High carbon hot rolled steel sheet and method for manufacturing the same

Information

  • Patent Grant
  • 10077491
  • Patent Number
    10,077,491
  • Date Filed
    Wednesday, December 26, 2012
    11 years ago
  • Date Issued
    Tuesday, September 18, 2018
    6 years ago
Abstract
A high carbon hot rolled steel sheet and a method for manufacturing the same are provided, wherein excellent cold workability and excellent hardenability are obtained stably. The high carbon hot rolled steel sheet has a composition containing C: 0.20% to 0.48%, Si: 0.1% or less, Mn: 0.5% or less, P: 0.03% or less, S: 0.01% or less, sol. Al: more than 0.10% and 1.0% or less, N: 0.005% or less, B: 0.0005% to 0.0050%, and the remainder composed of Fe and incidental impurities, on a percent by mass basis, and a microstructure composed of ferrite and cementite, wherein the average grain size of the above-described ferrite is 10 to 20 μm and the spheroidization ratio of the above-described cementite is 90% or more.
Description
CROSS REFERENCE TO RELATED APPLICATIONS

This is the U.S. National Phase application of PCT/JP2012/008318, filed Dec. 26, 2012, which claims priority to Japanese Patent Application No. 2012-000407, filed Jan. 5, 2012, the disclosures of each of these applications being incorporated herein by reference in their entireties for all purposes.


FIELD OF THE INVENTION

The present invention relates to a high carbon hot rolled steel sheet having excellent cold workability and hardenability and a method for manufacturing the same.


BACKGROUND OF THE INVENTION

At present, automotive parts, e.g., gears, transmissions, and seat recliners, have been produced by processing hot rolled steel sheets, which are carbon steels for machine structural use specified in JIS G 4051, through cold working into predetermined shapes and applying a hardening treatment to ensure a predetermined hardness. Consequently, a mother hot rolled steel sheet is required to have excellent cold workability and hardenability, and various steel sheets have been proposed previously.


For example, Patent Literature 1 discloses a hot rolled steel sheet having excellent toughness after hardening and containing, as steel components, C: 0.10% to 0.37%, Si: 1% or less, Mn: 1.4% or less, P: 0.1% or less, S: 0.03% or less, sol. Al: 0.01% to 0.1%, N: 0.0005% to 0.0050%, Ti: 0.005% to 0.05%, B: 0.0003% to 0.0050%, and the remainder composed of Fe and incidental impurities, on a percent by mass basis, while B−(10.8/14)N*≥0.0005% and N*=N−(14/48)Ti, where N*=0 when the right side ≤0, are satisfied, wherein the average grain size of TiN which is a precipitate in the steel is 0.06 to 0.30 μm and a prior austenite grain size after hardening is 2 to 25 μm.


Patent Literature 2 discloses a method for manufacturing a Ti-B base high carbon steel sheet without tempering. The steel sheet has excellent cold workability, hardenability, and toughness after a heat treatment and contains C: 0.15% to 0.40%, Si: 0.35% or less, Mn: 0.6% to 1.50%, P: 0.03% or less, S: 0.020% or less, sol. Al: 0.01% to 0.20%, N: 0.0020% to 0.012%, Ti: 0.005% to 0.1%, B: 0.0003% to 0.0030%, and the remainder composed of Fe and incidental impurities, on a percent by mass basis, where B 0.0032−0.014×sol. Al−0.029×Ti is satisfied.


Patent Literature 3 discloses a high carbon hot rolled steel sheet having excellent cold workability, a composition containing C: 0.20% to 0.48%, Si: 0.1% or less, Mn: 0.20% to 0.60%, P: 0.02% or less, S: 0.01% or less, sol. Al: 0.1% or less, N: 0.005% or less, Ti: 0.005% to 0.05%, B: 0.0005% to 0.003%, Cr: 0.05% to 0.3%, and the remainder composed of Fe and incidental impurities, on a percent by mass basis, where Ti−(48/14)N≥0.005 is satisfied, and a microstructure in which a ferrite average grain size is 6 μm or less, carbide average grain size is 0.1 μm or more and less than 1.20 μm, and a volume fraction of ferrite grains substantially not containing carbide is 5% or less.


PATENT LITERATURE

PTL 1: Japanese Patent No. 4265582


PTL 2: Japanese Unexamined Patent Application Publication No. 5-98356


PTL 3: Japanese Unexamined Patent Application Publication No. 2005-97740


SUMMARY OF THE INVENTION

Regarding the high carbon steel sheets described in Patent Literatures 1 to 3, there are problems that the high carbon steel sheet having both of excellent cold workability and excellent hardenability is not produced stably.


It is an object of the present invention to provide a high carbon hot rolled steel sheet and a method for manufacturing the same, wherein excellent cold workability and excellent hardenability are obtained stably.


The present inventors studied on the cold workability and the hardenability of a high carbon hot rolled steel sheet containing B and, as a result, found the following.


i) Excellent cold workability is obtained stably by establishing a microstructure composed of ferrite and cementite, specifying the average grain size of the ferrite to be 10 to 20 μm, and specifying the spheroidization ratio of the cementite to be 90% or more.


ii) An effect of solute B to improve the hardenability can be exerted effectively and excellent hardenability is obtained stably by specifying the amount of sol. Al to be more than 0.10%.


iii) The hardenability improving effect can be exerted effectively and, thereby, the amounts of Si and Mn serving as solution hardening elements can be reduced and stable cold workability is obtained on an as hot rolled basis.


The present invention has been made on the basis of the above-described findings, and provides a high carbon hot rolled steel sheet having a composition containing C: 0.20% to 0.48%, Si: 0.1% or less, Mn: 0.5% or less, P: 0.03% or less, S: 0.01% or less, sol. Al: more than 0.10% and 1.0% or less, N: 0.005% or less, B: 0.0005% to 0.0050%, and the remainder composed of Fe and incidental impurities, on a percent by mass basis, and a microstructure composed of ferrite and cementite, wherein the average grain size of the above-described ferrite is 10 to 20 μm and the spheroidization ratio of the cementite is 90% or more.


It is preferable that the high carbon hot rolled steel sheet according to the present invention further contain 2% or less in total of at least one of Cu and Ni, 1.0% or less in total of at least one of Cr and Mo, and 0.1% or less in total of at least one of Sb and Sn, on a percent by mass basis, together or individually in addition to the above-described composition.


The high carbon hot rolled steel sheet according to the present invention can be produced by rough rolling the steel having the above-described composition, performing finish rolling at a finishing temperature of 850° C. or higher, performing coiling at a coiling temperature of 600° C. or higher, and performing annealing at an annealing temperature of 680° C. or higher and the Ac1 transformation temperature or lower.


According to the present invention, a high carbon hot rolled steel sheet can be produced, wherein excellent cold workability and excellent hardenability are obtained stably. The high carbon hot rolled steel sheet according to the present invention is suitable for automotive gears, transmissions, seat recliners, and the like.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a diagram showing the maximum grain size a and the minimum grain size b of cementite, where a/b≤3 and a/b=1.5.



FIG. 2 is a diagram showing the maximum grain size a and the minimum grain size b of cementite, where a/b>3 and a/b=6.





DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

A high carbon hot rolled steel sheet and a method for manufacturing the same according to embodiments of the present invention will be described below in detail. In this regard, the term “%” which is the unit of the content of component refers to “percent by mass” unless otherwise specified.


1) Composition


C: 0.20% to 0.48%


Carbon is an element important for obtaining the strength after hardening. It is necessary that the amount of C is at least 0.20% or more so that cold forming into a part is performed and, thereafter, a predetermined hardness is obtained by a heat treatment. However, if the amount of C is more than 0.48%, the cold workability is degraded because of becoming hard. Therefore, the amount of C is specified to be 0.20% to 0.48%. In order to obtain sufficient hardness after the heat treatment, the amount of C is specified to be preferably 0.26% or more.


Si: 0.1% or less


Silicon is an element to enhance strength on the basis of solution hardening. However, if the amount of Si is more than 0.1%, the cold workability is degraded because of becoming hard. Therefore, the amount of Si is specified to be 0.1% or less. The amount of Si may be zero with no problem.


Mn: 0.5% or less


Manganese is an element to enhance strength on the basis of solution hardening. However, if the amount of Mn is more than 0.5%, the cold workability is degraded because of becoming hard and formation of a band structure resulting from segregation. Therefore, the amount of Mn is specified to be 0.5% or less, and preferably 0.4% or less. The amount of Mn may be zero with no problem, although the amount of Mn is specified to be preferably 0.2% or more because if Mn is reduced, graphite is precipitated easily.


P: 0.03% or less


Phosphorus is an element to enhance strength on the basis of solution hardening. However, if the amount of P is more than 0.03%, the toughness after hardening is degraded because grain boundary embrittlement is caused. Therefore, the amount of P is specified to be 0.03% or less. In order to obtain excellent toughness after hardening, the amount of P is specified to be preferably 0.02% or less. The amount of P may be zero with no problem, although the amount of P is specified to be preferably 0.005% or more in consideration of the cost because excessive reduction increases the production cost.


S: 0.01% or less


Sulfur forms sulfides and degrades the cold workability and the toughness after hardening and, therefore, is an element to be reduced. If the amount of S is more than 0.01%, the cold workability and the toughness after hardening are degraded significantly. Consequently, the amount of S is specified to be 0.01% or less. In order to obtain excellent cold workability and toughness after hardening, the amount of S is specified to be preferably 0.005% or less. The amount of S may be zero with no problem.


Sol. Al: more than 0.10% and 1.0% or less


Soluble Al facilitates spheroidization of cementite and improves the cold workability. However, in the case of a steel containing B, if the amount of sol. Al is 0.10% or less, in carburizing and quenching or bright quenching, BN is formed easily when heating is performed in an atmosphere gas containing a N2 gas mixed to control the C potential, solute B to improve the hardenability may be reduced, and the hardenability of the surface layer portion of a steel sheet may be degraded significantly. If the amount of sol. Al is specified to be more than 0.10%, AlN is formed preferentially and formation of BN is suppressed, so that although austenite grains are made fine because of formation of AlN, the amount of solute B is ensured and, thereby, the hardenability can be exerted stably. On the other hand, if the amount of sol. Al is more than 1.0%, the cold workability is degraded because of becoming excessively hard due to solution hardening.


N: 0.005% or less


If the amount of N is more than 0.005%, the amount of solute B is reduced because of formation of BN in heating of the hardening treatment, and austenite grains are made fine excessively because of formation of large amounts of BN and AlN, formation of ferrite is facilitated in cooling, and the toughness after hardening is degraded. Consequently, the amount of N is specified to be 0.005% or less. The amount of N may be zero with no problem.


B: 0.0005% to 0.0050%


Boron is an important element to enhance the hardenability. However, if the amount of B is less than 0.0005%, a sufficient hardenability enhancing effect is not observed. On the other hand, if the amount of B is more than 0.0050%, a load of hot rolling increases, the operability is degraded, and degradation in the cold workability is caused. Consequently, the amount of B is specified to be 0.0005% to 0.0050%.


The remainder is composed of Fe and incidental impurities. In order to facilitate spheroidization of cementite and further improve the cold workability and the hardenability, it is preferable that 2% or less in total of at least one of Cu and Ni, 1.0% or less in total of at least one of Cr and Mo, and 0.1% or less in total of at least one of Sb and Sn be contained together or individually. Meanwhile, an effect of Sb and Sn to improve the hardenability by suppressing nitriding of B, as with the above-described sol. Al, was newly ascertained. Therefore, for the purpose of improving the hardenability more reliably, it is particularly preferable that these elements be added.


2) Microstructure


In order to stably obtain excellent cold workability, it is necessary that a microstructure composed of ferrite and cementite be established, the average grain size of the ferrite is specified to be 10 to 20 μm, and the spheroidization ratio of the cementite is specified to be 90% or more. This is because if the average grain size of the ferrite is less than 10 μm, the steel sheet becomes hard, and if the average grain size of the ferrite is more than 20 μm or the spheroidization ratio of the cementite is less than 90%, the ductility is reduced in spite of becoming mild, so that the cold workability is degraded.


Here, the average grain size of the ferrite was determined by polishing a sheet thickness cross-section in the rolling direction of the steel sheet, performing corrosion with nital, observing 10 places in the vicinity of the sheet thickness central portion by using a scanning electron microscope at a magnification of 1,000 times, determining the average grain size of the ferrite at each place by a cutting method in conformity with JIS G0552: 1998, and further averaging the average grain sizes of the 10 places. In this regard, the phase configuration of the microstructure can also be examined at the same time with this.


Meanwhile, in the above-described microstructure observation, the ratio a/b of the maximum grain size a to the minimum grain size b of each cementite was calculated, and the proportion (%) of the number of grains of the cementite having the above-described ratio of 3 or less to the whole number of grains of the cementite was determined and taken as the spheroidization ratio of the cementite. For example, the maximum grain size a and the minimum grain size b can be determined as shown in FIGS. 1 and 2.


3) Production Condition


Finishing temperature: 850° C. or higher


The high carbon hot rolled steel sheet is made into a steel sheet having a predetermined sheet thickness by subjecting the steel having the above-described composition to hot rolling composed of rough rolling and finish rolling. At this time, if the finishing temperature is lower than 850° C., austenite grains become fine, so that the average grain size of the ferrite formed in the cooling process performed thereafter becomes less than 10 μm. Therefore, the finishing temperature is specified to be 850° C. or higher. In this regard, the upper limit of the finishing temperature is not specifically limited. However, if excessively high, the microstructure becomes uneven and variations in the hardenability may occur easily. Consequently, the upper limit is specified to be preferably 1,000° C.


Coiling temperature: 600° C. or higher


If the coiling temperature is lower than 600° C., the average grain size of the ferrite becomes less than 10 μm. Therefore, the coiling temperature is specified to be 600° C. or higher. In this regard, the upper limit of the coiling temperature is not specifically limited. However, in order to avoid degradation in surface quality due to scales, the upper limit is specified to be preferably 750° C.


Annealing temperature: 680° C. or higher and Ac1 transformation point or lower


It is necessary that the steel sheet after coiling be subjected to pickling and annealing at an annealing temperature of 680° C. or higher and the Ac1 transformation temperature or lower in order that pearlite is not allowed to be generated, a microstructure composed of ferrite and cementite be established, and the spheroidization ratio of the cementite is specified to be 90% or more. If the annealing temperature is lower than 680° C., it is not possible to make the spheroidization ratio of the cementite 90% or more, and if the Ac1 transformation temperature is exceeded, austenite is generated in the heating, pearlite is generated in the cooling, and the cold workability is degraded. Meanwhile, the annealing time in which the above-described temperature is maintained is preferably 20 hours or more and 40 hours or less. The annealing time is preferably 20 hours or more because the spheroidization ratio of the cementite is adjusted within a predetermined range easily and is preferably 40 hours or less because the effect of annealing is obtained sufficiently and, in addition, an increase in production cost due to a long time of execution of annealing is suppressed.


Meanwhile, the Ac1 transformation temperature can be determined from, for example, a changing point of a thermal expansion curve determined on the basis of a formastor experiment at a heating rate of 100° C./hr.


In order to make the high carbon steel sheet according to the present invention, either a converter or an electric furnace can be used. The thus melted high carbon steel is made into a slab by ingot rolling or continuous casting. The slab is usually heated and, thereafter, is hot-rolled. In this regard, in the case of the slab produced by continuous casting, direct rolling may be applied, where rolling is performed on an as-is basis or while heat is retained to suppress a decrease in temperature. Also, in the case where the slab is heated and is hot-rolled, the slab heating temperature is specified to be preferably 1,280° C. or lower to avoid degradation in the surface state due to scales. In the hot rolling, the member to be rolled may be heated by a heating device, e.g., a sheet bar heater, during the hot rolling in order to ensure the finish rolling temperature.


EXAMPLES

Hot rolled annealed sheets (Steel sheet Nos. 1 to 18) having a sheet thickness of 4.0 mm were produced by melting high carbon steels having the compositions of Steel Nos. A to O shown in Table 1, performing hot rolling under the hot rolling conditions shown in Table 2, performing pickling, and performing annealing at annealing temperatures shown in Table 2.


The phase configurations of the microstructure, the average grain sizes of the ferrite, and the spheroidization ratios of the cementite of the thus produced steel sheets were determined by the above-described methods. Meanwhile, a JIS No. 5 tensile test piece was taken in a direction parallel to the rolling direction. The tensile strength and the elongation were determined in conformity with JIS Z 2201. Furthermore, the hardenability was evaluated by the method described below.


Hardenability: A flat plate test piece (width 50 mm×length 50 mm) was taken from the steel sheet, and was heated and held at 900° C. for 1 hour in an atmosphere in which a carbon potential was controlled to become equal to the amount of C in the steel by mixing an RX gas and the air. A hardening test was immediately performed by a controlled atmosphere hardening method in which the test piece was put into an oil at 50° C. and the oil was agitated, so that the Rockwell hardness (HRC) was measured. Then, in accordance with the amount of C in the steel, the hardenability was evaluated as excellent when HRC≥42 at C: 0.20%, HRC≥54 at C: 0.35%, and HRC≥58 at C: 0.48%.


The results are shown in Table 2.


It is clear that the steel sheet in the invention example has a microstructure composed of ferrite and cementite, the average grain size of the ferrite is 10 to 20 μm, the spheroidization ratio of the cementite is 90% or more, the elongation is large to exhibit excellent cold workability and, in addition, excellent hardenability is exhibited because sufficient hardness is obtained in accordance with the amount of C after hardening.









TABLE 1







(percent by mass)


















Steel.









Ac1 transformation



No
C
Si
Mn
P
S
sol. Al
N
B
Others
point (° C.)
Remarks





A
0.20
0.02
0.50
0.02
0.01
0.20
0.0033
0.003
Cr: 0.1
719
Inventive steel


B
0.35
0.02
0.30
0.02
0.01
0.11
0.0033
0.003

723
Inventive steel


C
0.35
0.02
0.30
0.02
0.01
1.00
0.0033
0.003
Cr: 0.2, Ni: 0.5
718
Inventive steel


D
0.35
0.02
0.30
0.02
0.01
0.11
0.0033
0.003
Cu: 0.5, Mo: 0.2
723
Inventive steel


E
0.48
0.02
0.20
0.02
0.01
0.40
0.0033
0.003
Cr: 0.5
731
Inventive steel


F
0.35
0.02
0.30
0.02
0.01
1.00
0.0033
0.003
Sb: 0.02, Sn: 0.04
723
Inventive steel


G
0.20

0.2


0.75

0.02
0.01

0.03

0.0033
0.003

728
Comparative steel


H
0.35

0.2


0.75

0.02
0.01

0.03

0.0033
0.003

728
Comparative steel


I
0.48

0.2


0.75

0.02
0.01

0.03

0.0033
0.003

728
Comparative steel


J
0.35
0.02
0.30
0.02
0.01

0.07

0.0033
0.003

720
Comparative steel


K
0.48
0.02
0.20
0.02
0.01

0.07

0.0033
0.003
Cr: 0.05
722
Comparative steel


L
0.35
0.02
0.30
0.02
0.01
0.11
0.0033
0.003
Sb: 0.01, Sn: 0.04
720
Inventive steel


M
0.35
0.02

0.75

0.02
0.01
0.11
0.0033
0.003

715
Comparative steel


N
0.35

0.2

0.50
0.02
0.01
0.11
0.0033
0.003

723
Comparative steel


O
0.35
0.02
0.30
0.02
0.01
1.00
0.0033
0.003
Ni: 0.5
715
Inventive steel























TABLE 2













Hardness






Average

after



Hot rolling condition

grain

controlled


















Steel

Finishing
Coiling
Annealing

size

Tensile

atmosphere



sheet
Steel
temperature
temperature
temperature
Phase
of F
Spheroidization
strength
Elongation
hardening


No.
No.
(° C.)
(° C.)
(° C.)
configuration*
(μm)
ratio of C (%)
(MPa)
(%)
(HRC)
Remarks





















1
A
890
660
680
F + C
20
95
340
54
43
Invention













example


2
B
880
650
700
F + C
15
93
380
46
56
Invention













example


3
B

810

600
680
F + C
6
94
510
37
55
Comparative













example


4
B
850

500

680
F + C
8
95
490
38
56
Comparative













example


5
B
880
680

640

F + C

22


80

340
39
56
Comparative













example


6
C
880
650
700
F + C
13
95
410
45
55
Invention













example


7
D
880
650
700
F + C
14
95
440
43
55
Invention













example


8
E
880
650
700
F + C
12
90
390
44
59
Invention













example


9
F
880
650
700
F + C
15
94
382
47
57
Invention













example


10

G

880
650
700
F + C
18

87

430
46

38

Comparative













example


11

H

880
650
700
F + C
13

85

490
38

50

Comparative













example


12

I

880
650
700
F + C
10

80

540
30

54

Comparative













example


13

J

880
650
700
F + C
12
90
480
45

53

Comparative













example


14

K

880
650
700
F + C
13
91
500
47

56

Comparative













example


15
L
880
650
700
F + C
11
95
380
44
55
Invention













example


16

M

880
650
700
F + C
12

85

460
43

51

Comparative













example


17

N

880
650
700
F + C
11

81

470
42

50

Comparative













example


18
O
880
650
700
F + C
13
94
400
46
55
Invention













example





*F ferrite, C cementite





Claims
  • 1. A high carbon hot rolled steel sheet comprising a composition containing C: 0. 20% to 0.48%, Si: 0.1% or less, Mn: 0.5% or less, P: 0.03% or less, S: 0.01% or less, sol. Al: more than 0.10% and 1.0% or less, N: 0.005% or less, B: 0.0005% to 0.0050%, and the remainder composed of Fe and incidental impurities, on a percent by mass basis, and a microstructure composed of ferrite and cementite, wherein the average grain size of the ferrite is 10 to 20 μm and the spheroidization ratio of the cementite is 90% or more.
  • 2. The high carbon hot rolled steel sheet according to claim 1, further containing 2% or less in total of at least one of Cu and Ni on a percent by mass basis.
  • 3. The high carbon hot rolled steel sheet according to claim 1, further containing 1.0% or less in total of at least one of Cr and Mo on a percent by mass basis.
  • 4. The high carbon hot rolled steel sheet according to claim 1, further containing 0.1% or less in total of at least one of Sb and Sn on a percent by mass basis.
  • 5. A method for manufacturing a high carbon hot rolled steel sheet, the method comprising the steps of rough rolling the steel having the composition according to claim 1, performing finish rolling at a finishing temperature of 850° C. or higher, performing coiling at a coiling temperature of 600° C. or higher, and performing annealing at an annealing temperature of 680° C. or higher and the Ac1 transformation point or lower.
  • 6. The high carbon hot rolled steel sheet according to claim 2, further containing 1.0% or less in total of at least one of Cr and Mo on a percent by mass basis.
  • 7. The high carbon hot rolled steel sheet according to claim 2, further containing 0.1% or less in total of at least one of Sb and Sn on a percent by mass basis.
  • 8. The high carbon hot rolled steel sheet according to claim 3, further containing 0.1% or less in total of at least one of Sb and Sn on a percent by mass basis.
  • 9. A method for manufacturing a high carbon hot rolled steel sheet, the method comprising the steps of rough rolling the steel having the composition according to claim 2, performing finish rolling at a finishing temperature of 850° C. or higher, performing coiling at a coiling temperature of 600° C. or higher, and performing annealing at an annealing temperature of 680° C. or higher and the Ac1 transformation point or lower.
  • 10. A method for manufacturing a high carbon hot rolled steel sheet, the method comprising the steps of rough rolling the steel having the composition according to claim 3, performing finish rolling at a finishing temperature of 850° C. or higher, performing coiling at a coiling temperature of 600° C. or higher, and performing annealing at an annealing temperature of 680° C. or higher and the Ac1 transformation point or lower.
  • 11. A method for manufacturing a high carbon hot rolled steel sheet, the method comprising the steps of rough rolling the steel having the composition according to claim 4, performing finish rolling at a finishing temperature of 850° C. or higher, performing coiling at a coiling temperature of 600° C. or higher, and performing annealing at an annealing temperature of 680° C. or higher and the Ac1 transformation point or lower.
Priority Claims (1)
Number Date Country Kind
2012-000407 Jan 2012 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2012/008318 12/26/2012 WO 00
Publishing Document Publishing Date Country Kind
WO2013/102986 7/11/2013 WO A
US Referenced Citations (4)
Number Name Date Kind
5454887 Fukui Oct 1995 A
7879163 Nakamura Feb 2011 B2
7909950 Kimura Mar 2011 B2
8048237 Kimura Nov 2011 B2
Foreign Referenced Citations (8)
Number Date Country
4-124216 Apr 1992 JP
4-311546 Nov 1992 JP
05-098356 Apr 1993 JP
8-120405 May 1996 JP
2002-309345 Oct 2002 JP
2005-097740 Apr 2005 JP
4-265582 May 2009 JP
2010-255066 Nov 2010 JP
Non-Patent Literature Citations (2)
Entry
International Search Report dated Mar. 26, 2013, application No. PCT/US2012/008318.
Supplementary European Search Report for Application No. EP 12 86 4620 dated Jul. 6, 2015.
Related Publications (1)
Number Date Country
20150090376 A1 Apr 2015 US