EP1555902B1 - Multilayered, breathable textile fabric - Google Patents
Multilayered, breathable textile fabric Download PDFInfo
- Publication number
- EP1555902B1 EP1555902B1 EP03777848A EP03777848A EP1555902B1 EP 1555902 B1 EP1555902 B1 EP 1555902B1 EP 03777848 A EP03777848 A EP 03777848A EP 03777848 A EP03777848 A EP 03777848A EP 1555902 B1 EP1555902 B1 EP 1555902B1
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- EP
- European Patent Office
- Prior art keywords
- yarns
- aramid
- layer
- textile fabric
- fabric according
- 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.)
- Expired - Lifetime
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- 239000004744 fabric Substances 0.000 title claims description 110
- 239000004753 textile Substances 0.000 title claims description 36
- 239000000835 fiber Substances 0.000 claims description 42
- 239000004760 aramid Substances 0.000 claims description 37
- 229920003235 aromatic polyamide Polymers 0.000 claims description 34
- 229920001410 Microfiber Polymers 0.000 claims description 19
- 239000003658 microfiber Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 10
- 229920006231 aramid fiber Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920006376 polybenzimidazole fiber Polymers 0.000 claims description 4
- 239000004693 Polybenzimidazole Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 3
- 238000010891 electric arc Methods 0.000 claims description 2
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims 2
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229920000784 Nomex Polymers 0.000 description 12
- 239000004763 nomex Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 230000035515 penetration Effects 0.000 description 4
- 229920000271 Kevlar® Polymers 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 3
- 239000004761 kevlar Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 229920000544 Gore-Tex Polymers 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- 229920003367 Teijinconex Polymers 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 239000004951 kermel Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- 239000004765 teijinconex Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/08—Heat resistant; Fire retardant
- A41D31/085—Heat resistant; Fire retardant using layered materials
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
- A41D31/102—Waterproof and breathable
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/12—Hygroscopic; Water retaining
- A41D31/125—Moisture handling or wicking function through layered materials
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/26—Electrically protective, e.g. preventing static electricity or electric shock
- A41D31/265—Electrically protective, e.g. preventing static electricity or electric shock using layered materials
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
Definitions
- the present invention relates to a multilayered, breathable - that is to say, moisture vapor permeable - textile (including woven and knitted) fabric and especially, but not exclusively, to a textile fabric for clothing purposes.
- the invention relates to a fabric for manufacturing articles of work clothing for protection against the effects of heat, flames, electric arc, and the like. Therefore, the invention also relates to an article of fire protection clothing with a novel, breathable, moisture-transporting fabric as an inner layer.
- the textile fabric can also be used in the leisure sector, for example, to manufacture functional undergarments.
- Breathing fabric constructions such as, those sold under the name GORETEX ® .
- Breathable fabrics are essentially water impermeable on one side, while they allow water vapor to escape through the fabric on the other side. These fabrics are used for articles of clothing, especially for jackets and coats and pants.
- the fabric is waterproof, while, at the same time, it prevents the collection of water vapor under the coat caused by perspiration.
- U.S. Pat. No. 3,272,685 describes a waterproof fabric that has at least two different layers.
- German Patent DE 195 47 704 A1 describes a multilayered textile fabric consisting of two fabric layers with different denier values used to transport perspiration and other bodily fluids.
- the fabric layers have a material from the group consisting of polyester, nylon and acrylic resin. This fabric, however, is not suitable for manufacturing protective clothing.
- German Patent DE 43 07 501 A1 describes a multilayered textile fabric with an inner layer of microfibers, whereby the fabric has a wicking or capillary effect and improves the water vapor transport from the inside to the outside.
- the described textile fabrics are used to manufacture sports clothing, leisure clothing and the like.
- protective clothing for instance, for firefighters, is very heavy on its own.
- the protective outfits provide protection by being massive, but this greatly limits the wearer's ability to move and leads to severe heat stress, thus considerably impairing the wearing comfort.
- fire protection clothing has to meet national standards, for example, the standards DIN EN 469 or SN 054551.
- the textile fabric 1 comprises at least two separate layers 2, 3 that are bonded to each other by means of dots or lines or else over the entire surface, whose warp and weft yarns consist of aramid yarns or aramid twisted threads or aramid filament yarns or yarns made of blended fibers containing polybenzimidazole and aramid fibers, whereby the layers 2, 3 have different individual fiber degrees of fineness in order to bring about a fineness gradient over the thickness 7 of the fabric 1, whereby the side 6 of the layer 3 that essentially faces the skin has the coarser individual fiber titer and the layer of the side 4 facing away from the skin has the finer individual fiber titer.
- the fabric according to the invention while providing virtually identical thermal insulation, has a moisture absorption, relative to the square meter weight, that is about four to eight times as high in comparison to the prior art material.
- the time within which the drops of perspiration are absorbed is less than one second with the material according to the invention.
- this value is about five minutes.
- the mode of action of the textile fabric 1 according to the invention can be described as follows.
- the fabric 1 is composed of at least two separate single plies 2, 3 being bonded to each other at predefined positions 5 by the mean of selected bounding yarns which are part of the ply 3 which faces away from the skin.
- the bounding yarns are woven or knitted or stitched through the ply 2 on the skin side.
- the bounding yarns are visible on this predefined position on the skin side 6 in the form of dots.
- the moisture formed on the skin is absorbed by the microfiber composing the bounding yarns forming the dots 5 located on the skin side 6, it is then transported by the capillary action of the microfibers along the bounding yarns to the back of the ply or layer 3 by means of capillary action and the preferred direction of the bounding yarns towards the ply 3 facing away from the skin.
- On the side 6 which faces the skin it quickly evaporates due to the large surface of the waffle structure. Consequently, the side 6, which faces the skin, always remains relatively dry in comparison to normal material, for example, normal aramid lining fabric.
- the multilayered, breathable textile fabric 1 is used to manufacture an article of work clothing, for example, for firefighters.
- the textile fabric 1 consists of a base fabric, ply or layer 2 and a microfiber fabric, ply or layer 3, each layer 2,3 with warp and weft yarns.
- the warp and weft yarns for each of the layers 2,3 can be made of aramid spun yarn (made from staple fiber) as well as multifilament continuous yarn can be used. Combinations are also possible. According to the invention, however, it is also possible to use phenol formaldehyde fibers, polyamide/polyimide fibers, polybenzimidazole fibers or fiber mixtures made of the above-mentioned fibers or else fiber mixtures with aramid yarns or else blended fibers containing polybenzimidazole and aramid fibers.
- polyester and/or polyamide yarns can then used for either or both of the layers 2,3.
- Such materials are fundamentally known to the person skilled in the art.
- the aramid yarns consist of aramid fibers from the group made up of Nomex ® , Kevlar ® , Twaron ® , Technora ® , and Teijinconex ® .
- Products such as Kynol ® are used as the phenol formaldehyde fibers and products such as Kermel ® are used as the polyamide/polyimide fibers.
- Possible weaves are all basic woven or knit types of weaves and their variations.
- the aramid fibers are natural colored or dyed.
- the fabric layers 2, 3 have a square meter weight in the range from 50 to 450 g/m 2 .
- the breathable fabric 1 is a duplex construction comprising at least two layers or plies 2, 3 that are bonded to each other.
- the layers 2, 3 are bonded to each other by means of selected bounding yarns which are part of the ply 3 which faces away from the skin forming dots 5 or lines or else over the entire surface, whereby in one embodiment, the pattern shown in Figure 1 can be formed.
- the individual microfiber dots 5 are each at a distance of x 1 in the weft direction and x 2 in the warp direction from each other as indicated in the Figure 1 .
- the distances x 1 and x 2 should be selected in such a way that a water micro droplet on the surface 6 of the layer 2 facing the skin would touch at least one of the dots 5 or lines.
- the base fabric or layer 2 according to the invention consists fundamentally of a basic woven or knit base fabric, whereby the layers 2, 3 have different individual fiber deniers, i.e., degrees of fineness of the individual fibers, in order to bring about a fineness gradient over the thickness 7 of the fabric 1.
- the finer denier layer 3 is on the outside, that is to say, on the side 4 facing away from the skin.
- this layer 3 has individual fiber titers of less than 1.3 dtex, especially less than 1 dtex.
- the microfiber layer 3 has a highly structured surface 10.
- the fibers used in the layer 3 are microfibers, i.e., a new generation of ultrafine-titer fibers. With these microfiber yarns, one can manufacture very windproof, fine-pored, water-repellant fabrics that have a soft hand but that are good at dissipating water vapor or moisture of a perspiring person. This effect is shown in Figure 2 . Perspiration 8 formed on the skin is picked up via the microfiber dots 5 and transported to the outside by the capillary action of the bounding yarns of the fabric 3 (wicking effect 9). This wicking effect 9 is necessary for the transport of moisture 8 (perspiration, condensation water) from the inside 6 to the outside 4.
- the textile fabric 1 can be used in a fire-protection jacket.
- the textile fabric 1 or insulating lining can be in a composite with other materials.
- an article can be made comprising:
- a blend of fibers commercially available from E. I. du Pont de Nemours and Company, Wihnington, Delaware, U.S.A., under the trade name Nomex ® N301, having a cut length of 5 cm and consisting of:
- Y1 had a linear density of Nm 40/1 or 250 dtex and a twist of 700 Turns Per Meter (TPM) in Z direction and it was subsequently treated with steam to stabilize its tendency to wrinkle. Two Y1 yarns were then plied and twisted together. The resulting plied and twisted yarn (TY1) had a linear density of Nm 40/2 or 500 dtex and a twist of 500 TPM in S direction. TY1 was used as warp yarn and weft yarn for the ply or base fabric 2 facing the skin.
- TPM Turns Per Meter
- Nomex ® T 450 having a cut length of 5 cm and consisting of 100% of poly-metaphenylene isophthalamide (meta-aramid), 1.1 dtex staple fibers
- Y2 had a linear density ofNm 80/1 or 125 dtex and a twist of 1070 Turns Per Meter (TPM) in Z direction and it was subsequently treated with steam to stabilize its tendency to wrinkle.
- TPM Turns Per Meter
- Two Y2 yarns were then plied and twisted together.
- the resulting plied and twisted yarn had a linear density of Nm 80/2 or 250 dtex and a twist of 750 TPM in S direction.
- TY2 was used as warp yarn and weft yarn for the ply 3 facing away from the skin.
- TY2 were also used as the bounding yarns between the two plies as they have the highest capillarity.
- TY1 and TY2 were woven into a special double-face weave according to Sonja 0203 pattern as illustrated in Figures 3a-d .
- This fabric 1 was tested as an innerliner thermal barrier used in a multi layer structure (Garment in Table I) which further comprised (1) an intermediate water barrier layer of a polytetrafluoroethylene (PTFE) membrane laminate on a nonwoven fabric made of 85 wt-% Nomex ® and 15 wt-% Kevlar ® and having a specific weight of 135 g/m 2 (commercially available under the trade name GORETEX ® Fireblocker N from the company W. L. Gore and Associates, Delaware, U.S.A), and (2) an outershell having a specific weight of 195 g/m 2 and composed of a blend of fibers, commercially available from E. I du Pont de Nemours and Company, Wilmington, Delaware, U.S.A. under the trade name Nomex ® N305 having a cut length of 5 cm and consisting of:
- PTFE polytetrafluoroethylene
- the FFF was 5.3 compared to the prior art or benchmark which is between 5.2 and 6.7.
- This fabric 1 was also tested according to a water transmission test with a water drop of 60 ml applied with a syringe on the fabric 1. The test consisted of measuring the time for the penetration and absorption. This test was repeated for the ply 2 facing the skin alone without the second ply 3 and the bounding yarns. Results are in Table 2. TABLE 2 Sample Test Time for penetration Ply facing the skin alone Drop 1 2 sec. Drop 2 5 sec. Drop 3 3 sec. Drop 4 7 sec. Drop 5 3 sec. Average 4 sec. Fabric according to the invention Drop 1 immediate Drop 2 immediate Drop 3 immediate Drop 4 immediate Drop 5 immediate Average immediate Control fabric Drop 1 6 sec. Nomex ® comfort Quilted with Drop 2 7 sec. Felt 250g/m 2 Drop 3 7 sec. Drop 4 6 sec. Drop 5 8 sec. Average 7 sec.
- This fabric 1 was tested according to a water absorption test method. The test consisted of applying a colored water drop of 20 ml on the ply of the fabric facing the skin fabric and measured after 60 seconds the size of the drop on the each layer of the sample. Results are in Tables 3 and 4. TABLE 3 Fabric according to the invention Ply facing the skin Test Size in mm Drop 1 6 Drop 2 6 Drop 3 6 Average 6 TABLE 4 Test Minimum Size in mm after penetration Maximum size in mm after penetration Ply facing away from the skin Drop 1 25 33 Drop 2 27 35 Drop 3 26 38 Control Drop 1 0 0 Nomex ® comfort Quilted with Drop 2 0 0 Felt 250g/m2 Drop 3 0 0
- the fabric 1 was tested against moisture absorption on porous disk method STFI-Vorschr. PE03 from the Sambasisches Textilmaschine Institute, simulating the physiological properties of a fabric in contact with a wet skin. The moisture absorption was measured in g/dm 2 , and the relative moisture absorption was calculated according the fabric surface weight. The fabric 1 was also tested against the sweating guarded hot plate test ISO-11092 in order to obtain the Ret value. This fabric was compared with a control Fritsche 48101330022941 composed of a Nomex ® Comfort liner of 140 g/m 2 quilted with a Nomex ® knitted thermal barrier of 190 g/m 2 . The results are in Table 5. TABLE 5 Ret (M 2 Pa/W) Absolute moisture absorption (g/dm 2 ) Relative moisture absorption (%) Fabric 1 5.78 7.7 255 Function Control 6.86 2.4 67.5 Fritsche 48101330022941
- This fabric 1 was tested according to the contact heat resistance test in accordance with prEN 702.
- the threshold time t t (sec) at 100 °C was measured at 19.8 sec and was significantly better than a standard fabric out of Nomex ® N 307 having t t (sec) at 100 °C value of 18.4 sec.
- the articles of clothing according to the invention can be made up as desired.
- the fabric according to the invention is, of course, not limited to the use for manufacturing protective clothing.
- the fabric can be used to manufacture leisure clothing, especially to manufacture functional undergarments.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Woven Fabrics (AREA)
- Professional, Industrial, Or Sporting Protective Garments (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Multi-Layer Textile Fabrics (AREA)
Description
- The present invention relates to a multilayered, breathable - that is to say, moisture vapor permeable - textile (including woven and knitted) fabric and especially, but not exclusively, to a textile fabric for clothing purposes. In a special embodiment, the invention relates to a fabric for manufacturing articles of work clothing for protection against the effects of heat, flames, electric arc, and the like. Therefore, the invention also relates to an article of fire protection clothing with a novel, breathable, moisture-transporting fabric as an inner layer. However, the textile fabric can also be used in the leisure sector, for example, to manufacture functional undergarments.
- The state of the art already describes "breathing" fabric constructions such as, those sold under the name GORETEX®. Breathable fabrics are essentially water impermeable on one side, while they allow water vapor to escape through the fabric on the other side. These fabrics are used for articles of clothing, especially for jackets and coats and pants. Here, the fabric is waterproof, while, at the same time, it prevents the collection of water vapor under the coat caused by perspiration.
U.S. Pat. No. 3,272,685 describes a waterproof fabric that has at least two different layers. -
German Patent DE 195 47 704 A1 describes a multilayered textile fabric consisting of two fabric layers with different denier values used to transport perspiration and other bodily fluids. The fabric layers have a material from the group consisting of polyester, nylon and acrylic resin. This fabric, however, is not suitable for manufacturing protective clothing. -
German Patent DE 43 07 501 A1 describes a multilayered textile fabric with an inner layer of microfibers, whereby the fabric has a wicking or capillary effect and improves the water vapor transport from the inside to the outside. The described textile fabrics are used to manufacture sports clothing, leisure clothing and the like. - As a rule, protective clothing, for instance, for firefighters, is very heavy on its own. The protective outfits provide protection by being massive, but this greatly limits the wearer's ability to move and leads to severe heat stress, thus considerably impairing the wearing comfort.
- Moreover, it has to be taken into consideration that fire protection clothing has to meet national standards, for example, the standards DIN EN 469 or SN 054551.
- As explained above, it has been found that so far, due to the lack of perspiration transport out of the inner protective outfit, the persons in question, that is to say, firefighters, are very well protected against hazards from the outside, but the wearing comfort, in spite of the multilayered structure, is not optimal from a physiological standpoint. Moreover, a large accumulation of moisture on the skin is very dangerous in case of fire since severe burns are to be feared here as a result of the steam being generated.
- Therefore, in the area of protective clothing for firefighters, there has long been a need to find materials that combine a protective function, flame retardation, as well as thermal insulation and greater wearing comfort through facilitated perspiration transport, without storing the moisture in the fiber.
- Consequently, it is the objective of the invention to provide a novel multilayered, breathable fabric that can be used for manufacturing articles of clothing, especially fire protection clothing.
- This objective is achieved by multilayered,
breathable textile fabric 1 for articles of clothing with enhanced wearing comfort owing to easy moisture transport, characterized in that thetextile fabric 1 comprises at least twoseparate layers layers thickness 7 of thefabric 1, whereby the side 6 of thelayer 3 that essentially faces the skin has the coarser individual fiber titer and the layer of the side 4 facing away from the skin has the finer individual fiber titer. -
-
Figure 1 is a top view of themultilayered fabric 1 according to the invention with the side 6 facing the skin. -
Figure 2 is a section through themultilayered fabric 1 according to the invention ofFigure 1 along Line 2-2. -
Figure 3a is a mechanical illustration of a repeating portion of a plain weave pattern of an embodiment of adobble weave fabric 1 used in the Example viewed toward skin side 6. -
Figure 3b is a mechanical illustration of a repeating unit of thefabric 1 ofFigure 3a viewed from side 4. -
Figure 3c is a symbolic weaver design of thefabric 1 ofFigures 3a and 3b . -
Figure 3d is a loom harness lifting plan for the symbolic design inFigure 3c where each column corresponds to a separate harness. - Through the intelligent structuring of the textile fabric, a good insulating effect is achieved with a relatively low square meter weight. Furthermore, the perspiration generated by the wearers is immediately transported to the side facing away from the skin (wicking effect) so that the wearer no longer experiences any feeling of wetness and no moisture can accumulate.
- In comparison to the well-established reference material according to the state of the art, namely, aramid lining material, the fabric according to the invention, while providing virtually identical thermal insulation, has a moisture absorption, relative to the square meter weight, that is about four to eight times as high in comparison to the prior art material. The time within which the drops of perspiration are absorbed is less than one second with the material according to the invention. With the conventional material, that is to say, with aramid lining material, this value is about five minutes.
- The mode of action of the
textile fabric 1 according to the invention can be described as follows. Thefabric 1 is composed of at least two separatesingle plies predefined positions 5 by the mean of selected bounding yarns which are part of theply 3 which faces away from the skin. The bounding yarns are woven or knitted or stitched through theply 2 on the skin side. The bounding yarns are visible on this predefined position on the skin side 6 in the form of dots. - The moisture formed on the skin is absorbed by the microfiber composing the bounding yarns forming the
dots 5 located on the skin side 6, it is then transported by the capillary action of the microfibers along the bounding yarns to the back of the ply orlayer 3 by means of capillary action and the preferred direction of the bounding yarns towards theply 3 facing away from the skin. On the side 6 which faces the skin it quickly evaporates due to the large surface of the waffle structure. Consequently, the side 6, which faces the skin, always remains relatively dry in comparison to normal material, for example, normal aramid lining fabric. - According to a preferred embodiment of the present invention, the multilayered,
breathable textile fabric 1 is used to manufacture an article of work clothing, for example, for firefighters. Thetextile fabric 1 consists of a base fabric, ply orlayer 2 and a microfiber fabric, ply orlayer 3, eachlayer - The warp and weft yarns for each of the
layers - If the
fabric 1 according to the invention is to be used in the leisure sector, there is, of course, no longer a need to use aramid yarn. In this case, polyester and/or polyamide yarns can then used for either or both of thelayers - According to the invention, the aramid yarns consist of aramid fibers from the group made up of Nomex®, Kevlar®, Twaron®, Technora®, and Teijinconex®. Products such as Kynol® are used as the phenol formaldehyde fibers and products such as Kermel® are used as the polyamide/polyimide fibers.
- Possible weaves are all basic woven or knit types of weaves and their variations.
- The aramid fibers are natural colored or dyed.
- According to the invention, the
fabric layers - According to the invention, in a preferred embodiment, the
breathable fabric 1 is a duplex construction comprising at least two layers orplies layers ply 3 which faces away from theskin forming dots 5 or lines or else over the entire surface, whereby in one embodiment, the pattern shown inFigure 1 can be formed. Theindividual microfiber dots 5 are each at a distance of x1 in the weft direction and x2 in the warp direction from each other as indicated in theFigure 1 . The distances x1 and x2 should be selected in such a way that a water micro droplet on the surface 6 of thelayer 2 facing the skin would touch at least one of thedots 5 or lines. The base fabric orlayer 2 according to the invention consists fundamentally of a basic woven or knit base fabric, whereby thelayers thickness 7 of thefabric 1. According to the invention, however, thefiner denier layer 3 is on the outside, that is to say, on the side 4 facing away from the skin. In particular, thislayer 3 has individual fiber titers of less than 1.3 dtex, especially less than 1 dtex. Preferably, themicrofiber layer 3 has a highly structuredsurface 10. The fibers used in thelayer 3 are microfibers, i.e., a new generation of ultrafine-titer fibers. With these microfiber yarns, one can manufacture very windproof, fine-pored, water-repellant fabrics that have a soft hand but that are good at dissipating water vapor or moisture of a perspiring person. This effect is shown inFigure 2 .Perspiration 8 formed on the skin is picked up via themicrofiber dots 5 and transported to the outside by the capillary action of the bounding yarns of the fabric 3 (wicking effect 9). This wickingeffect 9 is necessary for the transport of moisture 8 (perspiration, condensation water) from the inside 6 to the outside 4. - In one embodiment, the
textile fabric 1 can be used in a fire-protection jacket. Thetextile fabric 1 or insulating lining can be in a composite with other materials. For example, an article can be made comprising: - (A) an outer layer or shell alone or as a 2-layered or 3-layered laminate;
- (B) an intermediate water barrier layer: laminate with or without a backing layer; and
- (C) an inner fabric 1: Fritsche "Function" (according to the invention), e.g., 95% Nomex®, 5% Kevlar®, mixed with 100% aramid microfiber, square meter weight ranging from 100 to 350 g/m2, especially 280 g/m2, width ranging from 100 to 200 cm, especially 160 cm; Yarn fineness, warp and weft: Nomex® III, Paris blue Nm 40/2 for
layer 2 offabric 1 and meta-aramid microfiber natural white Nm 80/2 forlayer 3 offabric 1; and weave type for fabric 1: fabric: special double-face (layer) weave, especially Sonja 0203 pattern. -
- 1
- textile fabric according to the invention "Fritsche Function"
- 2
- base fabric, ply or layer
- 3
- microfiber ply or layer with an individual fiber titer under 1.3 dtex
- 4
- side or surface of
layer 3 facing away from the skin - 5
- microfiber dot made of microfiber bounding yarn from or of
layer 3 - 6
- side or surface of
layer 2 facing the skin - 7
- thickness of the
fabric 1 - 8
- moisture (perspiration, condensation, vapor, water)
- 9
- wicking effect
- 10
- highly structured surface of
microfiber layer 3 - x1
- distance between the microfiber dots in weft direction
- x2
- distance between the microfiber dots in warp direction
- A blend of fibers, commercially available from E. I. du Pont de Nemours and Company, Wihnington, Delaware, U.S.A., under the trade name Nomex® N301, having a cut length of 5 cm and consisting of:
- 95 wt% of pigmented poly-metaphenylene isophthalamide (meta-aramid), 1.7 dtex staple fibers; and
- 5 wt% of poly-paraphenylene terephthalamide (para-aramid) fibers, was ring spun into a single staple yarn (Y1) using conventional cotton staple processing equipment.
- Y1 had a linear density of Nm 40/1 or 250 dtex and a twist of 700 Turns Per Meter (TPM) in Z direction and it was subsequently treated with steam to stabilize its tendency to wrinkle. Two Y1 yarns were then plied and twisted together. The resulting plied and twisted yarn (TY1) had a linear density of Nm 40/2 or 500 dtex and a twist of 500 TPM in S direction. TY1 was used as warp yarn and weft yarn for the ply or
base fabric 2 facing the skin. - A fiber commercially available from E. I. du Pont de Nemours and Company, Wilmington, Delaware, U.S.A., under the trade name Nomex® T 450, having a cut length of 5 cm and consisting of 100% of poly-metaphenylene isophthalamide (meta-aramid), 1.1 dtex staple fibers, was ring spun into a single staple yarn (Y2) using conventional cotton staple processing equipment.
- Y2 had a linear density ofNm 80/1 or 125 dtex and a twist of 1070 Turns Per Meter (TPM) in Z direction and it was subsequently treated with steam to stabilize its tendency to wrinkle. Two Y2 yarns were then plied and twisted together. The resulting plied and twisted yarn (TY2) had a linear density of Nm 80/2 or 250 dtex and a twist of 750 TPM in S direction. TY2 was used as warp yarn and weft yarn for the
ply 3 facing away from the skin. TY2 were also used as the bounding yarns between the two plies as they have the highest capillarity. - TY1 and TY2 were woven into a special double-face weave according to Sonja 0203 pattern as illustrated in
Figures 3a-d . - This
fabric 1 was tested as an innerliner thermal barrier used in a multi layer structure (Garment in Table I) which further comprised (1) an intermediate water barrier layer of a polytetrafluoroethylene (PTFE) membrane laminate on a nonwoven fabric made of 85 wt-% Nomex® and 15 wt-% Kevlar® and having a specific weight of 135 g/m2 (commercially available under the trade name GORETEX® Fireblocker N from the company W. L. Gore and Associates, Delaware, U.S.A), and (2) an outershell having a specific weight of 195 g/m2 and composed of a blend of fibers, commercially available from E. I du Pont de Nemours and Company, Wilmington, Delaware, U.S.A. under the trade name Nomex® N305 having a cut length of 5 cm and consisting of: - (1) 75 % pigmented pigmented poly-metaphenylene isophthalamide (meta-aramid) 1.7 dtex staple fibers;
- (2) 23% poly-paraphenylene terephthalamide (para-aramid) fibers; and
- (3) 2 % of carbon core polyamide sheath antistatic fibers.
- This fabric combination was tested against a combination of radiant and convective heat according to the thermal protection performance (TPP) method (ISO-FDIS 17492) ASTM D-4108 (NFPA 1971).
TABLE 1 Time to 2nd Fabric Description of assembly record pain degree bum TPP rating Failure (sec) (sec) (cal/m2) Factor Sample 7 (3 layers) 9.8 16.0 32.0 5.4 - Outershell 195 (g/m2) 9.5 15.7 31.4 5.3 - Water Barrier 135 (g/m2) 9.5 15.8 31.6 5.3 - Innerliner / Thermal Barrier 265 (g/m2) avg: 9.6 avg: 15.8 avg: 31.7 avg: 5.3 Total effective wt : 595 (g/m2) - Fabric Failure Factor (FFF) is defined by 100 times the TPP rating (being the energy in (cal/cm2) measured to simulate a second-degree burn) divided by the fabric weight in g/m2. FFF =100 x TPP/ fabric weight.
- The FFF was 5.3 compared to the prior art or benchmark which is between 5.2 and 6.7.
- This FFF of 5.3 shows that the fabric of this Example can be used in thermal protective garments.
- This
fabric 1 was also tested according to a water transmission test with a water drop of 60 ml applied with a syringe on thefabric 1. The test consisted of measuring the time for the penetration and absorption. This test was repeated for theply 2 facing the skin alone without thesecond ply 3 and the bounding yarns. Results are in Table 2.TABLE 2 Sample Test Time for penetration Ply facing the skin alone Drop 1 2 sec. Drop 25 sec. Drop 33 sec. Drop 4 7 sec. Drop 53 sec. Average 4 sec. Fabric according to the invention Drop 1 immediate Drop 2 immediate Drop 3 immediate Drop 4 immediate Drop 5 immediate Average immediate Control fabric Drop 1 6 sec. Nomex® comfort Quilted with Drop 27 sec. Felt 250g/m2 Drop 3 7 sec. Drop 4 6 sec. Drop 58 sec. Average 7 sec. - This test shows that the ply facing the skin without the use of the invention is not better than a standard fabric. This test therefore confirms that the invention is dependent on the effect of the dots composed by the bounding yarns by means of capillary action and the preferred direction of the bounding yarns towards the ply facing the skin.
- This
fabric 1 was tested according to a water absorption test method. The test consisted of applying a colored water drop of 20 ml on the ply of the fabric facing the skin fabric and measured after 60 seconds the size of the drop on the each layer of the sample. Results are in Tables 3 and 4.TABLE 3 Fabric according to the invention Ply facing the skin Test Size in mm Drop 1 6 Drop 26 Drop 36 Average 6 TABLE 4 Test Minimum Size in mm after penetration Maximum size in mm after penetration Ply facing away from the skin Drop 1 25 33 Drop 227 35 Drop 326 38 Control Drop 1 0 0 Nomex® comfort Quilted with Drop 20 0 Felt 250g/ m2 Drop 3 0 0 - This test demonstrates the capacity of the fabric to diffuse the water on the ply facing away from the skin. Consequently, the ply which faces the skin, always remains relatively dry in comparison to normal material, like the control aramid lining fabric quilted with felt 250 g/m2.
- The
fabric 1 was tested against moisture absorption on porous disk method STFI-Vorschr. PE03 from the Sächsisches Textil Forschung Institute, simulating the physiological properties of a fabric in contact with a wet skin. The moisture absorption was measured in g/dm2, and the relative moisture absorption was calculated according the fabric surface weight. Thefabric 1 was also tested against the sweating guarded hot plate test ISO-11092 in order to obtain the Ret value. This fabric was compared with a control Fritsche 48101330022941 composed of a Nomex® Comfort liner of 140 g/m2 quilted with a Nomex® knitted thermal barrier of 190 g/m2. The results are in Table 5.TABLE 5 Ret (M2Pa/W) Absolute moisture absorption (g/dm2) Relative moisture absorption (%) Fabric 15.78 7.7 255 Function Control 6.86 2.4 67.5 Fritsche 48101330022941 - These results are demonstrating that the fabric has a moisture absorption, relative to the square meter weight, that is about four times as high in comparison to the prior art material. These are good results and they show that the
fabric 1 will easily pick up the moisture away from the skin of the wearer. The Ret value of 5.78 is rated as very good (<6 very good, 6-13 good, 13-20 sufficient, >20 insufficient) and demonstrates that thisfabric 1 is very breathable. - This
fabric 1 was tested according to the contact heat resistance test in accordance with prEN 702. The threshold time tt(sec) at 100 °C was measured at 19.8 sec and was significantly better than a standard fabric out of Nomex® N 307 having tt(sec) at 100 °C value of 18.4 sec. - The articles of clothing according to the invention can be made up as desired.
- The fabric according to the invention is, of course, not limited to the use for manufacturing protective clothing. In particular, the fabric can be used to manufacture leisure clothing, especially to manufacture functional undergarments.
Claims (16)
- Multilayered, breathable textile fabric (1) for articles of clothing with enhanced wearing comfort owing to easy moisture transport, characterized in that the textile fabric (1) comprises at least two separate layers (2,3), the two separate layers being bonded to each other at predefined positions (5) by means of selected bounding yarns which are part of the layer (3) which faces away from the skin, the bounding yarns being woven or knitted or stitched through the ply (2) on the skin side, whose warp and weft yarns consist of aramid yarns or aramid twisted threads or aramid filament yarns or yarns made of blended fibers containing polybenzimidazole and aramid fibers, whereby the layers (2,3) have different individual fiber degrees of fineness in order to bring about a fineness gradient over the thickness (7) of the fabric (1), whereby the side (6) of the layer (2) that essentially faces the skin has the coarser individual fiber titer and the layer of the side (4) facing away from the skin has the finer individual fiber titer.
- The textile fabric according to Claim 1, characterized in that the layer (2) is a woven, a knitted fabric or a warp knitted fabric.
- The textile fabric according to Claim 1, characterized in that the second layer (3) is a woven, a knitted fabric or a warp knitted fabric.
- The textile fabric according to Claim 1, 2 or 3, characterized in that all of the layers (2,3) have a structure exhibiting at least two different individual fiber finenesses.
- The textile fabric according to Claim 1 to 4, characterized in that it is a duplex construction with two layers bonded to each other.
- The textile fabric according to one of Claims 1 to 5, characterized in that the layer (2) as well as the layer (3) are visible on the side (6) facing the skin, whereby, however, the surface proportion can vary.
- The textile fabric according to one of Claims 1 to 6, characterized in that the re-drying time of the side (6) facing the skin is optimally shortened by the combination of extremely fine fibers and a large surface area of the article.
- The textile fabric according to one of the preceding Claims 1 to 7, characterized in that the two layers (2,3) are bonded to each other by a special double-face weave, by a special double-face knit or by a special double-face warp knit.
- The textile fabric according to one of the preceding Claims 1 to 8, characterized in that the layers (2,3) have a square meter weight in the range from 50g/m2 to 450g/m2, whereby the square meter weight of the individual layers can be identical or different.
- The textile fabric according to one of the preceding Claims 1 to 9, characterized in that the layer (3) is arranged on the outside (4) or on the side (4) facing away from the skin and in that it has an individual fiber titer of less than 1.3 dtex.
- The textile fabric according to Claim 1, characterized in that the warp yarns comprise multifilament aramid yarns or multifilament aramid twisted yarns or aramid filament yarns and the weft yarns alternately comprise multifilament aramid yarns or multifilament aramid twisted yarns or aramid filament yarns.
- The textile fabric according to Claim 1 or 11, characterized in that the multifilament aramid yarns or multifilament aramid twisted threads or aramid filament yarns present in the weft yarns are similar or identical to one of the two alternately arranged, different multifilament yarns or multifilament twisted threads or aramid filament yarns that form the warp yarns.
- The textile fabric according to Claim 1 or 12, characterized in that the aramid yarn contains fibers that are selected from the group consisting ofpoly-m-phenylene isophthalamide fibers, poly-p-phenylene terephthalamide fibers or mixtures of poly-m-phenylene isophthalamide and poly-p-phenylene terephthalamide fibers.
- An article of clothing, characterized by a structure consisting of at least one two-layered textile composite having an inner layer, optionally a middle layer, made of a polyester or polyamide or aramid microfiber fabric, and an outer layer, whereby the multilayered, breathable textile fabric according to one of Claims 1 to 13 forms the inner layer.
- An article of work clothing for protection against the effects of heat, flames or electric arc and having a textile cover layer made of high-temperature-resistant fibers, characterized by a structure made up of at least a two-layered textile composite having an inner layer, optionally a middle layer made of a polyester or polyamide or aramid microfiber fabric, and an outer layer consisting of a textile material made of high-temperature-resistant fibers, whereby the inner layer contains a multilayered, breathable textile fabric according to one of Claims 1 to 13.
- The article of work clothing according to Claim 15, characterized in that it is a fireproof jacket or fireproof pants.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10248999 | 2002-10-21 | ||
DE10248999A DE10248999B3 (en) | 2002-10-21 | 2002-10-21 | Multi-layer, breathable textile fabric |
PCT/US2003/033701 WO2004037027A1 (en) | 2002-10-21 | 2003-10-21 | Multilayered, breathable textile fabric |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1555902A1 EP1555902A1 (en) | 2005-07-27 |
EP1555902B1 true EP1555902B1 (en) | 2008-02-27 |
Family
ID=32087062
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03777848A Expired - Lifetime EP1555902B1 (en) | 2002-10-21 | 2003-10-21 | Multilayered, breathable textile fabric |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP1555902B1 (en) |
JP (1) | JP4344697B2 (en) |
KR (1) | KR101210061B1 (en) |
CN (1) | CN100405941C (en) |
AU (1) | AU2003286641A1 (en) |
BR (1) | BR0314494B1 (en) |
CA (1) | CA2503014C (en) |
DE (2) | DE10248999B3 (en) |
ES (1) | ES2300629T3 (en) |
MX (1) | MXPA05004160A (en) |
WO (1) | WO2004037027A1 (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2416781A (en) * | 2004-08-04 | 2006-02-08 | Lightex Ltd | Breathable fabric |
ES2327883B1 (en) * | 2006-07-18 | 2010-09-06 | Tejidos Estambril, S.A. | THERMAL PROTECTION FABRIC. |
DE102006052695A1 (en) | 2006-11-07 | 2008-05-08 | Ofa Bamberg Gmbh | Flexible thread for knitted fabric or interlaced yarn for supporting and/or compressing e.g. socks, has winding thread exhibiting material that absorbs heat energy if ambient temperature is higher than upper limit temperature |
CN101126190B (en) * | 2007-09-25 | 2011-02-16 | 山东滨州亚光毛巾有限公司 | Method for producing untwisted towel |
US7744999B2 (en) * | 2008-07-11 | 2010-06-29 | E. I. Du Pont De Nemours And Company | Crystallized meta-aramid blends for improved flash fire and arc protection |
CN102177016B (en) * | 2008-08-28 | 2015-11-25 | 泰科保健集团有限合伙公司 | Antimicrobial fibre and correlated product and method |
CN101973148B (en) * | 2010-08-20 | 2014-02-12 | 圣欧芳纶(江苏)股份有限公司 | Arc protection fabric, manufacturing method and application thereof |
WO2012126102A1 (en) * | 2011-03-22 | 2012-09-27 | Barrday Inc. | Multilayer fabric platform designed for flame and thermal protection |
KR101237692B1 (en) * | 2011-05-25 | 2013-02-26 | 유건영 | duble knitting for cut gloves |
EP3385418B1 (en) | 2015-12-02 | 2021-07-14 | Teijin Limited | Fabric and protective product |
CN105350341A (en) * | 2015-12-04 | 2016-02-24 | 江南大学 | Heat-insulating fabric production method |
JP6666129B2 (en) * | 2015-12-11 | 2020-03-13 | 帝人株式会社 | Fabrics and textile products |
WO2018153844A1 (en) * | 2017-02-27 | 2018-08-30 | Teijin Aramid Gmbh | Textile fabric and workwear manufactured thereof |
EP3901339B1 (en) | 2018-12-17 | 2023-07-05 | Teijin Limited | Cloth and protective product |
JP7311314B2 (en) * | 2019-05-30 | 2023-07-19 | 帝人株式会社 | Two-layer fabric and thermal protective clothing using same |
CN111764020B (en) * | 2020-05-27 | 2022-02-18 | 深圳全棉时代科技有限公司 | Multilayer gauze jacquard fabric, air conditioning quilt and fabric product |
Family Cites Families (10)
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US3272685A (en) * | 1964-05-05 | 1966-09-13 | Kagan Joseph | Woven waterproof fabrics |
JPS63145496A (en) * | 1986-12-02 | 1988-06-17 | 日本フイルコン株式会社 | Papermaking multilayer fabric |
US5294258A (en) | 1992-04-08 | 1994-03-15 | Nordson Corporation | Apparatus for producing an integral adhesive matrix |
DE9205214U1 (en) * | 1992-04-15 | 1992-06-11 | Scheibler Peltzer Gmbh & Co, 4150 Krefeld | Three-layer textile web |
US5468537A (en) * | 1993-09-30 | 1995-11-21 | E. I. Du Pont De Nemours And Company | Protective garments comprising an outer shell fabric of woven aramid fibers which elongate when exposed to a flame |
DE69426397T2 (en) * | 1994-09-13 | 2001-07-19 | Lion Apparel, Inc. | PROTECTIVE CLOTHING WITH A CLOSED CELL INSIDE LAYER |
DE29501651U1 (en) * | 1995-02-02 | 1995-04-13 | Handschuhfabrik Seiz GmbH & Co. KG, 72555 Metzingen | Protective glove |
JPH0942894A (en) * | 1995-08-02 | 1997-02-14 | Toray Ind Inc | Anti-blade cloth |
DE19547704C2 (en) * | 1995-12-20 | 1999-03-25 | Patrick Yeh | Composite textile with moisture-wicking properties |
WO2002018702A2 (en) * | 2000-08-30 | 2002-03-07 | Warwick Mills, Inc. | Methods for improving the dyeability and puncture resistance of fabrics comprising high tenacity fibers and fabrics produced by such methods |
-
2002
- 2002-10-21 DE DE10248999A patent/DE10248999B3/en not_active Expired - Fee Related
-
2003
- 2003-10-21 MX MXPA05004160A patent/MXPA05004160A/en active IP Right Grant
- 2003-10-21 EP EP03777848A patent/EP1555902B1/en not_active Expired - Lifetime
- 2003-10-21 CN CNB2003801018036A patent/CN100405941C/en not_active Expired - Fee Related
- 2003-10-21 JP JP2004547107A patent/JP4344697B2/en not_active Expired - Fee Related
- 2003-10-21 BR BRPI0314494-1A patent/BR0314494B1/en not_active IP Right Cessation
- 2003-10-21 WO PCT/US2003/033701 patent/WO2004037027A1/en active IP Right Grant
- 2003-10-21 DE DE60319400T patent/DE60319400T2/en not_active Expired - Lifetime
- 2003-10-21 ES ES03777848T patent/ES2300629T3/en not_active Expired - Lifetime
- 2003-10-21 CA CA2503014A patent/CA2503014C/en not_active Expired - Fee Related
- 2003-10-21 KR KR1020057006793A patent/KR101210061B1/en not_active IP Right Cessation
- 2003-10-21 AU AU2003286641A patent/AU2003286641A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
JP4344697B2 (en) | 2009-10-14 |
DE10248999B3 (en) | 2004-05-06 |
DE60319400T2 (en) | 2009-03-12 |
JP2007535415A (en) | 2007-12-06 |
CA2503014C (en) | 2011-07-26 |
KR20050073566A (en) | 2005-07-14 |
BR0314494A (en) | 2005-08-02 |
MXPA05004160A (en) | 2005-06-22 |
ES2300629T3 (en) | 2008-06-16 |
BR0314494B1 (en) | 2012-12-25 |
WO2004037027A1 (en) | 2004-05-06 |
AU2003286641A1 (en) | 2004-05-13 |
EP1555902A1 (en) | 2005-07-27 |
CN1705445A (en) | 2005-12-07 |
CN100405941C (en) | 2008-07-30 |
DE60319400D1 (en) | 2008-04-10 |
CA2503014A1 (en) | 2004-05-06 |
KR101210061B1 (en) | 2012-12-07 |
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