CN101065523A - Highly cut-resistant yarn and protective articles made therefrom - Google Patents

Highly cut-resistant yarn and protective articles made therefrom Download PDF

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Publication number
CN101065523A
CN101065523A CNA2005800401877A CN200580040187A CN101065523A CN 101065523 A CN101065523 A CN 101065523A CN A2005800401877 A CNA2005800401877 A CN A2005800401877A CN 200580040187 A CN200580040187 A CN 200580040187A CN 101065523 A CN101065523 A CN 101065523A
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China
Prior art keywords
yarn
poly
fabric
gloves
grit
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CNA2005800401877A
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Chinese (zh)
Inventor
A·S·科拉尔克
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of CN101065523A publication Critical patent/CN101065523A/en
Pending legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/442—Cut or abrasion resistant yarns or threads
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/047—Blended or other yarns or threads containing components made from different materials including aramid fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3065—Including strand which is of specific structural definition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/40—Knit fabric [i.e., knit strand or strip material]
    • Y10T442/425—Including strand which is of specific structural definition

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Gloves (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Multicomponent Fibers (AREA)
  • Woven Fabrics (AREA)

Abstract

A cut-resistant composite yarn, comprising a high strength organic fiber having a tenacity greater than 15 grams per denier and a hard-particle-filled thermoplastic fiber useful in making fabrics from which protective articles, such as gloves are made.

Description

Highly cut-resistant yarn reaches the protective articles by its manufacturing
Background of invention
1. technical field
The present invention relates to anti-cutting fiber and yarn, and their uses in the clothes of gloves and other protectiveness especially.
2. background technology
People seek to improve the cutting resistance for sharp edge always for a long time.Cut resistant gloves is advantageously used in processing industry and automobile application.As U.S. Pat 4,004,295,4,384,449 and 4,470,251, and pointed among the EP 458,343, anti-cutting gloves are by comprising soft annealed wire or by having the yarn manufacturing that high-modulus and high-intensity highly oriented fibre constitute, for example aromatic polyamides, thermotropism liquid crystal polymer and extended chain polyethylene.Shortcoming by the gloves of those yarn manufacturings that comprise soft annealed wire is the possibility that causes that easily hand is tired and cause reducing productivity ratio thus and increase injury.In addition, wear and tear and bending owing to extend, the tired and disconnection of this metal wire possibility causes cutting and fraying hand.In addition, when the gloves of washing were at high temperature dry, this metal wire played radiator, and this can reduce the TENSILE STRENGTH of yarn or fiber, thereby reduces the protective effect and the life-span of gloves.
In the clothes of anti-cutting, protectiveness, improve pliability, comfortable and easy washing is made us expecting.Therefore, need a kind of pliable and tough, anti-cutting fiber that can in daily washing, keep performance.Such fiber can help making protective garment, especially highly flexible cut resistant gloves.
Polymer mixes with particulate matter and makes fiber, yet does not improve the anti-cutting of fiber significantly.For example, a spot of titanium dioxide fine particles uses as delustering agent in polyester fiber.A spot of cataloid also is used for polyester fiber, in order to improve gloss.Magnetic material adds fiber and produces magnetic fibre.Example comprises: in Japanese patent application 55/098909 (1980) disclosed in thermoplastic fibre cobalt/rare earth elemental metals change thing mutually; Japanese patent application 3-130413 (1991) disclosed in core sheath fiber cobalt/rare earth elemental metals change thing or strontium ferrite mutually; With people such as Poland Patent 251,452 and K.Turek, J.Magn.Magn.Mater. (1990), 83 (1-3), in the 279-280 page or leaf disclosed in thermoplastic polymer magnetic material.In addition, United States Patent (USP) 5,597,649 relate to a kind of yarn, are the composites of high modulus fibre and particles filled fiber, and wherein high modulus fibre can be an aramid fiber.
Multiple gloves on the make add metal to give the quality of gloves protect.For example, United States Patent (USP) U.S.2,328,105 and 3,185,751 have instructed a kind of flexible, X-ray protection gloves, make by the porous material thin slice that is fit to that uses heavy metal in small, broken bits to handle, heavy metal can be lead, barium, bismuth or tungsten, or can be by latex that comprises heavy metal particles or dispersion manufacturing.As U.S. Pat 5,020, shown in 161, make the gloves of anticorrosive property liquid with metal film layer.These gloves do not improve anti-cutting significantly yet.
Summary of the invention
In one embodiment, the present invention is a kind of composite yarn of anti-the cutting, comprise having toughness, can be used for making the cut resistant fabric that can be used for protective articles, for example gloves, apron, leggings, sleeve etc. greater than the high strength organic fiber and the grit filled thermoplastic fiber at 15 gram/dawn.
Description of drawings
Fig. 1 a and 1b are the schematic diagrames that is used for the chamber of torture chamber test.
Fig. 2 is the schematic diagram of the detection gloves of use in the torture chamber test.
Detailed Description Of The Invention
The present invention relates to yarn and the goods of height cutting resistance, the protectiveness that is used for the individual is used such as gloves, apron, leggings etc. and the method for making them. These goods are made by the thermoplasticity carrier fibre combination of high strength organic fiber and filling grit.
Term " high strength organic fiber " is meant that toughness greater than the fiber at 15 gram/dawn, is formed by arbitrary polymerisation well known in the art by the monomer based on carbochain in embodiments of the invention.Preferably, the high strength organic fiber does not comprise carbon fiber.The typical high strength organic fiber that the present invention comprises includes but not limited to toughness greater than the fiber at 15 gram/dawn, by to aromatic polyamides, poly-indoles, poly-benzoxazol, polybenzothiozole, polybenzimidazoles, polyacrylate and their copolymer.
In one embodiment of the invention, carrier fibre is formed by the isotropism semi-crystalline polymer.Typical fiber is by polymer for example poly-(terephthalic acid (TPA) alkylene ester), poly-(alkylene naphthalate), poly-(arylene sulfide), aliphatic series and aliphatic-aromatic polyamide, and the polyester that makes of the monomer of being derived by cyclohexanedimethanol and terephthalic acid (TPA).In another embodiment of the invention, carrier fibre is formed by liquid crystal polymer (LCP), and is preferably thermotropic.For example aromatic polyester, aliphatic-aromatic polyesters, aromatics poly-(ester carbonic acid ester) form typical LCP fiber, aliphatic-aromatic gathers (esteramides), aromatics poly-(ester acid imide), aromatics gathers (esteramides), aliphatic-aromatic polyamide and poly-(azomethine) by polymer.
The present invention is characterised in that in order to the grit of filling thermoplastic fibre Mohs' hardness can be greater than 5.Preferably, the average particle size distribution of grit is in the 1-6 micrometer range.The typical material that comprises this grit includes but not limited to tungsten, red metal, brass, bronze aluminium, steel, iron, monel metal, cobalt, titanium, magnesium, silver, molybdenum, tin, zinc, aluminium oxide, tungsten carbide, metal nitride, metal sulfate, phosphate, metal boride, silica, carborundum, baddelyte, chloritoid, clinozoiste, chondrodite, euclasite, petalite, sapphire, spodumene, staurolite, clay or aluminium oxide.
In one embodiment of the invention, the thermoplastic fibre that grit is filled is a kind of thermoplastic fibre, and wherein hard particle filler is equally distributed substantially.The amount that hard particle filler exists is 0.1-10 (randomly 0.1-5) weight %, based on the gross weight meter of particles filled fiber.
In another embodiment of the invention, the thermoplastic fibre that grit is filled is the core fibre of sheath/core fibre, and wherein hard particle filler is equally distributed substantially in the core material of sheath/core fibre.Preferably, the amount that hard particle filler exists is 0.1-10 (randomly 0.1-5) weight %, based on the gross weight meter of sheath/core fibre.
Goods are preferably by making by knitting, yarn is by E.I.du Pont de Nemours and Company (DuPont), Wilmington, poly-(poly P phenylene diamine terephthalamide) fiber and the polyester CRF (anti-cutting fiber) of the commodity that DE sells KEVLAR  by name form.Polyester CRF is preferably as U.S. Pat 5,851, disclosed alumina filled (about 10%) multifilament in 668.Polyester is poly-(ethylene terephthalate) preferably.The resistant polyester cutting fiber can be obtained by Honeywell, trade (brand) name Barricut .Yarn of the present invention comprises the polyester fiber of anti-cutting of about 32-65%, yet it is about 65% that the polyester of anti-cutting percentage surpasses, and the cutting protective value reduces.The cut resistant fabric of KEVLAR  and polyester combination is measured the fabric of anti-cutting greater than the similar weight of being made by arbitrary fiber fully with ASTM F1790-97.In addition, with different by the goods of resistant polyester cutting fabric manufacturing fully,, for example use scissors by goods very anti-cutting in shearing manipulation that fabric of the present invention is made.
In addition, these goods with form of gloves demonstrate the long especially life-span in punishment chamber test (TCT).Gloves of the present invention are verified than KEVLAR  completely or completely the gloves made of polyester CRF have more performance.Dupont discloses TCT (following open in detail) the anti-cutting material of evaluation and test performance under most severe condition, wherein cuts the performance of protective value test inaccuracy expectation in reality.
Folded yarn of the present invention by simultaneously twisting at least two kinds independently single thread prepare.It is known twisting single thread manufacturing folded yarn in the art simultaneously.Every kind of single thread can be that for example, many cut staples are spun into short fibre yarn in mode well known in the art.
Phrase " is twisted at least two kinds of independently single thread " simultaneously, and the meaning is that two kinds of single thread are twisted simultaneously, and a kind of yarn not exclusively covers another kind.The difference of folded yarn and covering or wrap yarn is that first kind of single thread is wrapped in around second kind of single thread fully, so that first kind of single thread only exposed on the surface of the folded yarn that forms.
Folded yarn of the present invention preferably is made up of at least two kinds of different single thread.The preferred total linear density of folded yarn is 300-2000dtex.Usually filament line density 0.5-7dtex in single yarn, preferable range is 1.5-3dtex.Folded yarn and the single thread of forming folded yarn can comprise other material, as long as the function or the not infringement of performance of the fabric of making for the yarn of wanting or by this yarn.
Method of testing
Cutting protective value test (CPPT) is carried out with ASTM F1790-97.
Tabor Abrasion Resistance measures according to ASTM D3389.
The scissors cut-through resistance test is to use 8 inches these goods of carbon steel scissors cut that are generally used for family or office's type, and subjective evaluation and test is relatively easy/difficulty when cutting.
The test of punishment chamber is in the Lucite cylinder 10 of the closed at both ends of 16 inches of diameters, shown in Fig. 1 a and 1b.Six (6) blade holders 12 are installed in the cylinder the inside, spend (cylinder bore is 14.5 inches) separately around the edge with 60.4 monolateral blades 14 of each blade holder clamping are with angled before and after 45 degree are in cylinder.Use Red Devil single edges industrial blade.Cylinder rotates round central shaft, by Motor Drive, does not show in the drawings.The rotary speed of cylinder is 35 revolutions per minutes.Various materials are with the form test of gloves.Each gloves is filled 400gm nylon particle, and the gloves that comprise particle are placed on alone among the Torture Chamber then in the position sealing near wrist.Detect gloves as shown in Figure 2.New razor blade is used in each gloves evaluation and test.Be defined as fault time when the time of in Torture Chamber, observing the nylon particle at first.Be not observed in 180 minutes as fruit granule and then stop to detect.When observing any pearl, Torture Chamber stops the rotation, and takes out gloves and affirmation inspection cutting directly perceived.Confirm that gloves have actual breaking, but not particle is dropped out owing to the carpal area belt is loosening.
Embodiment
Material is according to the needs of specific test, various fibers is made as fabric sample or gloves are evaluated and tested by knitting method.
Embodiment 1 and Comparative Examples A and B
Basis weight 12.5oz/yd 2(424g/m 2) the following manufacturing of knitting sample:
Comparative Examples A 100% polyester CRF
Comparative example B 100%KEVLAR
Embodiment 1-52%KEVLAR/48%CRF, wherein KEVLAR and CRF are merged into co-twisted (plying) yarn.Two kinds of co-twisted yarns feed knitting machine jointly to produce fabric then.
The result of CPPT and Tabor Abrasion test is as shown in table 1.
Table 1
Embodiment CPPT Tabor Abrasion resistance
A 1125g 325 circulations
B 775g 360 circulations
1 1255g 430 circulations
Embodiment 2-3 and comparative example C and D
Basis weight 19oz/yd 2(644g/m 2) knitted fabric and gloves make by the following method:
Comparative example C 100% polyester CRF
Comparative example D 100%KEVLAR
Embodiment 2-68%KEVLAR/2% polyester CRF, three kinds of wherein knitting uses feeding yarn, two kinds of yarns are as described in the embodiment 1, and the third feeding yarn is 100%KEVLAR.
Embodiment 3-35%KEVLAR/65% polyester CRF, three kinds of feed yarns yarns of wherein knitting use, two kinds of yarns are as described in the embodiment 1, and the third feed yarns yarn is 100% polyester CRF.
2 test results that provide of tabulating down except that punishment chamber test with on each textile gloves, carry out.
Table 2
Embodiment CPPT Tabor Abrasion The torture chamber life-span The scissors resistance
C 1525g 790 circulations 0.2 minute Easily
D 1185g 440 circulations 15 minutes Difficult
2 1750g 120 minutes Difficult
3 2259g 90 minutes Not test

Claims (20)

1. composite yarn of anti-the cutting, it comprises the thermoplastic fibre that toughness is filled greater than the high strength organic fiber and the grit at 15 gram/dawn.
2. the yarn of claim 1, wherein said thermoplastic fibre is a liquid crystal polymer, and described polymer is selected from aromatic polyester, aliphatic-aromatic polyesters, aromatics poly-(ester carbonic acid ester), aliphatic-aromatic poly-(esteramides), aromatics poly-(ester acid imide), aromatics poly-(esteramides), aromatic polyamides, aliphatic-aromatic polyamide and gathers (azomethine).
3. the yarn of claim 1, wherein said thermoplastic fibre is a semi-crystalline polymer, described polymer is selected from poly-(terephthalic acid (TPA) alkylene ester), poly-(alkylene naphthalate), poly-(arylene sulfide), aliphatic polyamide, aliphatic-aromatic polyamide, and the polyester that makes of the monomer of being derived by cyclohexanedimethanol and terephthalic acid (TPA).
4. the yarn of claim 3, it comprises 32-65 weight % poly-(ethylene terephthalate), based on yarn weight meter.
5. the yarn of claim 1, wherein said high strength organic fiber are selected from aromatic polyamides, poly-indoles, poly-benzoxazol, polybenzothiozole, polybenzimidazoles, polyacrylate and their copolymer.
6. the yarn of claim 5, wherein said is poly-(poly P phenylene diamine terephthalamide) to aromatic polyamides.
7. the yarn of claim 1, wherein said grit is selected from tungsten, red metal, brass, bronze, aluminium, steel, iron, monel metal, cobalt, titanium, magnesium, silver, molybdenum, tin, zinc, aluminium oxide, tungsten carbide, metal nitride, metal sulfate, metal phosphate, metal boride, carborundum, baddelyte, chloritoid, clinozoiste, chondrodite, euclasite, petalite, sapphire, spodumene, staurolite and clay.
8. the yarn of claim 7, wherein the average particle size distribution of grit is between the 1-6 micron.
9. the yarn of claim 7, wherein grit exists with the amount of 0.1-10 weight %, the gross weight meter of the thermoplastic fibre of filling based on grit.
10. the yarn of claim 1, wherein thermoplastic fibre has sheath-cored structure, and grit is included in in-core basically.
11. a cut resistant fabric, it comprises each cut resistant yarn of claim 1-10.
12. cut resistant fabric that comprises that the complex yarn of anti-the cutting is formed, wherein said yarn comprises poly-(poly P phenylene diamine terephthalamide) and poly-(ethylene terephthalate), the grit that it fills about 0.1-10 weight % adds the gross weight meter of poly-(ethylene terephthalate) based on grit.
13. claim 11 or 12 each cut resistant fabric, wherein said fabric is woven or knit goods.
14. claim 11 or 12 each fabrics, wherein said fabric is when testing according to ASTMF1790-97, at least 6 ounces every square yard (203g/m 2) the cutting protective value value of basis weight is at least 500 grams.
15. claim 11 or 12 each fabrics, wherein said fabric is when testing according to ASTMF1790-97, at least 12 ounces every square yard (407g/m 2) the cutting protective value value of basis weight is at least 1000 grams.
16. claim 11 or 12 each fabrics, wherein said fabric is when testing according to ASTMF1790-97, at least 19 ounces every square yard (644g/m 2) the cutting protective value value of basis weight is at least 1500 grams.
17. claim 11 or 12 each fabrics, wherein when testing according to ASTM F1790-97, the cutting protective value of described fabric is greater than the contained fabric that arbitrary single thread constituted of the composite yarn by claim 1 of identical basis weight and structure.
18. protection goods, it comprises each fabric of claim 11 or 12, and wherein said protection goods are selected from apron, leggings, sleeve and gloves.
19. according to the gloves of claim 18, the torture chamber life-span of wherein said gloves surpass to equate the torture chamber life-span of the gloves that only are made of a kind of fiber of described yarn of basis weight.
20. the gloves of claim 23 are when the fabric basis weight is 19oz/yd at least 2(644g/m 2) time, the torture chamber life-span is at least 90 minutes.
CNA2005800401877A 2004-11-23 2005-11-21 Highly cut-resistant yarn and protective articles made therefrom Pending CN101065523A (en)

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US10/997,721 US20060110597A1 (en) 2004-11-23 2004-11-23 Highly cut-resistant yarn and protective articles made therefrom
US10/997,721 2004-11-23

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EP (1) EP1815050A1 (en)
JP (1) JP2008520850A (en)
KR (1) KR20070084454A (en)
CN (1) CN101065523A (en)
BR (1) BRPI0516906A (en)
CA (1) CA2582962A1 (en)
MX (1) MX2007006080A (en)
WO (1) WO2006058001A1 (en)

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CN104629271A (en) * 2015-02-10 2015-05-20 扬州大学 Spodumene slag filled composite material of reclaimed polyethylene terephthalate and preparation method thereof
CN105273379A (en) * 2015-11-30 2016-01-27 扬州大学 Method for preparing polylactic acid nano composite material
CN107083590A (en) * 2009-02-09 2017-08-22 帝斯曼知识产权资产管理有限公司 The complex yarn of cut resistant
CN108411417A (en) * 2018-02-12 2018-08-17 浙江康隆达特种防护科技股份有限公司 A kind of anti-cut yarn and the product being produced from it
CN109355911A (en) * 2018-09-23 2019-02-19 南通嘉得利安全用品有限公司 A kind of composite yarn and its production method
CN112779623A (en) * 2020-09-17 2021-05-11 安丹达工业技术(上海)有限公司 Composition for cutting-resistant fiber, application and preparation method

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CN104629271A (en) * 2015-02-10 2015-05-20 扬州大学 Spodumene slag filled composite material of reclaimed polyethylene terephthalate and preparation method thereof
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US20080086790A1 (en) 2008-04-17
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JP2008520850A (en) 2008-06-19
EP1815050A1 (en) 2007-08-08
KR20070084454A (en) 2007-08-24
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BRPI0516906A (en) 2008-09-23
CA2582962A1 (en) 2006-06-01

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