JP4045006B2 - Stainless steel descaling solution and method of use - Google Patents
Stainless steel descaling solution and method of use Download PDFInfo
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- JP4045006B2 JP4045006B2 JP06499598A JP6499598A JP4045006B2 JP 4045006 B2 JP4045006 B2 JP 4045006B2 JP 06499598 A JP06499598 A JP 06499598A JP 6499598 A JP6499598 A JP 6499598A JP 4045006 B2 JP4045006 B2 JP 4045006B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/086—Iron or steel solutions containing HF
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Description
【０００１】
【発明の属する技術分野】
本発明は、熱間加工の際に、あるいは熱処理の際にステンレス鋼の表面にできたスケールを除去するための処理液とその使用方法に関する。
【０００２】
【従来の技術】
ステンレス鋼のスケールを除去するためには、通常は硝酸−弗酸の酸洗液が用いられている。しかし近年、廃棄された硝酸あるいは硝酸塩は環境汚染を起こすために規制が強化される趨勢にある。
【０００３】
【発明が解決しようとする課題】
本発明は、硝酸、硝酸塩の廃棄量を十分に低減する事ができ、かつ従来よりも高能率でスケールを除去する事が可能な、ステンレス鋼のデスケール処理液とその使用方法の提供を課題としている。
【０００４】
【課題を解決するための手段】
本発明は（１）硫酸を２５〜８０ｇ／Ｌ，塩酸を１〜１０ｇ／Ｌ，弗酸を１〜１５ｇ／Ｌ含有し且つＦｅ3+を５ｇ／Ｌ以上含有する事を特徴とする、フェライト系、マルテンサイト系ステンレス鋼のデスケール用処理液である。
【０００５】
また（２）硫酸を６０〜２５０ｇ／Ｌ，塩酸を１〜２５ｇ／Ｌ，弗酸を１０〜５０ｇ／Ｌ含有し且つＦｅ3+を５ｇ／Ｌ以上含有する事を特徴とする、オーステナイト系ステンレス鋼のデスケール用処理液である。
【０００６】
また（３）３０〜７０℃の前記（１）の処理液を用いて、過酸化水素水を継続あるいは断続的に添加し、同時に空気を１０ｍ3／ｈｒ／ｍ3以上継続吹き込むことによりＦｅ3+を５ｇ／Ｌ以上に維持して、フェライト系、マルテンサイト系ステンレス鋼のデスケーリングを行うことを特徴とする、前記（１）記載のデスケール用処理液の使用方法である。
【０００７】
また（４）３０〜７０℃の前記（２）の処理液を用いて、過酸化水素水を継続あるいは断続的に添加し、同時に空気を１０ｍ3／ｈｒ／ｍ3以上継続吹き込むことによりＦｅ3+を５ｇ／Ｌ以上に維持して、オーステナイト系ステンレス鋼のデスケーリングを行うことを特徴とする、前記（２）記載のデスケール用処理液の使用方法である。
【０００８】
本発明の処理液は、単一の処理槽を用いるバッチ式デスケーリングに使用してもよいが、連続式デスケーリング装置において、２以上の処理槽のそれぞれに収納して使用してもよい。この場合、浸漬型、スプレイ型両方式に適用可能である。またソルトバスを有する連続式デスケーリングにおいても使用する事ができる。尚本発明の処理液によるデスケーリングの前段階に、必要に応じて公知の予備洗浄を行い、また後段階で必要に応じて公知のデスマット、中和、水洗等を行う事はいうまでもない。また、公知の安定化剤を用いた過酸化水素を用いて添加する。
【０００９】
【発明の実施形態及び実施例】
本発明者等は、JIS SUS430ステンレス鋼（フェライト系ステンレス鋼）の熱延線材を焼鈍後、表１に示した各処理液に５分間浸漬し、デスケーリング状況を調査した。尚表１のＦｅ3+の濃度はＦｅ2(ＳＯ4)3の添加により調整した。表１でデスケールは目視観察の結果で、×：極めて不十分、△：不十分、○：良好である。また過酸洗は酸洗肌荒れの程度を拡大鏡を用いて観察した結果で、×：肌荒れ甚だしい、△：稍肌荒れ、○：良好である。
【００１０】
【表１】
表１で番号１および２はＨＣｌ、ＨＦを含有していない比較例である。Ｆｅ3+が２ｇ／Ｌの場合も、７ｇ／Ｌの場合もデスケールは極めて不十分である。
【００１２】
番号３はＨＣｌを含有しない比較例でありデスケールは不十分である。しかし番号３にＨＣｌを２ｇ／Ｌ添加した番号４（本発明例）ではデスケール性は顕著に改善されている。また番号４には過酸洗も発生していない。尚番号４はＨＣｌが２ｇ／ＬでＨＦが５ｇ／Ｌの例であるが、それぞれが１ｇ／Ｌ以上であれば、同様に良好な結果が得られる。また番号４はＨ2ＳＯ4が３０ｇ／Ｌの例であるが、２５ｇ／Ｌ以上であれば同様に良好な結果が得られる。
【００１３】
番号５はＦｅ3+が少ない比較例である。デスケールは良好であるが、過酸洗に起因する肌荒れがみられる。
【００１４】
番号６は比較例で、Ｈ2ＳＯ4及びＨＦは高濃度に含有するが、ＨＣｌを含有していない。この際はデスケールが不十分である。
【００１５】
番号７は番号６にＨＣｌを含有させた処理液で、Ｈ2ＳＯ4，ＨＣｌ，ＨＦの何れもが高濃度の本発明の処理液であるが、デスケールも良好で肌荒れもない。番号８はＦｅ3+濃度が低い比較例であるが、Ｆｅ3+の濃度が５ｇ／Ｌ以下になると肌荒れが発生する。
【００１６】
番号９はＨＣｌの濃度が１０ｇ／Ｌ超の高過ぎる比較例で、Ｎｏ１０はＨＦの濃度が１５ｇ／Ｌ超の高過ぎる比較例である。何れもデスケール性は良好であるが、本発明よりも濃度が高い場合には過酸洗が発生する。尚Ｈ2ＳＯ4の濃度が８０ｇ／Ｌを超えても格別の支障はないが、格別の効果もない。このため８０ｇ／Ｌ以下が経済的に好ましい。
【００１７】
これ等の結果に基づいて、本発明では硫酸：２５〜８０ｇ／Ｌ，塩酸：１〜１０ｇ／Ｌ，弗酸：１０〜１５ｇ／Ｌ，Ｆｅ3+：５ｇ／Ｌ以上とする。本発明の処理液を用いると、５分以内の短時間で、過酸洗を発生させる事なく、フェライト系ステンレス鋼をデスケール処理する事ができる。尚本発明者等は JIS 403ステンレス鋼（マルテンサイト系ステンレス鋼）についても同様のデスケール試験を行ったが、本発明の処理液を用いると、この際にも、５分以内の短時間で、過酸洗を発生させることなくデスケール処理することができた。
【００１８】
硝酸−弗酸系の従来の処理液を用いた場合は、フェライト系ステンレス鋼マルテンサイト系ステンレス鋼のデスケールは、５分の浸漬では不十分であり、このため、操業としては１０分間の浸漬が行われていた。本発明によると上記の如くこの浸漬時間を５分間に短縮する事ができた。
【００１９】
本発明の処理液は、３０〜７０℃にして用いる事が好ましい。３０℃未満では作業条件によりデスケール結果に変動が発生し易い。しかし７０℃以下で十分であり、これ以上の高温加熱は、熱経済的に好ましくない。
【００２０】
本発明でＦｅ3+は、ステンレス鋼のマトリックスと反応しＦｅ2+となるために、処理中にその濃度が低減する。過酸化水素水を継続添加すると、Ｆｅ2+は酸化されてＦｅ3+の濃度を維持する事ができる。この際には処理液の酸化還元電位を＋２５０ｍＶ以上とする量添加する事が好ましい。また処理液に空気を吹き込むと、Ｆｅ2+は酸化されてＦｅ3+の濃度を維持する事ができる。この際には継続して１０ｍ3／ｈｒ／ｍ3以上の割合で吹き込む事が好ましい。
【００２１】
本発明者等はまた、JIS SUS 304 ステンレス鋼（オーステナイト系ステンレス鋼）の熱延線材を溶体化熱処理後、表２に示した各処理液に５分間浸漬し、デスケーリング状況を調査した。尚Ｆｅ3+の濃度の調整、デスケールの評価基準、過酸洗の評価基準は表１と同じである。
【００２２】
【表２】
番号１１はＨＣｌを含有しない比較例でデスケールが極めて不十分である。ＨＣｌを５％含有する番号１２はデスケールは十分であるが、Ｆｅ3+が少ないために過酸洗となる。
【００２４】
番号１３は、本発明例でデスケールも十分で過酸洗もない。尚Ｈ2ＳＯ4は６０ｇ／Ｌ以上であれば、またＨＣｌは１ｇ／Ｌ以上であれば、またＨＦは１０ｇ／Ｌ以上であれば、またＦｅ3+は５ｇ／Ｌ以上であれば、番号１３と同様の好ましい結果が得られる。
【００２５】
番号１４は比較例で、Ｈ2ＳＯ4及びＨＦは高濃度に含有するが、ＨＣｌを含有していない。この際はデスケールが不十分となる。
【００２６】
番号１５は番号１４にＨＣｌを含有させた処理液で、Ｈ2ＳＯ4，ＨＣｌ，ＨＦの何れもが高濃度の本発明の処理液であるが、デスケールも良好で肌荒れもない。番号１６はＦｅ3+が少ない比較例であるが、Ｆｅ3+が５ｇ／Ｌ未満となると過酸洗が発生する。
【００２７】
番号１７はＨＦが過剰な比較例で、番号１８はＨＣｌが過剰な比較例であるが、何れの場合にも顕著な肌荒れが観察された。
【００２８】
尚Ｈ2ＳＯ4の濃度が２５０ｇ／Ｌを超えても格別の支障はないが、格別の効果もない。このため２５０ｇ／Ｌ以下が経済的に好ましい。
【００２９】
これ等の結果に基づいて、本発明では、硫酸：６０〜２５０ｇ／Ｌ，塩酸：１〜２５ｇ／Ｌ，弗酸：１０〜１５ｇ／Ｌ，Ｆｅ3+：５ｇ／Ｌ以上とする。本発明の処理液を用いると、５分以内の短時間内で、過酸洗を発生させることなく、オーステナイト系ステンレス鋼をデスケール処理する事ができる。
【００３０】
硝酸−弗酸系の従来の処理液を用いた場合は、オーステナイト系ステンレス鋼のデスケールは、５分間の浸漬では不十分であり、このため操業としては１０分間の浸漬が行われていた。本発明によると、上記の如く、この浸漬時間を５分間に短縮する事ができた。
【００３１】
表２の本発明の処理液も、表１で述べたと同様に、３０〜７０℃にして用いる事が好ましく、また表１で述べたと同じ理由で処理中には過酸化水素水を処理液の酸化還元電位が＋２５０ｍＶとなる量継続添加し、あるいは空気を１０ｍ3／ｈｒ／ｍ3以上継続して吹き込む事が好ましい。
【００３２】
本発明では短時間内にデスケールができるが、これは本発明の処理液中の塩酸が、高温時にステンレス鋼の表面に形成されたクロム欠乏層の優先的な溶失に大きく寄与したことによるものと想考される。また本発明では過酸洗が発生しないが、これは、本発明の処理液中のＦｅ3+が、クロム欠乏層が溶失した後のステンレス鋼の表面の溶失の防止に寄与したことによるものと想考される。
【００３３】
【発明の効果】
本発明では、硝酸を使用しないために、硝酸あるいは硝酸塩の廃棄による環境汚染を防止する事ができる。本発明によると従来よりも高能率でスケールを除去する事ができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a treatment liquid for removing scale formed on the surface of stainless steel during hot working or heat treatment, and a method for using the same.
[0002]
[Prior art]
In order to remove the stainless steel scale, a pickling solution of nitric acid-hydrofluoric acid is usually used. In recent years, however, discarded nitric acid or nitrates have been in a tendency to be tightened in order to cause environmental pollution.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a stainless steel descaling solution capable of sufficiently reducing the amount of nitric acid and nitrate discarded, and capable of removing scales more efficiently than before, and a method for using the same. Yes.
[0004]
[Means for Solving the Problems]
The present invention is (1) a ferrite containing 25 to 80 g / L of sulfuric acid, 1 to 10 g / L of hydrochloric acid, 1 to 15 g / L of hydrofluoric acid, and 5 g / L or more of Fe 3+ It is a processing solution for descaling of martensitic stainless steel.
[0005]
(2) Austenitic stainless steel characterized by containing 60 to 250 g / L sulfuric acid, 1 to 25 g / L hydrochloric acid, 10 to 50 g / L hydrofluoric acid, and 5 g / L or more Fe 3+. This is a processing solution for steel descaling.
[0006]
(3) Using the treatment solution of (1) at 30 to 70 ° C., hydrogen peroxide solution is continuously or intermittently added, and at the same time, air is continuously blown in at least 10 m 3 / hr / m 3 to obtain Fe 3. The method for using the descaling treatment liquid according to (1) above, wherein descaling of ferritic and martensitic stainless steel is performed while maintaining + at 5 g / L or more.
[0007]
(4) Using the treatment solution of (2) at 30 to 70 ° C., hydrogen peroxide solution is continuously or intermittently added, and at the same time, air is continuously blown in at least 10 m 3 / hr / m 3 to thereby reduce Fe 3. The method for using the descaling treatment liquid according to (2) above, wherein descaling of austenitic stainless steel is performed while maintaining + at 5 g / L or more.
[0008]
The treatment liquid of the present invention may be used for batch-type descaling using a single treatment tank, but may be used in each of two or more treatment tanks in a continuous descaling apparatus. In this case, it is applicable to both immersion type and spray type. It can also be used in continuous descaling with a salt bath. Needless to say, prior to the descaling with the treatment liquid of the present invention, a known preliminary cleaning is performed as necessary, and a known desmut, neutralization, water washing, etc. are performed at a later stage as necessary. . Further, hydrogen peroxide using a known stabilizer is added.
[0009]
Embodiments and Examples of the Invention
The inventors investigated the descaling situation by annealing a hot-rolled wire of JIS SUS430 stainless steel (ferritic stainless steel) for 5 minutes in each treatment solution shown in Table 1. The concentration of Fe 3+ in Table 1 was adjusted by adding Fe 2 (SO 4 ) 3 . In Table 1, descale is the result of visual observation, x: extremely insufficient, Δ: insufficient, ○: good. Further, peracid washing is a result of observing the degree of roughening of pickled skin with a magnifying glass. ×: Extremely rough skin, Δ: Rough rough skin, ○: Good.
[0010]
[Table 1]
In Table 1, numbers 1 and 2 are comparative examples containing no HCl or HF. When Fe 3+ is 2 g / L and 7 g / L, descaling is extremely insufficient.
[0012]
No. 3 is a comparative example that does not contain HCl, and descaling is insufficient. However, in No. 4 (invention example) in which 2 g / L of HCl is added to No. 3, the descalability is remarkably improved. In No. 4, no peracid washing occurred. The number 4 is an example in which HCl is 2 g / L and HF is 5 g / L. If each of them is 1 g / L or more, the same good results can be obtained. In addition, No. 4 is an example in which H 2 SO 4 is 30 g / L, but if it is 25 g / L or more, good results can be obtained similarly.
[0013]
No. 5 is a comparative example with less Fe 3+ . Although descaling is good, rough skin due to peracid washing is observed.
[0014]
No. 6 is a comparative example, and H 2 SO 4 and HF are contained in a high concentration, but HCl is not contained. At this time, descaling is insufficient.
[0015]
No. 7 is a treatment liquid containing HCl in No. 6, and all of H 2 SO 4 , HCl, and HF are the treatment liquids of the present invention, but the descaling is good and the skin is not rough. No. 8 is a comparative example in which the Fe 3+ concentration is low, but rough skin occurs when the Fe 3+ concentration is 5 g / L or less.
[0016]
No. 9 is a comparative example in which the HCl concentration is too high, exceeding 10 g / L, and No. 10 is a comparative example in which the HF concentration is too high, exceeding 15 g / L. In all cases, the descaling property is good, but when the concentration is higher than that of the present invention, peracid washing occurs. Even if the concentration of H 2 SO 4 exceeds 80 g / L, there is no particular problem, but there is no particular effect. For this reason, 80 g / L or less is economically preferable.
[0017]
Based on these results, in the present invention, sulfuric acid: 25-80 g / L, hydrochloric acid: 1-10 g / L, hydrofluoric acid: 10-15 g / L, Fe 3+ : 5 g / L or more. When the treatment liquid of the present invention is used, the ferritic stainless steel can be descaled in a short time of 5 minutes or less without causing peracid washing. In addition, although the present inventors performed the same descale test also about JIS 403 stainless steel (martensitic stainless steel), when using the process liquid of this invention, in this case also in a short time within 5 minutes, The descaling process could be performed without causing per pickling.
[0018]
When using nitric acid-hydrofluoric acid-based conventional treatment liquid, the descaling of ferritic stainless steel and martensitic stainless steel is not sufficient when immersed for 5 minutes. It was done. According to the present invention, as described above, this immersion time could be shortened to 5 minutes.
[0019]
The treatment liquid of the present invention is preferably used at 30 to 70 ° C. If it is less than 30 ° C., the descaling result is likely to vary depending on the working conditions. However, 70 ° C. or lower is sufficient, and heating at a higher temperature is not preferable in terms of thermoeconomics.
[0020]
In the present invention, Fe 3+ reacts with the stainless steel matrix to become Fe 2+ , so its concentration decreases during processing. When hydrogen peroxide solution is continuously added, Fe 2+ is oxidized and the concentration of Fe 3+ can be maintained. In this case, it is preferable to add in an amount such that the oxidation-reduction potential of the treatment liquid is +250 mV or more. When air is blown into the treatment liquid, Fe 2+ is oxidized and the concentration of Fe 3+ can be maintained. In this case, it is preferable to continuously blow in at a rate of 10 m 3 / hr / m 3 or more.
[0021]
The present inventors also investigated the descaling situation by immersing a hot-rolled wire of JIS SUS 304 stainless steel (austenitic stainless steel) in each treatment solution shown in Table 2 for 5 minutes after solution heat treatment. The adjustment of Fe 3+ concentration, descale evaluation criteria, and peracid wash evaluation criteria are the same as in Table 1.
[0022]
[Table 2]
No. 11 is a comparative example that does not contain HCl, and the descaling is extremely insufficient. No. 12 containing 5% HCl is sufficient for descaling, but is peracid washed because Fe 3+ is low.
[0024]
No. 13 is an example of the present invention, and descaling is sufficient and there is no peracid washing. If H 2 SO 4 is 60 g / L or more, HCl is 1 g / L or more, HF is 10 g / L or more, and Fe 3+ is 5 g / L or more, the number Preferred results similar to 13 are obtained.
[0025]
No. 14 is a comparative example, and H 2 SO 4 and HF are contained at a high concentration, but HCl is not contained. At this time, descaling is insufficient.
[0026]
No. 15 is a treatment liquid containing HCl in No. 14, and all of H 2 SO 4 , HCl, and HF are the treatment liquids of the present invention having high concentration, but the descaling is good and the skin is not rough. No. 16 is a comparative example with a small amount of Fe 3+, but when the Fe 3+ is less than 5 g / L, peracid washing occurs.
[0027]
No. 17 is a comparative example in which HF is excessive, and No. 18 is a comparative example in which HCl is excessive. In each case, remarkable skin roughness was observed.
[0028]
Even if the concentration of H 2 SO 4 exceeds 250 g / L, there is no particular problem, but there is no particular effect. For this reason, 250 g / L or less is economically preferable.
[0029]
Based on these results, in the present invention, sulfuric acid: 60 to 250 g / L, hydrochloric acid: 1 to 25 g / L, hydrofluoric acid: 10 to 15 g / L, Fe 3+ : 5 g / L or more. When the treatment liquid of the present invention is used, the austenitic stainless steel can be descaled within a short time of 5 minutes or less without causing peracid washing.
[0030]
When a nitric acid-hydrofluoric acid-based conventional processing solution is used, the austenitic stainless steel is not sufficiently descaled for 5 minutes, so that the operation has been performed for 10 minutes. According to the present invention, as described above, this immersion time could be shortened to 5 minutes.
[0031]
The treatment liquid of the present invention in Table 2 is also preferably used at a temperature of 30 to 70 ° C. as described in Table 1, and for the same reason as described in Table 1, hydrogen peroxide water is used during the treatment. It is preferable to continuously add an amount such that the oxidation-reduction potential becomes +250 mV or to blow air continuously for 10 m 3 / hr / m 3 or more.
[0032]
In the present invention, the descaling can be performed within a short time because the hydrochloric acid in the treatment liquid of the present invention greatly contributed to the preferential erosion of the chromium-deficient layer formed on the surface of the stainless steel at a high temperature. It is thought. In the present invention, peracid washing does not occur, but this is because Fe 3+ in the treatment liquid of the present invention contributed to prevention of loss of the surface of the stainless steel after the chromium-deficient layer was lost. It is considered a thing.
[0033]
【The invention's effect】
In the present invention, since no nitric acid is used, environmental pollution due to disposal of nitric acid or nitrate can be prevented. According to the present invention, scale can be removed with higher efficiency than in the past.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06499598A JP4045006B2 (en) | 1998-03-16 | 1998-03-16 | Stainless steel descaling solution and method of use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06499598A JP4045006B2 (en) | 1998-03-16 | 1998-03-16 | Stainless steel descaling solution and method of use |
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| Publication Number | Publication Date |
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| JPH11264087A JPH11264087A (en) | 1999-09-28 |
| JP4045006B2 true JP4045006B2 (en) | 2008-02-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP06499598A Expired - Lifetime JP4045006B2 (en) | 1998-03-16 | 1998-03-16 | Stainless steel descaling solution and method of use |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003089900A (en) * | 2001-09-17 | 2003-03-28 | Daido Steel Co Ltd | Method of descaling metallic strip |
| DE10160318A1 (en) * | 2001-12-07 | 2003-06-18 | Henkel Kgaa | Process for pickling martensitic or ferritic stainless steel |
| ATE478975T1 (en) * | 2002-10-15 | 2010-09-15 | Henkel Ag & Co Kgaa | SOLUTION AND METHOD FOR PICKLING STAINLESS STEEL |
| US20050037935A1 (en) | 2003-08-11 | 2005-02-17 | Abd Elhamid Mahmoud H. | Composition and method for surface treatment of oxidized metal |
| JP4514032B2 (en) * | 2004-06-10 | 2010-07-28 | 新日鐵住金ステンレス株式会社 | Method for producing ferritic stainless steel strip with good paint adhesion |
| EP1980650A1 (en) * | 2007-04-05 | 2008-10-15 | Kerma S.A. | Pickling composition free from nitrates and peroxides, and method using such a composition |
| CN102912369A (en) * | 2012-11-08 | 2013-02-06 | 安徽昌泰特钢有限公司 | Automatic acid-washing process for steel tubes |
| CN103820777A (en) * | 2013-12-16 | 2014-05-28 | 攀钢集团江油长城特殊钢有限公司 | Stainless steel passivating method and used mixed solution |
| CN104018166A (en) * | 2014-06-13 | 2014-09-03 | 中国船舶重工集团公司第七二五研究所 | In-service austenitic stainless steel cleaning passivator in marine environment |
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1998
- 1998-03-16 JP JP06499598A patent/JP4045006B2/en not_active Expired - Lifetime
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| JPH11264087A (en) | 1999-09-28 |
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