing hardened steel parts |
JP2019173863A (en) * | 2018-03-28 | 2019-10-10 | 川田工業株式会社 | Fastening structure for steel material structure and fastening method |
JP2020143361A (en) * | 2019-03-04 | 2020-09-10 | 日本製鉄株式会社 | Alloy material and method for manufacturing the same |
-
1991
- 1991-12-26 JP JP34521991A patent/JPH05171491A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007500285A (en) * | 2003-07-29 | 2007-01-11 | フェストアルピネ シュタール ゲーエムベーハー | Method for manufacturing hardened steel parts |
JP2019173863A (en) * | 2018-03-28 | 2019-10-10 | 川田工業株式会社 | Fastening structure for steel material structure and fastening method |
JP2020143361A (en) * | 2019-03-04 | 2020-09-10 | 日本製鉄株式会社 | Alloy material and method for manufacturing the same |
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