EP2676746B1 - Method for straightening - Google Patents
Method for straightening Download PDFInfo
- Publication number
- EP2676746B1 EP2676746B1 EP12747318.9A EP12747318A EP2676746B1 EP 2676746 B1 EP2676746 B1 EP 2676746B1 EP 12747318 A EP12747318 A EP 12747318A EP 2676746 B1 EP2676746 B1 EP 2676746B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- straightening
- roll
- rolls
- hard alloy
- wear
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 56
- 229910045601 alloy Inorganic materials 0.000 claims description 65
- 239000000956 alloy Substances 0.000 claims description 65
- 229910000831 Steel Inorganic materials 0.000 claims description 35
- 239000010959 steel Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 description 11
- 229910001315 Tool steel Inorganic materials 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- 238000005336 cracking Methods 0.000 description 8
- 238000007730 finishing process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 230000002950 deficient Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 5
- 229910009043 WC-Co Inorganic materials 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 101000803685 Homo sapiens Vacuolar protein sorting-associated protein 4A Proteins 0.000 description 1
- 101000803689 Homo sapiens Vacuolar protein sorting-associated protein 4B Proteins 0.000 description 1
- 238000007550 Rockwell hardness test Methods 0.000 description 1
- 102100035085 Vacuolar protein sorting-associated protein 4A Human genes 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B23/00—Tube-rolling not restricted to methods provided for in only one of groups B21B17/00, B21B19/00, B21B21/00, e.g. combined processes planetary tube rolling, auxiliary arrangements, e.g. lubricating, special tube blanks, continuous casting combined with tube rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D3/00—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts
- B21D3/02—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts by rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D3/00—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts
- B21D3/02—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts by rollers
- B21D3/04—Straightening or restoring form of metal rods, metal tubes, metal profiles, or specific articles made therefrom, whether or not in combination with sheet metal parts by rollers arranged on axes skew to the path of the work
Definitions
- the present invention relates to a method for straightening a steel pipe or bar. More particularly, the present invention relates to a method for straightening, in which the wear of a roll of a straightening machine is suppressed, concavity and convexity of roll surface caused by the wear are prevented from being transferred to the steel product, and time for changeover and/or setup of rolls can be shortened to improve the efficiency of a finishing process.
- Hard alloy straightening roll a straightening roll made of a tungsten carbide-cobalt (WC-Co) based sintered material (hard alloy). Also referred simply to as a “hard alloy roll”.
- Hardness The hardness of a roll or a product to be straightened is represented by Rockwell hardness (scale A) measured by the Rockwell hardness test specified in JIS Z 2245, and is expressed, for example, as "HRA86".
- a steel product such as a pipe or bar is produced through a hot or cold working process, and bends of the steel product are generated during such processing stages and/or during heat treatment that is carried out midway through such processing stages. These bends are straightened, in a finishing process, usually by using a straightening machine that uses specific rolls, such as a cross roll type straightening machine (straightener) in which a plurality of concave globoidal drum type rolls are arranged .
- a cross roll type straightening machine straightener
- Patent Literature 1 discloses a method in which, to prevent stress corrosion cracking in a product on account of residual stress occurring at the time of straightening, a pipe is straightened while an amount of crush required in pipe straightening is controlled in such a manner that the occurrence of excessive residual stress is avoided.
- Patent Literature 1 does not describe the suppression of roll wear, so that the method described in this Literature cannot be a solution for the above-described problems.
- Patent Literature 2 discloses a method for straightening bends of a steel pipe, in which the bends are removed by moving the steel pipe forward while an enforced deflection is given to the steel pipe by sets of offset rolls, wherein the direction of offset for all sets of offset rolls can be reversed every time when a predetermined number of pipes are straightened.
- a method and a device for manufacturing a tube are described in JP 2005/103557 , wherein straightening rolls alternately press the side of the curved center side.
- JP 2004/136296 a composite rolling roll is described.
- the present invention has been made to solve such problems, and accordingly an objective thereof is to provide a method for straightening, in which when bends of a steel pipe or bar, especially when bends of a high-strength product such as a steel pipe for a motor vehicle air bag, are straightened by means of a straightening machine using rolls such as a straightener, roll wear is suppressed, the concavity and convexity of roll surface caused by the roll wear are prevented from being transferred to a product being straightened and a defective roll mark(s) is prevented from being formed, and time for changeover and/or setup of rolls can be reduced to improve the efficiency in a finishing process and, in turn, the productivity.
- the "method for straightening in which rolls are used” as used herein is a straightening method using a roll-type straightening machine that includes upper and lower rolls as being arranged above and below the product to be straightened and that is used to straighten bends while the product to be straightened is moved forward, and is usually a straightening method using a cross roll type straightening machine (straightener).
- the "steel product” is a pipe or bar the bends of which can be straightened by this method for straightening regardless of material grade.
- the method for straightening in accordance with the present invention is a straightening method using hard alloy straightening rolls each having a hardness of HRA85 to 87. According to this method, when bends of a pipe or bar are straightened by using rolls of a straightener or the like, roll wear is suppressed, a defective roll mark(s) attributable to the roll wear is prevented from being formed on the surface of a product being straightened, and time for changeover and/or setup of rolls is shortened to enhance the operation rate of the straightening machine, whereby the efficiency of a finishing process and, in turn, the productivity can be improved.
- the present inventors made an attempt to suppress roll wear by optimizing the material grade of roll, and tried to use a WC-Co based sintered material as a material grade of roll.
- the WC-Co based sintered material is a composite material in which Co is added as a binder to the fine powder of WC to form a sintered material, and is called hard alloy. Because of having high hardness and excellent wear resistance, the WC-Co based sintered material is frequently used as a starting material especially for a cutting tool.
- the wear resistance and heat crack resistance of this hard alloy were examined. As a result, the present inventors have confirmed that the hard alloy has wear resistance that is about 100 times that of a tool steel (SKD1: 2.1C-12Cr specified in JIS G 4404, hereinafter, referred simply to as "SKD") having been used conventionally as a starting material for a roll. Also, it has been found that the hard alloy has heat crack resistance (evaluated by the number of repetitions before crack generation as a result of repetition of heating-water cooling) sufficiently applicable for a roll as a starting material.
- SKD1 tool steel
- JIS G 4404 JIS G 4404
- the present invention has been made based on the above-described findings, and as described above, provides a method for straightening a steel pipe or bar the method comprising using hard alloy straightening rolls, wherein the hardness of each rolls is HRA85 to 87.
- the hard alloy which is a composite material of ceramics and metals, is hard and excellent in wear resistance, and also has heat crack resistance, so that the hard alloy is suitable as a starting material for a roll. That is, hardness, wear resistance, and heat resistance (withstanding heat generation at the time of straightening using rolls) are necessary for the material of straightener roll, and the hard alloy is excellent in all of such properties.
- the reason why the hardness of the straightening roll is controlled to be in the range of HRA85 to 87 in the present invention is that both of the wear resistance and heat resistance can be high owing to the controlled hardness. If the roll hardness is less than HRA85, the difference in hardness between the product to be straightened and the rolls becomes small, and the wear resistance becomes insufficient. Above the roll hardness of HRA87, although the wear resistance increases, the heat resistance decreases, and the tendency of degradation of the heat crack resistance appears.
- the method for straightening in accordance with the present invention is especially effective in the case where a product to be straightened is a steel pipe for a motor vehicle air bag.
- the steel pipe for a motor vehicle air bag is made of a high-strength steel having tensile strength of approximately 800 to 1100 MPa. In the case where the tensile strength is 1100 MPa, the corresponding hardness is about HRA68.5.
- a steel pipe for the air bag having high strength and high hardness are straightened, if rolls each made of an ordinary tool steel (SKD, for example, SKD11: 1.5C-12Cr-1.0Mo, etc.) are used, roll wear is liable to occur, and defective roll mark(s) is formed on the surface of the product being straightened.
- an ordinary tool steel for example, SKD11: 1.5C-12Cr-1.0Mo, etc.
- the method for straightening in accordance with the present invention comprising using the hard alloy straightening rolls, is applied, as described in the after-described Examples, the roll wear is substantially perfectly suppressed, the surface roughness does not exhibit any significant change (that is, the formation of defective roll mark(s) is not discernible), and time for changeover and/or setup of rolls is shortened.
- the wear resistance and heat crack resistance thereof were examined.
- the same examination was performed on the tool steel SKD (used after being subjected to sub-zero treatment), which is the conventional starting material for a roll.
- Table 1 shows material grades and characteristics of test specimens.
- the "grain size” is the grain size in hard alloy.
- hard alloys A, B and C are materials in which amounts of addition of Co to WC are about 15%, 16% and 17% (all: mass-percent), respectively. With the increase in addition amount of Co, the hardness varies from HRA88.0 to HRA85.0.
- FIG. 1 is an explanatory view for a method for evaluating the wear resistance of a starting material for a roll.
- a ball 1 material grade: SUJ, diameter: 15 mm
- an amount of wear wear (wear volume) of the test specimen 2 by the test was measured.
- FIG. 2 is a diagram showing the examination result of wear resistance.
- the specific wear amount of any of hard alloys A, B and C was remarkably small, being one-hundredth or less of the case of the tool steel SKD. It is convinced that any of hard alloys has wear resistance of about 100 times that of the conventional roll material. Also, in comparison among hard alloys A, B and C, for the hardest hard alloy A having a hardness of HRA88.0, the specific wear amount was small, so that the wear resistance was the most excellent.
- the heat crack resistance of the hard alloy was evaluated as described below.
- a test specimen was subjected to a repetition test process of "heating (700°C)" ⁇ "water cooling”, and evaluation was done by the number of repetitions before cracking is generated on the test specimen. The larger the number of repetitions is, the more excellent the heat crack resistance is.
- Table 2 gives the evaluation result of heat crack resistance.
- mark ⁇ indicates that the generation of cracking was not discerned, and mark ⁇ indicates that cracking was generated. The presence or absence of crack generation was judged by visual observation.
- Table 3 gives the result of comprehensive evaluation of wear resistance, heat crack resistance, and hardness for hard alloys A, B and C. Since any of hard alloys exhibited a good wear resistance, all of them were to be rated as " ⁇ " (good). In particular, the case where the specific wear resistance was less than 100 ⁇ 10 -12 mm2/N (hard alloy A) was rated to be " " (superior) (refer to FIG. 2 ).
- hard alloy A (hardness: HRA88.0) was the hardest among the alloys subjected to examination and had excellent wear resistance, but had poorer heat crack resistance than those of hard alloys B and C, so that, in the comprehensive evaluation, hard alloy A was rated to be " ⁇ " (fair) (the heat crack resistance was relatively poor).
- the hard alloys that are used as a starting material for the hard alloy roll to be used in the method for straightening in accordance with the present invention are very high in wear resistance, and the hardness of hard alloy is preferably controlled within the range of HRA85 to 87.
- the method for straightening in accordance with the present invention was applied for the straightening of a steel pipe using a straightener to examine an amount of wear and the surface roughness of the roll and to check how much a required time for changeover and/or setup of rolls was shortened at the time that a steel pipe for a motor vehicle air bag was straightened. For comparison, the same examination was performed for the case where the conventional rolls (material grade: tool steel SKD11) were used.
- Table 4 summarizedly gives the characteristics of the straightener roll material grades used in the examinations.
- the material grade of the hard alloy roll used in the method for straightening in accordance with the present invention is hard alloy B used in Example 1.
- FIG. 3 is a schematic view showing an outline configuration of a straightener used for the straightening of a steel pipe for an air bag and the positions at which the hard alloy rolls were arranged.
- the straightener was of a 2-2-2-1 type.
- hard alloy rolls were applied (in FIG. 3 , relevant rolls are indicated by hatched line), and for Position #1 rolls as being guide rolls and the final Position #4 roll, conventional SKD11-made rolls were used.
- the dimensions of roll were 190 mm in roll mid-length (minimum) diameter and 180 mm in roll width.
- a steel pipe to be straightened was a pipe having an outside diameter of 15.90 to 42.7 mm.
- Table 5 summarizedly gives the rolls on which an amount of wear and the surface roughness were measured, the measurement locations, and the measurement methods.
- Table 5 Amount of wear Surface roughness Target roll for measurement Position #2 lower roll (roll to which highest load is applied by offset) Measurement location Mid-length (minimum diameter) portion of roll Measurement method Measured with vernier calipers Resin impression of roll surface is formed, and concavity and convexity (roughness) transferred to resin impression is measured with stylus-type surface roughness measuring instrument.
- FIG. 4 is a diagram showing the examination result of an amount of wear of a roll at a time when the method for straightening in accordance with the present invention is applied, comparing with the case where the conventional rolls are used.
- the vertical axis of FIG. 4 represents wear rate (mm/km) obtained by dividing the amount of wear (amount of decrease in diameter caused by wear: mm) by the cumulative length (km) subjected to straightening.
- the wear rate at the time that the roll was used up until the conventional roll life expires was 1.6 ⁇ 10 -3 mm/km.
- the method for straightening in accordance with the present invention the method comprising using the hard alloy rolls, is applied, even after the cumulative straightening length had reached 4300 km (1.7 times the conventional roll life), the wear rate was 0 mm/km, and wear was not discerned at all.
- FIG. 5 is a diagram showing the examination result of the surface roughness of a roll at the time that the method for straightening in accordance with the present invention is applied.
- the surface roughness is represented by maximum height (Rz).
- FIG. 6 is a diagram showing the required time for changeover and/or setup of rolls at a time when a steel pipe for an air bag (outside diameter: 25 mm) is straightened by applying the method for straightening in accordance with the present invention, comparing with the case where the conventional rolls are used.
- FIG. 7 is a diagram showing operation rates of a straightener at a time when steel pipes for an air bag (outside diameter: 20 mm, 25 mm or 30 mm) are straightened by applying the method for straightening in accordance with the present invention, comparing with the case where the conventional rolls are used.
- the method for straightening in accordance with the present invention can be used effectively for straightening a bend occurring on a pipe or bar, especially for straightening a bend of a high-strength product such as a steel pipe for a motor vehicle air bag.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Bending Of Plates, Rods, And Pipes (AREA)
- Powder Metallurgy (AREA)
- Pistons, Piston Rings, And Cylinders (AREA)
- Heat Treatment Of Articles (AREA)
- Reduction Rolling/Reduction Stand/Operation Of Reduction Machine (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011028905A JP5462202B2 (ja) | 2011-02-14 | 2011-02-14 | 曲がり矯正方法 |
PCT/JP2012/000896 WO2012111291A1 (ja) | 2011-02-14 | 2012-02-10 | 曲がり矯正方法 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2676746A1 EP2676746A1 (en) | 2013-12-25 |
EP2676746A4 EP2676746A4 (en) | 2016-09-07 |
EP2676746B1 true EP2676746B1 (en) | 2018-10-24 |
Family
ID=46672238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12747318.9A Active EP2676746B1 (en) | 2011-02-14 | 2012-02-10 | Method for straightening |
Country Status (9)
Country | Link |
---|---|
US (1) | US20130327110A1 (ja) |
EP (1) | EP2676746B1 (ja) |
JP (1) | JP5462202B2 (ja) |
KR (1) | KR20130118960A (ja) |
CN (1) | CN103370149A (ja) |
BR (1) | BR112013017469B8 (ja) |
MX (1) | MX363214B (ja) |
TW (1) | TWI538751B (ja) |
WO (1) | WO2012111291A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103691774A (zh) * | 2013-12-20 | 2014-04-02 | 鞍钢股份有限公司 | 一种无缝管的矫直方法 |
KR102059036B1 (ko) | 2018-09-12 | 2019-12-24 | 김덕현 | 강재 휨 변형 교정방법 및 장치 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55128318A (en) | 1979-03-29 | 1980-10-04 | Sumitomo Metal Ind Ltd | Straightening method of pipe |
US4756180A (en) * | 1984-09-07 | 1988-07-12 | Sumitomo Electric Industries, Ltd. | Method of hot rolling for iron and iron alloy rods |
JPH0847722A (ja) | 1994-08-08 | 1996-02-20 | Nippon Steel Corp | 鋼管用曲がり矯正方法及び装置 |
JP2004136296A (ja) * | 2002-10-15 | 2004-05-13 | Hitachi Metals Ltd | 圧延用複合ロール |
JP2004195515A (ja) * | 2002-12-19 | 2004-07-15 | Jfe Steel Kk | ステンレス鋼の熱間圧延方法 |
JP2005103557A (ja) * | 2003-09-26 | 2005-04-21 | Kobe Steel Ltd | 内面溝付管の製造装置及び内面溝付管の製造方法 |
WO2007119817A1 (ja) * | 2006-04-14 | 2007-10-25 | Sumitomo Metal Industries, Ltd. | 管の矯正方法およびその矯正方法を用いた管の製造方法 |
CN101522930B (zh) * | 2006-10-25 | 2012-07-18 | Tdy工业公司 | 具有改进的抗热开裂性的制品 |
JP2008173643A (ja) * | 2007-01-16 | 2008-07-31 | Sumitomo Metal Ind Ltd | 二相ステンレス鋼管の製造方法、矯正方法および強度調整方法、ならびに、二相ステンレス鋼管の矯正機の操業方法 |
DE112007003349A5 (de) * | 2007-02-20 | 2010-04-15 | Siemens Aktiengesellschaft | Walze und/oder Rolle sowie ein Verfahren zur Herstellung einer Walze und/oder Rolle |
JP4770922B2 (ja) * | 2008-12-08 | 2011-09-14 | 住友金属工業株式会社 | エアバッグ用鋼管とその製造方法 |
CN101507990A (zh) * | 2009-03-25 | 2009-08-19 | 江苏诚德钢管股份有限公司 | 一种端部加厚钢管的矫直方法 |
CN101927278B (zh) * | 2010-06-03 | 2012-11-07 | 天津商业大学 | 采用六辊矫直机实现薄壁无缝钢管精密矫直的方法 |
-
2011
- 2011-02-14 JP JP2011028905A patent/JP5462202B2/ja active Active
-
2012
- 2012-02-10 WO PCT/JP2012/000896 patent/WO2012111291A1/ja active Application Filing
- 2012-02-10 BR BR112013017469A patent/BR112013017469B8/pt active IP Right Grant
- 2012-02-10 EP EP12747318.9A patent/EP2676746B1/en active Active
- 2012-02-10 CN CN2012800089207A patent/CN103370149A/zh active Pending
- 2012-02-10 KR KR1020137021946A patent/KR20130118960A/ko not_active Application Discontinuation
- 2012-02-10 US US13/985,296 patent/US20130327110A1/en not_active Abandoned
- 2012-02-10 MX MX2013008855A patent/MX363214B/es unknown
- 2012-02-14 TW TW101104718A patent/TWI538751B/zh active
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
KR20130118960A (ko) | 2013-10-30 |
JP5462202B2 (ja) | 2014-04-02 |
MX2013008855A (es) | 2013-08-14 |
BR112013017469B1 (pt) | 2020-06-16 |
TWI538751B (zh) | 2016-06-21 |
CN103370149A (zh) | 2013-10-23 |
BR112013017469B8 (pt) | 2020-09-29 |
JP2012166233A (ja) | 2012-09-06 |
EP2676746A1 (en) | 2013-12-25 |
WO2012111291A1 (ja) | 2012-08-23 |
EP2676746A4 (en) | 2016-09-07 |
TW201302337A (zh) | 2013-01-16 |
MX363214B (es) | 2019-03-15 |
BR112013017469A2 (ja) | 2018-09-04 |
US20130327110A1 (en) | 2013-12-12 |
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