JP2005154857A - Alloyed hot dip galvanized steel sheet, and method for manufacturing the same - Google Patents
Alloyed hot dip galvanized steel sheet, and method for manufacturing the same Download PDFInfo
- Publication number
- JP2005154857A JP2005154857A JP2003396826A JP2003396826A JP2005154857A JP 2005154857 A JP2005154857 A JP 2005154857A JP 2003396826 A JP2003396826 A JP 2003396826A JP 2003396826 A JP2003396826 A JP 2003396826A JP 2005154857 A JP2005154857 A JP 2005154857A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- bath
- dip galvanized
- hot
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
本発明は、鋼の高強度化のために合金元素としてSi、Alを含有し、さらにめっき性および表面性状に優れた合金化溶融亜鉛めっき鋼板およびその製造方法に関するものである。 The present invention relates to an alloyed hot-dip galvanized steel sheet containing Si and Al as alloy elements for increasing the strength of steel and having excellent plating properties and surface properties, and a method for producing the same.
近年、地球温暖化防止の観点から、自動車の燃費向上の必要性が高まり、鋼板の薄肉化による車体軽量化が積極的に行われている。一方、自動車の安全性に対するニーズも高まってきていることから、車体を軽量化しつつ、高い車体強度を維持することが望まれている。このため、自動車用部材に対して高強度鋼板を採用しようとする動きが高まっている。 In recent years, from the viewpoint of preventing global warming, the need for improving the fuel efficiency of automobiles has increased, and the weight reduction of the vehicle body has been actively carried out by reducing the thickness of the steel sheet. On the other hand, since the needs for safety of automobiles are also increasing, it is desired to maintain high vehicle body strength while reducing the weight of the vehicle body. For this reason, the movement which is going to employ | adopt a high strength steel plate with respect to the member for motor vehicles is increasing.
一方、自動車用部材は形状が複雑なものが多く、大半がプレス成形により加工されるが、高強度鋼板は軟質系鋼板と比較すると、延性が低いためプレス成形性に劣るという欠点がある。そこで、高強度と高延性を兼ね備えたプレス成形性に優れる高強度鋼板の開発が盛んに行われてきた。 On the other hand, many automotive members have complicated shapes, and most of them are processed by press forming. However, compared with soft steel plates, high-strength steel plates have a disadvantage that they are inferior in press formability because of low ductility. Therefore, development of high-strength steel sheets having both high strength and high ductility and excellent press formability has been actively conducted.
例えば、特許文献1には、残留オーステナイトの加工誘起変態を利用することで、優れた強度-延性バランスを有する冷延鋼板が開示されている。この冷延鋼板は、C、Si、Mnなどを含有する鋼板を、オーステナイト域あるいはフェライト+オーステナイト二相域で焼鈍した後、フェライト・パーライト変態を起こさないようにベイナイト変態温度域まで急冷し、その温度域で一定時間保持してオーステナイト→ベイナイト変態をある程度進行させることによって、残ったオーステナイト中にCを濃化させ、C濃度の高いオーステナイトが存在する状態で室温まで冷却し、残留オーステナイトを生成させることによって得られる冷延鋼板である。 For example, Patent Document 1 discloses a cold-rolled steel sheet having an excellent strength-ductility balance by utilizing a processing-induced transformation of retained austenite. This cold-rolled steel sheet is a steel sheet containing C, Si, Mn, etc., annealed in the austenite region or ferrite + austenite two-phase region, and then rapidly cooled to the bainite transformation temperature region so as not to cause ferrite-pearlite transformation. By maintaining the temperature for a certain period of time and advancing the austenite to bainite transformation to some extent, C is concentrated in the remaining austenite and cooled to room temperature in the presence of high C austenite to generate residual austenite. It is a cold-rolled steel sheet obtained by this.
また、自動車用鋼板に要求される特性の1つに耐食性があるため、電気めっきあるいは溶融めっきを施した鋼板が求められており、特に厚めっきが可能でコスト的にも有利な溶融亜鉛めっき鋼板が多く使用されている。しかしながら、前述した鋼板は、Siを多量に含有しており、焼鈍時の選択酸化により鋼板表面にSi酸化物が生成するため、亜鉛めっき浴との濡れ性に劣り、不めっきの発生など満足のいく溶融亜鉛めっき鋼板を得ることができない欠点がある。 In addition, one of the characteristics required for steel sheets for automobiles is corrosion resistance, so steel sheets that have undergone electroplating or hot dipping are required. Hot-dip galvanized steel sheets that are particularly thick and can be cost-effective Is often used. However, the steel sheet described above contains a large amount of Si, and Si oxides are generated on the steel sheet surface by selective oxidation during annealing, so that the wettability with the galvanizing bath is inferior and the occurrence of non-plating is satisfactory. There is a disadvantage that it is impossible to obtain a hot dip galvanized steel sheet.
このため、めっき性およびめっき密着性と強度・延性バランスを両立させるために、鋼板中にAlを添加し、C、Si、Mn、P、S、Al、Nの含有量を適正化した溶融亜鉛めっき鋼板が特許文献2に開示されている。しかしながら、高強度化に必要なSi量およびAl量についてSi<0.5%、Al<1.5%の上限がめっき密着性の観点から記述されており、より高強度化を狙うためにSi量やAl量を増加させることはできない。 For this reason, in order to achieve both the plateability and plating adhesion and the balance between strength and ductility, Al is added to the steel sheet, and the content of C, Si, Mn, P, S, Al, and N is optimized. A plated steel sheet is disclosed in Patent Document 2. However, the upper limits of Si <0.5% and Al <1.5% for Si and Al required for increasing strength are described from the viewpoint of plating adhesion, and in order to achieve higher strength, the amount of Si and Al Cannot be increased.
また、残留オーステナイトを生成させるのにSiは有効であるが、同様の効果が得られるAlに着目し、さらにSi量を減らしつつAl量で補う発明が特許文献3に開示されている。この発明の特徴は、550℃〜750℃の範囲で前酸化処理を施し、表面の酸化鉄量を2〜4g/m2形成した後に、N2-H2雰囲気中で還元することで、還元Fe量の増加によりめっき性を確保していることが特徴である。しかしこの方法であってもSi量が多いと、前酸化時に酸化鉄の生成量が十分ではなくめっき性が改善されないため、上限が1.0%に規定されている。 Further, although Si is effective in generating retained austenite, Patent Document 3 discloses an invention that pays attention to Al that can provide the same effect, and further compensates with Al content while reducing Si content. The feature of the present invention is that the pre-oxidation treatment is performed in the range of 550 ° C. to 750 ° C., the amount of iron oxide on the surface is formed to 2 to 4 g / m 2 , and then the reduction is performed in an N 2 —H 2 atmosphere. The feature is that the plating property is secured by increasing the amount of Fe. However, even with this method, if the amount of Si is large, the amount of iron oxide produced during pre-oxidation is not sufficient and the plating property is not improved, so the upper limit is defined as 1.0%.
一方、Si量およびAl量を比較的多く含む鋼板に対してめっき性を確保するために、めっき浴中にMnを含有させる方法が、特許文献4に開示されているが、めっき浴中にMnを含有させる方法はこのような難めっき性の鋼板に対しては有効であるが、その他の鋼板、特に軟質系鋼板に対してはめっき浴中でのFe-Zn反応を活性化し、ドロスの発生やめっき密着性の劣化を招くことから、一連の操業を行う上で問題がある。 On the other hand, in order to ensure plating properties for a steel sheet containing a relatively large amount of Si and Al, a method of containing Mn in the plating bath is disclosed in Patent Document 4, but Mn is contained in the plating bath. Is effective for such difficult-to-plate steel sheets, but for other steel sheets, especially soft steel sheets, it activates the Fe-Zn reaction in the plating bath and generates dross. This causes a problem in performing a series of operations.
以下に先行技術文献情報について記載する。
このように、高強度化の観点からSiやAlを多く含有させたいニーズはあるものの、溶融めっき鋼板ではめっき性の観点から上限があり、また上限を緩和するためにめっき浴の工夫などを行ったとしても、その他の鋼種ではめっき性に悪影響を及ぼすなどの問題があるのが現状である。 As described above, although there is a need to contain a large amount of Si and Al from the viewpoint of increasing the strength, there is an upper limit from the viewpoint of plating properties with hot-dip plated steel sheets, and a plating bath is devised to ease the upper limit. Even so, other steel types currently have problems such as adversely affecting plating properties.
本発明は、前記問題点を解決し、SiとAlを含有し、さらにめっき性も確保できる合金化溶融亜鉛めっき鋼板およびその製造方法を提供することを課題とする。 This invention solves the said problem, and makes it a subject to provide the alloyed hot-dip galvanized steel plate which contains Si and Al, and can also ensure plating property, and its manufacturing method.
本発明者らは、上記の課題を解決すべく、SiとAlを含有し、さらにめっき性も確保した鋼板の開発に取り組んだ。その結果、SiおよびAlを含有する鋼板でも、あらかじめ弱酸化を施し表面にFe酸化物層を形成した後、N2-H2雰囲気中でFe酸化物層を還元することで、めっき性を十分確保できること、また、弱酸化を施す際に急速加熱を施す手法が有効であることを見出した。 In order to solve the above-mentioned problems, the present inventors have worked on the development of a steel sheet containing Si and Al and further ensuring plating properties. As a result, even with steel sheets containing Si and Al, after weak oxidation is performed in advance and an Fe oxide layer is formed on the surface, the Fe oxide layer is reduced in an N 2 -H 2 atmosphere, thereby ensuring sufficient plating properties. It has been found that a method of applying rapid heating is effective when performing weak oxidation.
さらに、Si、Alを含有する鋼板を還元雰囲気中で焼鈍すると、表面にAlが濃化することでSiの濃化が抑制され、このAlはめっき性にほとんど影響を及ぼさないために、Si添加量に応じてAl添加量を適正化すると、めっき性を十分確保できることを見出した。 Furthermore, when steel sheets containing Si and Al are annealed in a reducing atmosphere, the concentration of Si is suppressed by the concentration of Al on the surface, and this Al has little effect on the plating properties. It has been found that if the Al addition amount is optimized according to the amount, sufficient plating properties can be secured.
本発明は、以上の知見に基づきなされたものであり、その要旨は以下のとおりである。 The present invention has been made based on the above findings, and the gist thereof is as follows.
第一発明は、鋼板を、直火還元加熱方式の加熱炉を用いて加熱し、さらに還元炉に導き鋼板表面の還元ならびに焼鈍を行った後、溶融亜鉛浴に侵入させ亜鉛めっきを施したうえで合金化処理した合金化溶融亜鉛めっき鋼板において、下地鋼板の成分が、Si(%)≦2.0mass%、Al(%)≦3.0mass%、かつ0.6Si(%)≦Al(%)+0.3を満足することを特徴とする合金化溶融亜鉛めっき鋼板を提供する。 In the first invention, the steel sheet is heated by using a direct-fire reduction heating type heating furnace, further led to the reduction furnace and subjected to reduction and annealing of the steel sheet surface, and then intruded into a hot dip zinc bath and galvanized. In the alloyed hot-dip galvanized steel sheet alloyed with, the components of the base steel sheet are Si (%) ≦ 2.0 mass%, Al (%) ≦ 3.0 mass%, and 0.6 Si (%) ≦ Al (%) + 0.3 An alloyed hot-dip galvanized steel sheet is provided.
第二発明は、第一発明において、上記合金化溶融亜鉛めっき鋼板の亜鉛付着量が30〜90g/m2であり、かつめっき皮膜中のFe濃度およびAl濃度が、それぞれ8〜14%、0.1〜0.5%の範囲にあることを特徴とする合金化溶融亜鉛めっき鋼板を提供する。 The second invention, in the first invention, the zinc coating weight of the galvannealed steel sheet is 30~90g / m 2, and Fe concentration and the Al concentration in the plating film, respectively from 8 to 14%, 0.1 An alloyed hot-dip galvanized steel sheet characterized by being in the range of ˜0.5% is provided.
第三発明は、鋼成分が、Si(%)≦2.0mass%、Al(%)≦3.0mass%、かつ0.6Si(%)≦Al(%)+0.3を満足する鋼板を、直火還元加熱方式の加熱炉を用いて加熱し、さらに還元炉に導き鋼板表面の還元ならびに焼鈍を行った後、溶融亜鉛浴に侵入させ亜鉛めっきを施したうえで合金化処理した合金化溶融亜鉛めっき鋼板を製造する方法において、直火還元加熱方式の加熱炉における空燃比が0.7〜1.2の範囲にあり、かつ加熱炉の前段の空燃比が1.0以上で後段の空燃比が1.0未満であることを特徴とする合金化溶融亜鉛めっき鋼板の製造方法を提供する。 The third invention is a direct heating reduction heating of a steel plate whose steel components satisfy Si (%) ≦ 2.0 mass%, Al (%) ≦ 3.0 mass%, and 0.6 Si (%) ≦ Al (%) + 0.3. An alloyed hot-dip galvanized steel sheet that was heated using a heating furnace of the type, led to a reduction furnace, reduced and annealed on the surface of the steel sheet, penetrated into a hot-dip galvanized bath, and then galvanized and alloyed. In the manufacturing method, the air-fuel ratio in the direct-fire reduction heating type heating furnace is in the range of 0.7 to 1.2, the air-fuel ratio in the front stage of the heating furnace is 1.0 or more, and the air-fuel ratio in the rear stage is less than 1.0. A method for producing an alloyed hot-dip galvanized steel sheet is provided.
第四発明は、鋼成分が、Si(%)≦2.0mass%、Al(%)≦3.0mass%、かつ0.6Si(%)≦Al(%)+0.3を満足する鋼板を、直火還元加熱方式の加熱炉を用いて加熱し、さらに還元炉に導き鋼板表面の還元ならびに焼鈍を行った後、溶融亜鉛浴に侵入させ亜鉛めっきを施したうえで合金化処理した合金化溶融亜鉛めっき鋼板を製造する方法において、溶融亜鉛浴中のAl濃度が0.05〜0.20%、かつ浴温が450〜480℃であり、さらに溶融亜鉛浴中への鋼板の侵入時間が2〜5秒の範囲にあることを特徴とする合金化溶融亜鉛めっき鋼板の製造方法を提供する。 The fourth invention is a direct heating reduction heating of a steel plate whose steel components satisfy Si (%) ≦ 2.0 mass%, Al (%) ≦ 3.0 mass%, and 0.6 Si (%) ≦ Al (%) + 0.3. An alloyed hot-dip galvanized steel sheet that was heated using a heating furnace of the type, led to a reduction furnace, reduced and annealed on the surface of the steel sheet, penetrated into a hot-dip galvanized bath, and then galvanized and alloyed. In the manufacturing method, the Al concentration in the molten zinc bath is 0.05 to 0.20%, the bath temperature is 450 to 480 ° C., and the penetration time of the steel sheet into the molten zinc bath is in the range of 2 to 5 seconds. The manufacturing method of the galvannealed steel plate characterized by these is provided.
第五発明は、鋼成分が、Si(%)≦2.0mass%、Al(%)≦3.0mass%、かつ0.6Si(%)≦Al(%)+0.3を満足する鋼板を、直火還元加熱方式の加熱炉を用いて加熱し、さらに還元炉に導き鋼板表面の還元ならびに焼鈍を行った後、溶融亜鉛浴に侵入させ亜鉛めっきを施したうえで合金化処理した合金化溶融亜鉛めっき鋼板を製造する方法において、直火還元加熱方式の加熱炉における空燃比が0.7〜1.2の範囲にあり、加熱炉の前段の空燃比が1.0以上で後段の空燃比が1.0未満であり、溶融亜鉛浴中のAl濃度が0.05〜0.20%、かつ浴温が450〜480℃であり、さらに溶融亜鉛浴中への鋼板の侵入時間が2〜5秒の範囲にあることを特徴とする合金化溶融亜鉛めっき鋼板の製造方法を提供する。 The fifth aspect of the present invention is a direct heating reduction heating of a steel sheet whose steel components satisfy Si (%) ≦ 2.0 mass%, Al (%) ≦ 3.0 mass%, and 0.6 Si (%) ≦ Al (%) + 0.3. An alloyed hot-dip galvanized steel sheet that was heated using a heating furnace of the type, led to a reduction furnace, reduced and annealed on the surface of the steel sheet, penetrated into a hot-dip galvanized bath, and then galvanized and alloyed. In the manufacturing method, the air-fuel ratio in the direct-fire reduction heating type heating furnace is in the range of 0.7 to 1.2, the air-fuel ratio in the front stage of the heating furnace is 1.0 or more and the air-fuel ratio in the rear stage is less than 1.0, and in the molten zinc bath Alloying hot dip galvanizing characterized in that the Al concentration of the steel is 0.05 to 0.20%, the bath temperature is 450 to 480 ° C., and the penetration time of the steel sheet into the hot dip zinc bath is in the range of 2 to 5 seconds A method for producing a steel sheet is provided.
なお、本明細書において、鋼の成分を示す%はmass%である。 In addition, in this specification,% which shows the component of steel is mass%.
本発明によれば、合金元素としてSi、Alを含有しても、めっき性および表面性状に優れた合金化溶融亜鉛めっき鋼板を安定して得ることができる。 According to the present invention, even if Si and Al are contained as alloy elements, an alloyed hot-dip galvanized steel sheet having excellent plating properties and surface properties can be stably obtained.
以下、本発明について具体的に説明する。 Hereinafter, the present invention will be specifically described.
本発明では、鋼板を直火還元加熱方式の加熱炉を用いて加熱し、さらに還元炉に導き鋼板表面の還元ならびに焼鈍を行った後、溶融亜鉛浴に侵入させ亜鉛めっきを施したうえで合金化処理した合金化溶融亜鉛めっき鋼板を前提としている。 In the present invention, the steel sheet is heated using a direct-fire reduction heating furnace, and further led to the reduction furnace to reduce and anneal the steel sheet surface, and then penetrated into a molten zinc bath and galvanized, and then alloyed. It is premised on an alloyed hot-dip galvanized steel sheet.
直火還元加熱方式の加熱炉は、火炎を鋼板に直接衝突させることで鋼板の急速加熱を行うことができるが、この際に、空燃比を調整することで、還元炎と酸化炎の比率を任意に制御でき、鋼板の酸化状態および還元状態を容易に制御できることが特徴である。 The direct-fire reduction heating furnace can rapidly heat the steel sheet by directly colliding the flame with the steel sheet. At this time, by adjusting the air-fuel ratio, the ratio of the reducing flame to the oxidizing flame can be adjusted. It can be controlled arbitrarily, and is characterized in that the oxidation state and reduction state of the steel sheet can be easily controlled.
ここで、鋼板を直火還元加熱方式の加熱炉で急速加熱することなく、一般的に使用されるラジアントチューブ方式の還元炉のみで焼鈍を行うと、比較的低速で加熱が進行すること、および鋼板表面に存在する自然酸化膜の還元は比較的短時間で完了することから、鋼板中のSiの選択酸化が生じるため、めっき直前までに鋼板表面をSi系酸化物が覆うことで、不めっきが発生する。 Here, when annealing is performed only in a commonly used radiant tube type reducing furnace without rapidly heating the steel sheet in a direct flame reduction heating type heating furnace, heating proceeds at a relatively low speed, and Since the reduction of the natural oxide film on the surface of the steel sheet is completed in a relatively short period of time, selective oxidation of Si in the steel sheet occurs. Will occur.
一方、鋼板を直火還元加熱方式の加熱炉で急速加熱すると、鋼板表面に残存していた圧延油などの不純物成分が燃焼すると同時に、鋼板表面がわずかに酸化する現象が生じる。また、鋼板表面が急速に加熱されることで、めっきの際に有害となるSi系酸化物の形成は生じない。その後、還元炉に導かれると、わずかに酸化した鋼板表面の還元反応が生じ、清浄なFeが表面に形成された鋼板となる。直火還元加熱方式の加熱炉でわずかに形成される酸化物層は、自然酸化膜と比較すると厚く、還元炉内での還元反応に時間を要し、同時にSiの選択酸化も抑制されるため、比較的多量のSiを含有した鋼板に対しても不めっきの発生しない溶融亜鉛めっき鋼板を得ることができる。しかしながら、鋼板の強度・延びなどの要求によりSi含有量を増加させると、直火還元加熱方式の加熱炉で弱酸化されたとしてもSiの選択酸化を抑制できず、不めっきが発生しやすくなる。ここで、Siと同時にAlを含有させた鋼板では、還元炉での焼鈍の際に、表面にAlが濃化しAl系酸化物が形成されるが、Siの表面濃化が生じないという特徴がある。このようにAlの表面濃化が生じ、Siの表面濃化が抑制されるのは、酸素との親和力がSiよりAlで高いためであると考えられる。 On the other hand, when a steel sheet is rapidly heated in a direct flame reduction heating furnace, impurity components such as rolling oil remaining on the steel sheet surface burn, and at the same time, a phenomenon occurs in which the steel sheet surface is slightly oxidized. Further, since the surface of the steel sheet is rapidly heated, formation of Si-based oxides that are harmful during plating does not occur. Thereafter, when guided to a reduction furnace, a reduction reaction of the slightly oxidized steel sheet surface occurs, and the steel sheet has clean Fe formed on the surface. The oxide layer slightly formed in the direct-fire reduction heating furnace is thicker than the natural oxide film, and it takes time for the reduction reaction in the reduction furnace, and at the same time, selective oxidation of Si is suppressed. Moreover, a hot-dip galvanized steel sheet that does not cause non-plating can be obtained even for a steel sheet containing a relatively large amount of Si. However, if the Si content is increased due to demands such as strength and elongation of the steel sheet, even if it is weakly oxidized in a direct-fire reduction heating furnace, selective oxidation of Si cannot be suppressed, and non-plating is likely to occur. . Here, in the steel sheet containing Al at the same time as Si, when annealing in a reduction furnace, Al is concentrated on the surface and an Al-based oxide is formed, but the surface concentration of Si does not occur. is there. The reason why the surface concentration of Al occurs in this way and the surface concentration of Si is suppressed is thought to be because the affinity for oxygen is higher in Al than in Si.
また、Alが表面に濃化しAl系酸化物が形成された場合でも、その後、溶融亜鉛めっき浴に浸漬した際に、不めっきなどの濡れ性不良は生じない。このメカニズムについては明確ではないが、次のように考えることができる。一般に、溶融亜鉛めっき浴中には、鋼板との間で過剰なFe-Zn反応を抑制するために、微量のAlが添加されている。この浴中のAlは、Znよりも優先的にFeと反応し、Fe-Al合金層が鋼板表面に形成されるが、鋼板表面に存在するAl系酸化物もFe-Al合金層の形成に関与するため、溶融亜鉛との濡れ性劣化を招かないと考えられる。 Further, even when Al is concentrated on the surface and an Al-based oxide is formed, no wettability failure such as non-plating occurs when immersed in a hot dip galvanizing bath. Although this mechanism is not clear, it can be considered as follows. In general, a small amount of Al is added to the hot dip galvanizing bath in order to suppress an excessive Fe—Zn reaction with the steel sheet. Al in this bath reacts preferentially with Fe over Zn, and an Fe-Al alloy layer is formed on the surface of the steel sheet, but Al-based oxides present on the surface of the steel sheet also contribute to the formation of the Fe-Al alloy layer. It is considered that it does not cause wettability deterioration with molten zinc.
このように、SiとAlを同時に鋼板中に含有させることにより、還元炉での加熱焼鈍時にSi系酸化物の鋼板表面への濃化が抑制され、良好なめっき性が得られるが、SiとAlの濃度バランスを0.6Si(%)≦Al(%)+0.3とする必要がある。これは、この濃度バランスを満足しない成分の鋼板を焼鈍すると、鋼板中に存在するAlがSi系酸化物の表面濃化を抑制するのに十分でなく、めっき性の劣化を招く恐れがあるためである。一方、Siは、その含有量が増すにつれて、Alを同時に含有させたとしてもSi系酸化物の表面濃化量が増加し、めっき性の劣化を招く恐れがあること、またSiの含有量によりその後の合金化処理速度は変化し、多量にSiを含有すると合金化処理温度の上昇や処理時間の長大化を招くことから、含有量を2.0mass%以下とする必要がある。また、Alは、高価である上に、多量に含有させると、介在物の増加による延性の劣化やフラッシュバット溶接の劣化を招くことから、含有量を3.0mass%以下とする必要がある。 Thus, by simultaneously containing Si and Al in the steel sheet, concentration of the Si-based oxide on the steel sheet surface during heat annealing in the reduction furnace is suppressed, and good plating properties are obtained. The Al concentration balance needs to be 0.6 Si (%) ≦ Al (%) + 0.3. This is because if steel sheets with components that do not satisfy this concentration balance are annealed, the Al present in the steel sheet is not sufficient to suppress the surface concentration of the Si-based oxides, which may lead to deterioration of the plating properties. It is. On the other hand, as the content of Si increases, even if Al is contained at the same time, the surface concentration of the Si-based oxide increases, which may lead to deterioration of the plating property. Thereafter, the alloying treatment speed changes, and if a large amount of Si is contained, the alloying treatment temperature rises and the treatment time is lengthened, so the content needs to be 2.0 mass% or less. Moreover, since Al is expensive and contains a large amount, it causes deterioration of ductility due to increase of inclusions and deterioration of flash butt welding, so the content needs to be 3.0 mass% or less.
本発明が対象とする鋼板は、強度と延性のバランス確保の観点からSiとAl量の合計が0.2mass%以上であることが望ましく、さらにTRIP鋼などの高延性を確保する場合においては、SiとAl量の合計が0.4mass%以上であることがより好ましい。 In the steel sheet targeted by the present invention, the total amount of Si and Al is preferably 0.2 mass% or more from the viewpoint of ensuring a balance between strength and ductility. Furthermore, when ensuring high ductility such as TRIP steel, And the total amount of Al is more preferably 0.4 mass% or more.
なお、本発明では、鋼板中のSiおよびAl量が本発明範囲内にあればよく、その他の成分は特に制限されず、Feおよび不可避的不純物の他に、C、Mn、S、Mg、Cr、Ni、Cu、Taなどの1種または2種以上を含有してもよい。また、IF鋼ベースとするために、Nb、Tiを添加してもよく、さらに耐二次加工性脆化を防止するために、数ppmのBを添加してもよい。 In the present invention, the amount of Si and Al in the steel sheet only needs to be within the scope of the present invention, and other components are not particularly limited. In addition to Fe and unavoidable impurities, C, Mn, S, Mg, Cr , Ni, Cu, Ta or the like may be contained. Further, Nb and Ti may be added for the IF steel base, and several ppm of B may be added for preventing secondary work resistance embrittlement.
前述したように、本発明では、還元炉での還元焼鈍の前に、直火還元加熱方式の加熱炉により急速加熱させることを前提としているが、直火還元加熱方式の加熱炉の空燃比を0.7〜1.2の範囲で調整する必要がある。また、この直火還元加熱方式の加熱炉の目的は、鋼板の急速加熱であるのと同時に、鋼板表面に微量に残存した圧延油などの不純物を燃焼除去することと、鋼板表面を微量酸化させることであることから、加熱炉の前段を弱酸化雰囲気の空燃比1.0以上とする必要がある。また、直火還元加熱方式の加熱炉全体を弱酸化雰囲気とすると、鋼板表面が過剰に酸化され、その後の還元炉での還元焼鈍において十分に還元されず、未還元のFeが鋼板表面に残存し、めっき性の劣化を招くことから、後段の空燃比は還元雰囲気の1.0未満とする必要がある。これら空燃比を制御する領域の長さについては、特に制限はなく、直火還元加熱方式の加熱炉の長さおよびラインスピードの関係から調整すればよいが、それぞれの長さが長すぎると生産性の阻害を招くことから、通過時間に換算してそれぞれ20秒以内であることが好ましい。 As described above, in the present invention, it is assumed that rapid heating is performed by a direct-fire reduction heating type heating furnace before reduction annealing in the reduction furnace. It is necessary to adjust in the range of 0.7-1.2. In addition, the purpose of this direct-fire reduction heating furnace is rapid heating of the steel sheet, and simultaneously burns and removes impurities such as rolling oil remaining on the surface of the steel sheet and oxidizes the surface of the steel sheet in a small amount. Therefore, it is necessary to set the front stage of the heating furnace to an air-fuel ratio of 1.0 or more in a weakly oxidizing atmosphere. In addition, if the entire direct heating reduction heating furnace is made into a weakly oxidizing atmosphere, the steel sheet surface is excessively oxidized and is not sufficiently reduced in the subsequent reduction annealing in the reducing furnace, and unreduced Fe remains on the steel sheet surface. However, since the plating property is deteriorated, the air-fuel ratio in the subsequent stage needs to be less than 1.0 in the reducing atmosphere. There are no particular restrictions on the lengths of these air-fuel ratio control areas, and it may be adjusted based on the relationship between the length of the direct-fire reduction heating furnace and the line speed. Each of them is preferably within 20 seconds in terms of the passage time because it causes the inhibition of sex.
還元焼鈍の際の雰囲気は、一般的に使用されるH2-N2雰囲気やCO-CO2雰囲気などを使用することができるが、直火加熱時に形成された鋼板表面の微量酸化物をめっき直前までに還元できる雰囲気であればよく、使用する雰囲気ガスにより本発明の効果が損なわれるものではない。 The atmosphere during reduction annealing can be the commonly used H 2 -N 2 atmosphere or CO-CO 2 atmosphere, but it is plated with a small amount of oxide on the surface of the steel sheet formed during direct fire heating It is sufficient that the atmosphere can be reduced immediately before, and the effect of the present invention is not impaired by the atmospheric gas used.
本発明で規定した成分の鋼板は、高強度鋼板での添加成分として有用なSiを多量に含有しても良好なめっき性が得られることを特徴としており、用途としては自動車用の内外板が多いことが予想される。また、溶融めっき後に合金化処理を施し、Fe-Zn合金のめっき層が形成された合金化溶融亜鉛めっき鋼板を対象としていることから、亜鉛の付着量は30〜90g/m2であることが望ましい。これは、亜鉛の付着量が30g/m2未満であると、塗装を施した後でも十分な耐食性を得ることができないためであり、逆に90g/m2を越えると、合金化処理後の鋼板-めっき界面に脆弱なΓ相が形成されパウダリング不良を招くためである。 The steel plate of the component specified in the present invention is characterized in that good plating properties can be obtained even if it contains a large amount of Si useful as an additive component in a high-strength steel plate. Many are expected. In addition, since it is intended for alloyed hot-dip galvanized steel sheets that have been subjected to alloying treatment after hot dipping and have been formed with an Fe-Zn alloy plating layer, the amount of zinc deposited should be 30-90 g / m 2 desirable. This is because if the amount of zinc deposited is less than 30 g / m 2 , sufficient corrosion resistance cannot be obtained even after coating, and conversely if it exceeds 90 g / m 2 , This is because a brittle Γ phase is formed at the steel plate-plating interface, resulting in poor powdering.
また、鋼板を溶融亜鉛めっき浴に浸漬した際やその後の合金化処理時における過剰なFe-Zn反応を抑制するために、めっき浴中に微量のAlを添加することで、めっき浴浸漬時に、めっき−鋼板界面にFe-Al合金層を形成することが必要である。この観点からめっき皮膜中のAl濃度は0.1〜0.5%の範囲にあることが望ましい。これは、めっき皮膜中のAl濃度が0.1%未満であると、Fe-Zn反応を抑制する効果が十分でないためであり、一方、0.5%を越えると、逆にFe-Zn合金化反応を抑制し、その後の合金化処理速度が遅延するためである。また、合金化溶融亜鉛めっき鋼板の摺動性および耐パウダリング性を満足するために、皮膜中のFe濃度は8〜14%の範囲にあることが望ましい。これは、皮膜中のFe濃度が8%未満であるとめっき表面と金型の凝着によりプレス割れなどを生じる恐れがあるためであり、また14%を越えると、プレス割れの懸念は少なくなるものの、鋼板-めっき界面に脆弱なΓ相が形成され、パウダリング不良を生じる恐れがあるためである。 In addition, in order to suppress excessive Fe-Zn reaction at the time of immersing the steel sheet in the hot dip galvanizing bath or during the subsequent alloying treatment, by adding a small amount of Al to the plating bath, It is necessary to form an Fe-Al alloy layer at the plating-steel interface. From this point of view, the Al concentration in the plating film is desirably in the range of 0.1 to 0.5%. This is because if the Al concentration in the plating film is less than 0.1%, the effect of suppressing the Fe-Zn reaction is not sufficient, while if it exceeds 0.5%, the Fe-Zn alloying reaction is suppressed. This is because the subsequent alloying process speed is delayed. In order to satisfy the slidability and powdering resistance of the galvannealed steel sheet, it is desirable that the Fe concentration in the film is in the range of 8 to 14%. This is because if the Fe concentration in the film is less than 8%, there is a risk of press cracking due to adhesion between the plating surface and the mold, and if it exceeds 14%, there is less concern about press cracking. However, this is because a fragile Γ phase is formed at the steel plate-plating interface, which may cause poor powdering.
このように、皮膜中にはAlを含有させる必要があるが、このような合金化溶融亜鉛めっき鋼板を製造する際には、めっき浴中のAl濃度は0.05〜0.20%、浴温は450〜480℃の範囲に制御する必要がある。これは、この範囲をはずれると、前述したAl濃度をめっき皮膜中に含有させることができないためである。また、これらのめっき浴中への浸漬時間は、2〜5秒の範囲にあることが望ましい。これは、2秒未満であると、浴中での反応が十分でなく、適切な成分の鋼板を使用してもめっき不良が生じる恐れがあるためであり、一方、5秒を越えると、Fe-Zn反応が過剰となり、めっき浴中にAlを添加したとしてもその抑制作用を期待できないそれ以上の反応は期待できないためである。めっき浴に浸漬した後の鋼板は、ガスワイピングなどの常法の手段により、付着量を30〜180g/m2に調整すればよい。 Thus, although it is necessary to contain Al in the film, when manufacturing such an alloyed hot-dip galvanized steel sheet, the Al concentration in the plating bath is 0.05 to 0.20%, and the bath temperature is 450 to It is necessary to control to the range of 480 ℃. This is because the Al concentration described above cannot be contained in the plating film if it is out of this range. The immersion time in these plating baths is preferably in the range of 2 to 5 seconds. This is because if it is less than 2 seconds, the reaction in the bath is not sufficient, and even if a steel plate having an appropriate component is used, plating failure may occur. This is because the -Zn reaction becomes excessive, and even if Al is added to the plating bath, no further reaction that cannot be expected to suppress the reaction can be expected. What is necessary is just to adjust the adhesion amount of the steel plate after being immersed in a plating bath to 30-180 g / m < 2 > by means of conventional methods, such as gas wiping.
合金化処理工程においては、ガス加熱方式、誘導加熱方式、直接通電加熱方式などの方法を採用することができるが、合金化炉加熱方式の相違によって本発明の効果に変わりはない。また、皮膜中のFe濃度が本発明で規定する範囲にするために、処理温度や処理時間を調整すればよく、何ら制限はない。 In the alloying treatment step, methods such as a gas heating method, an induction heating method, and a direct current heating method can be adopted, but the effect of the present invention is not changed depending on the difference in the alloying furnace heating method. Moreover, what is necessary is just to adjust process temperature and process time in order for Fe density | concentration in a film to be the range prescribed | regulated by this invention, and there is no restriction | limiting at all.
これまで説明してきたように、本発明の合金化溶融亜鉛めっき層中には、ZnとAlおよびFeを最低限含有していればよく、耐食性向上などを目的として、As、Bi、Cd、Ce、Co、Cr、In、La、Li、Mg、Mn、Ni、O、P、Pb、S、Sb、Sn、Ti、Zrなどのうち1種または2種以上を含有させてもよく、これらを含有していても本発明の効果は損なわれない。 As described so far, the alloyed hot-dip galvanized layer of the present invention only needs to contain Zn, Al, and Fe at a minimum. For the purpose of improving corrosion resistance, etc., As, Bi, Cd, Ce , Co, Cr, In, La, Li, Mg, Mn, Ni, O, P, Pb, S, Sb, Sn, Ti, Zr, etc. Even if it contains, the effect of this invention is not impaired.
表1に示す化学成分の鋼を溶製、鋳造し、加熱温度1200℃、仕上げ温度900℃、巻取温度600℃の条件で熱間圧延を施し、3.2mm厚の鋼板とした後、酸洗、冷間圧延によって1.2mm厚の冷延鋼板とした。その後、直火加熱炉を有する連続溶融亜鉛めっきラインで、焼鈍、めっきを行った。なお、直火加熱炉においては、鋼板が加熱炉に侵入して最初の15秒間を1.0の空燃比とし、その後15秒間を0.9の空燃比に調整し,その後の、還元炉での焼鈍は、N2-10%H2雰囲気中で行った。ここで、直火加熱炉の出側での板温を650℃とし、還元炉での焼鈍温度は700〜850℃の範囲にあるように調整した。また、めっきの際には、Alを0.20%含有する470℃のめっき浴を用い、浸漬時間は3秒とした。なお、めっき付着量は45g/m2程度となるように調整し、その後の合金化処理は誘導加熱方式の合金化炉を用いて、めっき皮膜中のFe濃度が10%程度となるようにした。湿式分析の結果、めっき皮膜中のAl量は0.15〜0.25%の範囲にあった。 Steels with the chemical components shown in Table 1 are melted and cast, hot-rolled under conditions of a heating temperature of 1200 ° C, a finishing temperature of 900 ° C, and a winding temperature of 600 ° C to form a 3.2mm thick steel plate, and then pickling A cold rolled steel sheet having a thickness of 1.2 mm was obtained by cold rolling. Thereafter, annealing and plating were performed in a continuous hot dip galvanizing line having a direct-fired heating furnace. In the direct-fired heating furnace, the steel sheet enters the heating furnace and the first 15 seconds is adjusted to an air-fuel ratio of 1.0, then 15 seconds is adjusted to an air-fuel ratio of 0.9, and the subsequent annealing in the reduction furnace is: Performed in N 2 -10% H 2 atmosphere. Here, the plate temperature on the outlet side of the direct-fired heating furnace was set to 650 ° C., and the annealing temperature in the reduction furnace was adjusted to be in the range of 700 to 850 ° C. In the plating, a 470 ° C. plating bath containing 0.20% Al was used, and the immersion time was 3 seconds. In addition, the plating adhesion amount was adjusted to be about 45 g / m 2 , and the subsequent alloying treatment was performed using an induction heating type alloying furnace so that the Fe concentration in the plating film was about 10%. . As a result of wet analysis, the amount of Al in the plating film was in the range of 0.15 to 0.25%.
このように製造した合金化溶融亜鉛めっき鋼板について、不めっきの有無について評価を行った。評価は、目視での判定を行い、不めっきが全く発生していないものを○、わずかでも不めっきが認められるものを×とした。また、その後の合金化処理時において、十分に合金化が完了せず焼けムラが認められるものを×とし、合金化が完了したものについては○と評価した。 The galvannealed steel sheet produced in this way was evaluated for the presence or absence of non-plating. In the evaluation, visual judgment was made, and a case where no plating was not generated was evaluated as “◯”, and a case where even a slight amount of non-plating was observed was evaluated as “X”. Further, in the subsequent alloying treatment, the case where the alloying was not completely completed and the burning unevenness was recognized was evaluated as x, and the case where the alloying was completed was evaluated as ◯.
評価結果を表1に示す。 The evaluation results are shown in Table 1.
表1に示すように、鋼中のSiおよびAlの含有量が本発明範囲内にある場合は、不めっきが発生せず、またその後の合金化過程においても焼けムラなどは発生せず、良好な外観が得られたのに対して、Siを多量に含有するにもかかわらず、Alが添加されていない比較例(No.12、18、24)や、Alが添加されていてもAl含有量がSi含有量に対して本発明で規定する量に満たない比較例(No.13、19、25、26)は、不めっきが発生していた。また、Si含有量が本発明で規定する2.0%を越えかつAl含有量がSi含有量に対して十分でない比較例(No.30〜33)は、不めっきが発生し、加えて合金化が十分に完了せず焼けムラが発生していた。さらに、Si含有量が本発明で規定する2.0%を越えかつAl含有量がSi含有量に対して十分である比較例(No.34〜36)は、不めっきの発生は見られないものの焼けムラが生じ、良好な表面外観が得られなかった。 As shown in Table 1, when the content of Si and Al in the steel is within the range of the present invention, no plating is not generated, and in the subsequent alloying process, no burning unevenness is generated, which is good. Compared to a comparative example (No. 12, 18, 24) in which Al is not added despite the fact that it contains a large amount of Si, Al is contained even if Al is added. In the comparative examples (No. 13, 19, 25, 26) in which the amount was less than the amount specified in the present invention with respect to the Si content, non-plating occurred. Further, in Comparative Examples (No. 30 to 33) in which the Si content exceeds 2.0% specified in the present invention and the Al content is not sufficient with respect to the Si content, non-plating occurs, and in addition, alloying occurs. Unsatisfactory and burn unevenness occurred. Furthermore, in the comparative examples (No. 34 to 36) in which the Si content exceeds 2.0% specified in the present invention and the Al content is sufficient with respect to the Si content, the occurrence of non-plating is not observed. Unevenness occurred, and a good surface appearance could not be obtained.
本発明の合金化溶融亜鉛めっき鋼板の製造方法は、鋼の高強度化のために合金元素としてSi、Alを含有し、さらにめっき性および表面性状に優れた合金化溶融亜鉛めっき鋼板の製造に利用できる。 The method for producing an alloyed hot-dip galvanized steel sheet according to the present invention is used for producing an alloyed hot-dip galvanized steel sheet that contains Si and Al as alloying elements in order to increase the strength of the steel, and further has excellent plating properties and surface properties. Available.
本発明の合金化溶融亜鉛めっき鋼板は、高強度と高延性が要求される自動車用部材に利用できる。 The alloyed hot-dip galvanized steel sheet of the present invention can be used for automobile members that require high strength and high ductility.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003396826A JP4306427B2 (en) | 2003-11-27 | 2003-11-27 | Alloyed hot-dip galvanized steel sheet and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003396826A JP4306427B2 (en) | 2003-11-27 | 2003-11-27 | Alloyed hot-dip galvanized steel sheet and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005154857A true JP2005154857A (en) | 2005-06-16 |
JP4306427B2 JP4306427B2 (en) | 2009-08-05 |
Family
ID=34722151
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003396826A Expired - Fee Related JP4306427B2 (en) | 2003-11-27 | 2003-11-27 | Alloyed hot-dip galvanized steel sheet and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4306427B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007043273A1 (en) * | 2005-10-14 | 2007-04-19 | Nippon Steel Corporation | Method of continuous annealing/hot-dipping of steel sheet containing silicon and apparatus for continuous annealing/hot-dipping |
JP2008001935A (en) * | 2006-06-21 | 2008-01-10 | Kobe Steel Ltd | Steel sheet pretreatment method in annealing furnace for hot dip galvanization |
JP2010532428A (en) * | 2007-06-29 | 2010-10-07 | アルセロールミタル・フランス | Method for producing galvanized or alloyed galvanized steel sheet by DFF adjustment |
JP2013237923A (en) * | 2012-04-20 | 2013-11-28 | Jfe Steel Corp | High strength steel sheet and method for producing the same |
CN113699474A (en) * | 2021-08-30 | 2021-11-26 | 宝钢湛江钢铁有限公司 | Method for producing alloyed hot-dip galvanized GA product without bottom slag |
-
2003
- 2003-11-27 JP JP2003396826A patent/JP4306427B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007043273A1 (en) * | 2005-10-14 | 2007-04-19 | Nippon Steel Corporation | Method of continuous annealing/hot-dipping of steel sheet containing silicon and apparatus for continuous annealing/hot-dipping |
KR101011897B1 (en) * | 2005-10-14 | 2011-02-01 | 신닛뽄세이테쯔 카부시키카이샤 | Method of continous annealing/hot-dipping of steel sheet containing silicon and apparatus for continuous annealing/hot-dipping |
JP2008001935A (en) * | 2006-06-21 | 2008-01-10 | Kobe Steel Ltd | Steel sheet pretreatment method in annealing furnace for hot dip galvanization |
JP4563347B2 (en) * | 2006-06-21 | 2010-10-13 | 株式会社神戸製鋼所 | Steel plate pretreatment method in hot dip galvanizing annealing furnace |
JP2010532428A (en) * | 2007-06-29 | 2010-10-07 | アルセロールミタル・フランス | Method for producing galvanized or alloyed galvanized steel sheet by DFF adjustment |
JP2013237923A (en) * | 2012-04-20 | 2013-11-28 | Jfe Steel Corp | High strength steel sheet and method for producing the same |
CN113699474A (en) * | 2021-08-30 | 2021-11-26 | 宝钢湛江钢铁有限公司 | Method for producing alloyed hot-dip galvanized GA product without bottom slag |
Also Published As
Publication number | Publication date |
---|---|
JP4306427B2 (en) | 2009-08-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4741376B2 (en) | High-strength galvannealed steel sheet with good appearance, manufacturing method and manufacturing equipment thereof | |
JP6025867B2 (en) | High-strength hot-dip galvanized steel sheet excellent in plating surface quality and plating adhesion and method for producing the same | |
JP5720856B2 (en) | Galvanized steel sheet for hot forming | |
JP4192051B2 (en) | Manufacturing method and equipment for high-strength galvannealed steel sheet | |
US8592049B2 (en) | High strength hot dip galvanized steel sheet and high strength galvannealed steel sheet excellent in shapeability and plateability | |
JP4932376B2 (en) | High-strength hot-dip galvanized steel sheet with excellent plating properties and method for producing the same | |
JP4119804B2 (en) | High-strength galvannealed steel sheet with excellent adhesion and method for producing the same | |
JP2016084543A (en) | Hot-dip plating steel sheet excellent in plating adhesion and method for manufacturing the same | |
JP5354600B2 (en) | High-strength galvanized DP steel sheet with excellent mechanical properties and surface quality and method for producing the same | |
JP5799819B2 (en) | Method for producing hot-dip galvanized steel sheet with excellent plating wettability and pick-up resistance | |
JPH11279691A (en) | High strength hot dip galvannealed steel sheet good in workability and its production | |
JP5842942B2 (en) | Alloyed hot-dip galvanized steel sheet with excellent plating adhesion and method for producing the same | |
JP3716718B2 (en) | Alloyed hot-dip galvanized steel sheet and manufacturing method thereof | |
JP4264373B2 (en) | Method for producing molten Al-based plated steel sheet with few plating defects | |
JPH11131145A (en) | Production of high strength and high ductility hot-dip galvanized steel sheet | |
JP4306427B2 (en) | Alloyed hot-dip galvanized steel sheet and method for producing the same | |
JP3870891B2 (en) | High strength cold-rolled steel sheet | |
JP3126911B2 (en) | High strength galvanized steel sheet with good plating adhesion | |
JP4306426B2 (en) | Hot-dip galvanized steel sheet | |
JP5594559B2 (en) | Method for producing high-tensile hot-dip galvanized steel sheet | |
JP3577930B2 (en) | High-strength, high-ductility hot-dip galvanized steel sheet and alloyed hot-dip galvanized steel sheet | |
JPH0797670A (en) | Galvanizing method for silicon-containing steel sheet | |
JP3875958B2 (en) | High strength and high ductility hot dip galvanized steel sheet with excellent workability and manufacturing method thereof | |
JP2002173714A (en) | High tensile strength hot dip plated steel sheet and its production method | |
JP3631584B2 (en) | Method for producing alloyed hot-dip galvanized steel sheet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20060921 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060929 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080205 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080407 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090414 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090427 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120515 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120515 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130515 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140515 Year of fee payment: 5 |
|
LAPS | Cancellation because of no payment of annual fees |