EP1694895B1 - A composite nonwoven material containing continuous filaments and short fibres - Google Patents
A composite nonwoven material containing continuous filaments and short fibres Download PDFInfo
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- EP1694895B1 EP1694895B1 EP04800360A EP04800360A EP1694895B1 EP 1694895 B1 EP1694895 B1 EP 1694895B1 EP 04800360 A EP04800360 A EP 04800360A EP 04800360 A EP04800360 A EP 04800360A EP 1694895 B1 EP1694895 B1 EP 1694895B1
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- filaments
- fibres
- continuous filaments
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 230000010354 integration Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
- D04H5/02—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by mechanical methods, e.g. needling
- D04H5/03—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length strengthened or consolidated by mechanical methods, e.g. needling by fluid jet
Definitions
- the present invention relates to a composite nonwoven material according to the preamble of claim 1 and a method of manufacturing a nonwoven material according to the preamble of claim 8.
- a nonwoven material for wiping applications should be strong, absorbent, abrasion resistant and exhibit low linting, i.e. fibres should not loosen from the material during normal use.
- Nonwoven materials One way of manufacturing nonwoven materials is to use hydroentangling or spunlacing to mix and bond the constituents in the material. Hydroentangling is e.g. described in CA patent No. 841 938 . It is known to produce composite nonwoven materials comprising continuous filaments and short fibres by hydroentangling, see for example EP-E31-0 333228 , EP-B1- 0 938 601 and WO 99/20821 .
- a problem encountered in the manufacture of such composite materials is that it is difficult to obtain a good integration of the continuous filaments and short fibres only by hydroentangling which results in that the composite materials produced often have a more or less pronounced two-sidedness, i.e. one side predominately containing short fibres and the other predominately containing continuous filaments.
- Such two-sidedness have several drawbacks. Firstly, the bonding of the filaments and short fibres will be weaker than in a composite material in which the short fibres and continuous filaments are well integrated, i.e. homogeneously mixed, the strength in the direction of thickness will be low and there is a risk that the composite delaminate if the two-sidedness is pronounced.
- the "short fibre side" of such a material will be sensitive to linting, i.e. that fibres loosen from the surface, and the "filament side” will be sensitive to "pilling” when abraded, i.e. that parts of the filaments will be protruding from the surface of this side.
- WO 99/20821 the problem associated with poor mixing of the materials is solved by applying a bonding material to at least one side of a hydraulically entangled web comprising a fibrous component and a nonwoven layer of substantially continuous filaments. Also in US-A-5,389,202 a bonded web of continuous filaments is used. In EP-B1- 0 333 228 this problem is solved by co-deposition of an admixture of non-elastic meltblown filaments and fibre material on a conveyer surface. The fibrous material is intermingled with the meltblown fibres just after extruding of the material of the meltblown fibres through the meltblowing die so that the materials are thoroughly mixed before the entangling.
- EP-B1-0 938 601 it is known to manufacture a nonwoven material by foam forming a fibrous web of natural and/or synthetic staple fibres directly on a layer of unbonded continuous filaments and hydroentangling together the foamed fibre dispersion with the continuous filaments for forming a composite material.
- foamforming there is achieved an improved mixing of the natural and/or synthetic fibres with synthetic filaments before the entangling.
- a drawback of this method is the necessity of equipment for foamforming and for taking care of the surfactants used for the foam forming, which circulates in the water circuit.
- the web of continuous filaments is too dense, it is difficult to get a good integration of the short fibres in the material.
- the material will then be more like a laminate than a composite having one side predominately containing short fibres and the other side predominately containing continuous filaments. In such a material the bonding of the continuous filaments will be poor and the side predominately containing short fibres will be sensitive to abrasion and linting.
- the objective of the present invention is to provide a composite nonwoven material containing continuous filaments and short fibres in which the continuous filaments and short fibres are well integrated in the material and which can be produced by a method of manufacturing which is cost effective and by which it is ensured that the integration of the filaments and fibres can be performed by entangling without the need of a premixing step of filaments and fibres.
- a nonwoven composite material according to claim 1 By ensuring that the web of continuous filaments used in the manufacture of such a material be neither too open or too dense a nonwoven composite material composed of continuous filaments and short fibres in which the filaments and fibres are well integrated can be obtained by entangling without a pre-mixing step and with a low consumption of energy. Such a composite will have similar properties on both sides thereof.
- the short fibres comprises natural fibres and/or synthetic staple fibres.
- the short fibres comprise at least 60 weight% of cellulose fibres, preferably at least 70 weight%, more preferably at least 75 weight% and most preferably at least 85 weight%.
- the short fibres comprise 85-95 weight% of cellulose fibres, preferably about 90 weight%.
- the content of continuous filaments in the material is preferably about 25-40 weight%.
- the basis weight of the material is 40-100 g/m 2 , preferably 50-80 g/m 2 and the short fibres are preferably wetlaid fibres.
- the invention also relates to a method of manufacturing a nonwoven material according to claim 8.
- the energy supply at the hydroentangling is at the most about 500 kWh/ton, preferably about 300-400 kWh/ton and most preferably about 350 kWh/ton.
- FIG. 1 schematically illustrates a process line for manufacturing a nonwoven material according to a preferred embodiment of the method according to the invention.
- a web of unbonded continuous filaments is laid on a transport belt 1.
- the transport belt I is air-permeable and can for example consist of a woven forming fabric or a wire.
- the continuous filaments laid onto the transport web are delivered by a conventional device 2 for producing spunbond filaments.
- Spunbond filaments are produced by extruding a molten polymer through a spinneret which can have 3000-5000 holes/m width with a typical diameter of 0.5 mm.
- the extruded polymer is then accelerated by high speed air either by a slot drawing attenuator or by quench air.
- the slot drawing attenuator works as a wide ejector and is fed with compressed air that is released in a narrow gap resulting in a very high air velocity (10000-20000 m/min). Very high filaments velocities up to 6000 m/min can be obtained.
- the velocity of the air is increased by narrowing the width of the attenuation chamber.
- filament velocities up to 4000 m/min can be obtained.
- the velocity of the filaments decrease and they are sucked and laid down onto the transport web 1.
- the production of spunbonded nonwoven webs is described in patents, such as US-A-5,389,202 , US-A-4,340,563 and US-A-3,692,618 .
- the continuous filaments When the continuous filaments are delivered to the transport web 1 they normally have a diameter of 10-50 ⁇ m.
- the continuous filaments are delivered to the transport web with a much higher velocity than the velocity of the transport web, for example the velocity of the filaments is 2000-4000 m/min and the velocity of the transport web is 100-300 m/min. This means that the filaments will form irregular loops and bends on the transport web so that a randomised web 4 of continuous filaments is obtained.
- a suction box 3 is disposed under the air permeable transport web 1, whereby the filaments will be drawn against the transport web by the suction provided and the web of continuous filaments will assume a more or less two-dimensional appearance, i.e. that loops or bends of filaments upstanding from transport web at the deliverance thereto will be drawn by the suction to a horizontal or near horizontal position.
- filaments that are spunlaid on the transport web are unbonded and free to move relative to each other.
- the filaments consist of preferably of polypropylene or polyesters but can also consist of other polymeres, such as polyethylene, or polyamides and polyactides. Copolymers of these polymers may also be used, as well as natural polymers with thermoplastic properties. All thermoplastic polymers are in principle possible to use.
- the web 4 of continuous filaments is then advanced to a device 5 for wetlaying a layer 6 of short fibres onto the web 4 of filaments.
- This device is also of conventional construction.
- the layer 6 of short fibres consists preferably of natural fibres, preferably cellulose fibres, or a mixture of natural fibres and staple fibres.
- the cellulose fibres are preferably wood pulp fibres but any type of cellulose fibres is possible to use, such as grass or straw. Both softwood fibres and hardwood fibres are suitable.
- the staple fibres can be synthetic fibres made from the same materials as the continuous filaments and copolymers of these materials can of course also be used. It is also possible to use regenerated cellulose fibres, such as rayon, lyocell.
- the short fibres should comprise at least 60 weight% of cellulose fibres, preferably at least 70 weight%, more preferably at least 75 weight% and most preferably at least 85 weight%.
- the short fibres comprise 85-95 weight% of cellulose fibres, preferably about 90 weight%.
- the web 4 of continuous filaments and the layer 6 of fibres laid thereon are then advanced to a hydroentangling device 7.
- a hydroentangling device 7 In such a device, several manifolds of water jets under high pressure, such as 50-120 bars, are directed against the fibre layer 6 and web 4 of filaments. During this step the fibres and filaments will mix and entangle with each other, with other fibres and with filaments.
- the mixed nonwoven material obtained in the entangling step is advanced to a drying device 8.
- This device can be of conventional construction, such as a through-air drier.
- the continuous filaments in the web 4 are unbonded to each other.
- unbonded means that the continuous filaments in the web 4 are free to move relative to each other, i.e. the possible attachments of filaments to each other due to possible remaining stickiness when the filaments are laid onto the transport web 1 are so weak that such possible attachments will be broken when the filaments are hit by the water jets.
- a great advantage by the use of a layer of unbonded continuous filaments is that the entangling can be performed with a low energy consumption in the hydroentangling step compared to the energy consumption of a layer of continuous filaments thermobonded to each other.
- the energy supply at the entangling is in the present invention at the most about 500 kWh/ton, preferably about 300-400 kWh/ton and most preferably about 350 kWh/ton.
- the energy supply at the hydroentangling is calculated as the product of water flow (l/min) and pressure during entangling (bar) divided by the amount of produced material per hour (kg/h).
- Another reason for the use of a layer of unbonded continuous filaments in the present invention is that it has been proven very difficult to obtain a good enough integration of short fibres and continuous filaments with a layer of bonded continuous filaments even if several entangling steps are used. This is probably caused by the passages between bonded portions of adjacent filaments very quickly gets occupied by short fibres which prevent penetration of short fibres through the filament layer later during the entangling process.
- the known use of a layer of bonded continuous filaments therefore has a tendency to produce nonwoven composites with a more or less pronounced two-sidedness.
- bonds between the fibres and filaments in a nonwoven material manufactured by the process described above will thus mainly be mechanical bonds due to entangling of fibres and filaments.
- hydrogen bonds between cellulosic fibres will be present in the material.
- the integration of the two layers i.e. the web of continuous filaments 1 and the fibre layer 6, is however very critical. If the two layers are not integrated well, also this material will have a pronounced two-sided appearance and the bonding of the continuous filaments will be poor. Such a material will have a reduced strength, especially in the direction of thickness.
- the short fibre side of such a two-sided material will have a high linting, i.e. a tendency for the short fibres to loosen from material.
- the bonds on the short fibre side will predominately consist of bonds between short fibres and the strength of the material on the short fibre side will be poor.
- the filament side of such a material will be sensitive to "piling" while abraded, i.e. portions and ends of filaments will have a tendency to be projecting out From the surface of the filament side of the material.
- a composite nonwoven material containing short fibres and continuous filaments only bonded by entangling, in which the integration of short fibres and continuous filaments have failed to some extent, will thus have worse properties than a similar material containing short fibres and continuous filaments prebonded to each other before the entangling step.
- the entangling step starts the structure of layer 4 of continuous filaments is relatively open and it is easy for the water jets to move the short fibres in the layer 6 overlaying the filaments into the filament layer through the width thereof.
- the more short fibres that are moved into the filament layer the less space is available for easy transport of short fibres remaining on top of the filament layer.
- the period during entangling in which short fibres can be moved into the filament layer is prolonged compared to the period for a prebonded filament layer. The mixing of short fibres and continuous filament thus mainly occurs in the beginning of the entangling step.
- the entangling can thus be said to contain a mixing step followed by a bonding step. Of course some bonding will occur during the mixing step but most of the bonds will be obtained after the short fibres have been mixed with the continuous filaments.
- the inventors have found that to obtain a composite nonwoven material in which the two layers 4 and 6 are well integrated and which have high strength and an even basis weight distribution, the web of continuous filaments should have a projected coverage of between 1.3-1.6.
- the projected coverage is the sum of projected surface area of all filaments in one unit area and is obtained by multiplying the sum of lengths of filaments in one unit area with the average diameter of the filaments.
- the filaments in a web of continuous filaments having a projected coverage of 1.0 would thus cover the whole unit area if they were placed in one layer in straight lines adjacent to each other and in one layer.
- the nonwoven materials are 80 gsm spunlaid composites comprising 25% (20gsm) continuous spunlaid filaments of polypropylene and pulp fibres with or without 10% of 19 mm long, 1.7 dtex staple fibres of polyester mixed therein.
- the nonwoven materials were manufactured in the following way. A 0.4 m wide web of spunlaid filaments was laid down onto a forming fabric at 20m/min such that the filaments were not bonded to each other.
- the Taber resistance values refer to the pulp side of the composite nonwoven material.
- the strength of the pulp side is optimised at a projected coverage between 1.3 and 1.5 corresponding to filament titre of 3.2 and 2.5 dtex (g/10 000 m), respectively.
- the integration or mixing of fibres and filaments in the material was not good, resulting in very poor surface strength on the pulp side of the material.
- the structure of the filament web became too open to hold the pulp and the surface strength of the pulp side became poor.
- the Taber abrasion resistance is measured by Taber test equipment 5151 with two rubber wheel CS-10. Such equipment is well known to the skilled man and need not be described in detail.
- the testing is performed by mounting a circular test sample of the nonwoven material on a rotatable disk on the Taber test equipment. In the test, the test sample is subjected to the pressure of the two rubber wheel running on the top surface of the test sample. Depending on the basis weight of the test sample the disk is rotated with a different number of revolutions, the number of revolutions increasing with increased basis weight of the test sample.
- the Taber value of a tested sample is determined by visual comparison with a scale, i.e. five reference samples having Taber values 1-5, where 1 defines a very poor abrasion resistance and 3 defines an acceptable abrasion resistance.
- Table 2 there is shown Taber values for three nonwoven materials, manufactured as described above, having different basis weight and content of continuous filaments.
- the continuous filaments are spunbond filaments of polypropylene and the short fibres are pulp fibres.
- the Taber value in the table represents the average of two identical test samples.
- the projected coverage lies between 1.1 and 1.6 well integrated composite nonwovens can be provided for nonwovens with a basis weight of 80 g/m 2 or more.
- the projected coverage shall be at least 1.2 in order for an acceptable material to be provided.
- acceptable nonwovens are provided even for nonwovens with a low basis weight and high content of continuous filaments.
- the ideal projected coverage lie between 1.3-1.6
- filament titre is shown as function of spunlaid content and coverage in Tables 3-5.
- COV The projected coverage
- the projected surface area is obtained by multiplying the total length (L) of all spunlaid filaments with the average diameter (d) in m of all spunlaid filaments within the unit area.
- a projected L * d
- the total length of the filaments within the unit area is obtained by dividing the total weight of spunlaid filaments with the average filament titre (Titre) in dtex as shown in equation (3) below.
- the weight of the spunlaid filament web is obtained by myltiplying the basis weight of the spunlaid filament (BW S ) web in g/m 2 with the unit area (A).
- the filament titre in dtex is the weight of the filaments corresponding 10 000 m, i.e. g/10 000m.
- L B ⁇ W S Titre ⁇ * A * 10000
- L BW * X * A 100 * Titre * 10000
- the specific gravity for polypropylene is around 900 kg/m 3 for polyester around 1350 kg/m 3 .
- the ideal projected coverage is the product of filament length and average diameter of the filaments, the ideal projected coverage can be obtained by varying the filament length/m 2 , i.e. the velocity by which the filaments are laid on the transport web 1, or the diameter of the filaments. It is thus relatively easy for a skilled man to adapt the process parameters within the given limits.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Multicomponent Fibers (AREA)
Abstract
Description
- The present invention relates to a composite nonwoven material according to the preamble of claim 1 and a method of manufacturing a nonwoven material according to the preamble of claim 8.
- A nonwoven material for wiping applications should be strong, absorbent, abrasion resistant and exhibit low linting, i.e. fibres should not loosen from the material during normal use.
- One way of manufacturing nonwoven materials is to use hydroentangling or spunlacing to mix and bond the constituents in the material. Hydroentangling is e.g. described in
CA patent No. 841 938 . It is known to produce composite nonwoven materials comprising continuous filaments and short fibres by hydroentangling, see for example ,EP-E31-0 333228 EP-B1- 0 938 601 and .WO 99/20821 - A problem encountered in the manufacture of such composite materials is that it is difficult to obtain a good integration of the continuous filaments and short fibres only by hydroentangling which results in that the composite materials produced often have a more or less pronounced two-sidedness, i.e. one side predominately containing short fibres and the other predominately containing continuous filaments. Such two-sidedness have several drawbacks. Firstly, the bonding of the filaments and short fibres will be weaker than in a composite material in which the short fibres and continuous filaments are well integrated, i.e. homogeneously mixed, the strength in the direction of thickness will be low and there is a risk that the composite delaminate if the two-sidedness is pronounced. Moreover, the "short fibre side" of such a material will be sensitive to linting, i.e. that fibres loosen from the surface, and the "filament side" will be sensitive to "pilling" when abraded, i.e. that parts of the filaments will be protruding from the surface of this side.
- In
the problem associated with poor mixing of the materials is solved by applying a bonding material to at least one side of a hydraulically entangled web comprising a fibrous component and a nonwoven layer of substantially continuous filaments. Also inWO 99/20821 US-A-5,389,202 a bonded web of continuous filaments is used. InEP-B1- 0 333 228 this problem is solved by co-deposition of an admixture of non-elastic meltblown filaments and fibre material on a conveyer surface. The fibrous material is intermingled with the meltblown fibres just after extruding of the material of the meltblown fibres through the meltblowing die so that the materials are thoroughly mixed before the entangling. - From
EP-B1-0 938 601 it is known to manufacture a nonwoven material by foam forming a fibrous web of natural and/or synthetic staple fibres directly on a layer of unbonded continuous filaments and hydroentangling together the foamed fibre dispersion with the continuous filaments for forming a composite material. Through the foamforming there is achieved an improved mixing of the natural and/or synthetic fibres with synthetic filaments before the entangling. A drawback of this method is the necessity of equipment for foamforming and for taking care of the surfactants used for the foam forming, which circulates in the water circuit. - By the use of a layer of unbonded continuous filaments it is easier to obtain a well integrated material than with a layer of bonded continuous filaments, whereby the energy consumption in the entangling step will be less than is needed to integrate fibres with a layer of bonded continuous filaments. However, it has been showed that the properties of the material obtained by such a manufacturing method is very sensitive to the amount and size of the continuous filaments in the web of continuous filaments with which the layer of short fibres should be integrated. If the web of continuous filaments is too open, it is a risk that short fibres are flushed out of the material in the entangling step. This can lead to holes in the material and an uneven basis weight distribution in the material obtained. If the web of continuous filaments is too dense, it is difficult to get a good integration of the short fibres in the material. The material will then be more like a laminate than a composite having one side predominately containing short fibres and the other side predominately containing continuous filaments. In such a material the bonding of the continuous filaments will be poor and the side predominately containing short fibres will be sensitive to abrasion and linting.
- The objective of the present invention is to provide a composite nonwoven material containing continuous filaments and short fibres in which the continuous filaments and short fibres are well integrated in the material and which can be produced by a method of manufacturing which is cost effective and by which it is ensured that the integration of the filaments and fibres can be performed by entangling without the need of a premixing step of filaments and fibres.
- This objective is according to the invention accomplished by a nonwoven composite material according to claim 1. By ensuring that the web of continuous filaments used in the manufacture of such a material be neither too open or too dense a nonwoven composite material composed of continuous filaments and short fibres in which the filaments and fibres are well integrated can be obtained by entangling without a pre-mixing step and with a low consumption of energy. Such a composite will have similar properties on both sides thereof.
- In a preferred embodiment the short fibres comprises natural fibres and/or synthetic staple fibres. Preferably, the short fibres comprise at least 60 weight% of cellulose fibres, preferably at least 70 weight%, more preferably at least 75 weight% and most preferably at least 85 weight%. Advantageously, the short fibres comprise 85-95 weight% of cellulose fibres, preferably about 90 weight%. The content of continuous filaments in the material is preferably about 25-40 weight%. The basis weight of the material is 40-100 g/m2, preferably 50-80 g/m2 and the short fibres are preferably wetlaid fibres.
- The invention also relates to a method of manufacturing a nonwoven material according to claim 8.
- In a preferred embodiment the energy supply at the hydroentangling is at the most about 500 kWh/ton, preferably about 300-400 kWh/ton and most preferably about 350 kWh/ton.
- The invention will now be described with reference to the enclosed
Figure 1 , which schematically illustrates a process line for manufacturing a nonwoven material according to a preferred embodiment of the method according to the invention. - In the process line schematically illustrated in
Figure 1 , a web of unbonded continuous filaments is laid on a transport belt 1. The transport belt I is air-permeable and can for example consist of a woven forming fabric or a wire. The continuous filaments laid onto the transport web are delivered by aconventional device 2 for producing spunbond filaments. - Spunbond filaments are produced by extruding a molten polymer through a spinneret which can have 3000-5000 holes/m width with a typical diameter of 0.5 mm. The extruded polymer is then accelerated by high speed air either by a slot drawing attenuator or by quench air. The slot drawing attenuator works as a wide ejector and is fed with compressed air that is released in a narrow gap resulting in a very high air velocity (10000-20000 m/min). Very high filaments velocities up to 6000 m/min can be obtained. As the filaments are drawn by quench air in a closed system, the velocity of the air is increased by narrowing the width of the attenuation chamber. By this process filament velocities up to 4000 m/min can be obtained. After filaments have left the slot drawing attenuator or the narrowest passage in the quench chamber, the velocity of the filaments decrease and they are sucked and laid down onto the transport web 1. The production of spunbonded nonwoven webs is described in patents, such as
US-A-5,389,202 ,US-A-4,340,563 andUS-A-3,692,618 . - When the continuous filaments are delivered to the transport web 1 they normally have a diameter of 10-50 µm. The continuous filaments are delivered to the transport web with a much higher velocity than the velocity of the transport web, for example the velocity of the filaments is 2000-4000 m/min and the velocity of the transport web is 100-300 m/min. This means that the filaments will form irregular loops and bends on the transport web so that a randomised web 4 of continuous filaments is obtained.
- A suction box 3 is disposed under the air permeable transport web 1, whereby the filaments will be drawn against the transport web by the suction provided and the web of continuous filaments will assume a more or less two-dimensional appearance, i.e. that loops or bends of filaments upstanding from transport web at the deliverance thereto will be drawn by the suction to a horizontal or near horizontal position.
- It is essential for the present invention that the filaments that are spunlaid on the transport web are unbonded and free to move relative to each other.
- The filaments consist of preferably of polypropylene or polyesters but can also consist of other polymeres, such as polyethylene, or polyamides and polyactides. Copolymers of these polymers may also be used, as well as natural polymers with thermoplastic properties. All thermoplastic polymers are in principle possible to use.
- The web 4 of continuous filaments is then advanced to a device 5 for wetlaying a layer 6 of short fibres onto the web 4 of filaments. This device is also of conventional construction.
- The layer 6 of short fibres consists preferably of natural fibres, preferably cellulose fibres, or a mixture of natural fibres and staple fibres. The cellulose fibres are preferably wood pulp fibres but any type of cellulose fibres is possible to use, such as grass or straw. Both softwood fibres and hardwood fibres are suitable. The staple fibres can be synthetic fibres made from the same materials as the continuous filaments and copolymers of these materials can of course also be used. It is also possible to use regenerated cellulose fibres, such as rayon, lyocell.
- The short fibres should comprise at least 60 weight% of cellulose fibres, preferably at least 70 weight%, more preferably at least 75 weight% and most preferably at least 85 weight%. Advantageously, the short fibres comprise 85-95 weight% of cellulose fibres, preferably about 90 weight%.
- The web 4 of continuous filaments and the layer 6 of fibres laid thereon are then advanced to a hydroentangling device 7. In such a device, several manifolds of water jets under high pressure, such as 50-120 bars, are directed against the fibre layer 6 and web 4 of filaments. During this step the fibres and filaments will mix and entangle with each other, with other fibres and with filaments.
- Finally, the mixed nonwoven material obtained in the entangling step is advanced to a drying device 8. This device can be of conventional construction, such as a through-air drier.
- As stated before it is essential for the present invention that the continuous filaments in the web 4 are unbonded to each other. By unbonded means that the continuous filaments in the web 4 are free to move relative to each other, i.e. the possible attachments of filaments to each other due to possible remaining stickiness when the filaments are laid onto the transport web 1 are so weak that such possible attachments will be broken when the filaments are hit by the water jets. A great advantage by the use of a layer of unbonded continuous filaments is that the entangling can be performed with a low energy consumption in the hydroentangling step compared to the energy consumption of a layer of continuous filaments thermobonded to each other. This is due to the fact that unbonded filaments are easy to move by the water jets compared to bonded filaments, the movements of which usually will involve movements of other filaments bonded thereto. The energy supply at the entangling is in the present invention at the most about 500 kWh/ton, preferably about 300-400 kWh/ton and most preferably about 350 kWh/ton. The energy supply at the hydroentangling is calculated as the product of water flow (l/min) and pressure during entangling (bar) divided by the amount of produced material per hour (kg/h).
- Another reason for the use of a layer of unbonded continuous filaments in the present invention is that it has been proven very difficult to obtain a good enough integration of short fibres and continuous filaments with a layer of bonded continuous filaments even if several entangling steps are used. This is probably caused by the passages between bonded portions of adjacent filaments very quickly gets occupied by short fibres which prevent penetration of short fibres through the filament layer later during the entangling process. The known use of a layer of bonded continuous filaments therefore has a tendency to produce nonwoven composites with a more or less pronounced two-sidedness.
- The bonds between the fibres and filaments in a nonwoven material manufactured by the process described above will thus mainly be mechanical bonds due to entangling of fibres and filaments. However, hydrogen bonds between cellulosic fibres will be present in the material.
- When using a web of unbonded filaments as a base for a nonwoven material, the integration of the two layers, i.e. the web of continuous filaments 1 and the fibre layer 6, is however very critical. If the two layers are not integrated well, also this material will have a pronounced two-sided appearance and the bonding of the continuous filaments will be poor. Such a material will have a reduced strength, especially in the direction of thickness. The short fibre side of such a two-sided material will have a high linting, i.e. a tendency for the short fibres to loosen from material. The bonds on the short fibre side will predominately consist of bonds between short fibres and the strength of the material on the short fibre side will be poor. The filament side of such a material will be sensitive to "piling" while abraded, i.e. portions and ends of filaments will have a tendency to be projecting out From the surface of the filament side of the material. A composite nonwoven material containing short fibres and continuous filaments only bonded by entangling, in which the integration of short fibres and continuous filaments have failed to some extent, will thus have worse properties than a similar material containing short fibres and continuous filaments prebonded to each other before the entangling step.
- When the entangling step starts the structure of layer 4 of continuous filaments is relatively open and it is easy for the water jets to move the short fibres in the layer 6 overlaying the filaments into the filament layer through the width thereof. The more short fibres that are moved into the filament layer, the less space is available for easy transport of short fibres remaining on top of the filament layer. However, due to the low resistance to movement of the filaments caused by the absence of bond between them when entering the entangling station, the period during entangling in which short fibres can be moved into the filament layer is prolonged compared to the period for a prebonded filament layer. The mixing of short fibres and continuous filament thus mainly occurs in the beginning of the entangling step. During the rest of the entangling step, portions of the filaments and portions of short fibres will entangle, entwine and entwist with each other and with filaments and/or other fibres. The entangling can thus be said to contain a mixing step followed by a bonding step. Of course some bonding will occur during the mixing step but most of the bonds will be obtained after the short fibres have been mixed with the continuous filaments.
- Even if the use of a layer 4 of unbonded continuous filaments facilitates the integration between short fibres and continuous filaments, a two-sided material can be obtained if the layer of continuous filaments is overly dense.
- On the other hand, if the structure of the layer 4 of continuous filaments is overly open, there is a risk that the fibres will be flushed out of the material by the water jets during entangling. This could create holes in the material and an uneven basis weight distribution.
- The inventors have found that to obtain a composite nonwoven material in which the two layers 4 and 6 are well integrated and which have high strength and an even basis weight distribution, the web of continuous filaments should have a projected coverage of between 1.3-1.6.
- The projected coverage is the sum of projected surface area of all filaments in one unit area and is obtained by multiplying the sum of lengths of filaments in one unit area with the average diameter of the filaments. The filaments in a web of continuous filaments having a projected coverage of 1.0 would thus cover the whole unit area if they were placed in one layer in straight lines adjacent to each other and in one layer.
- In Table 1 is shown the Taber abrasion resistance as a function of projected coverage for nonwoven material produced as described above with reference to
Figure 1 . The nonwoven materials are 80 gsm spunlaid composites comprising 25% (20gsm) continuous spunlaid filaments of polypropylene and pulp fibres with or without 10% of 19 mm long, 1.7 dtex staple fibres of polyester mixed therein. The nonwoven materials were manufactured in the following way. A 0.4 m wide web of spunlaid filaments was laid down onto a forming fabric at 20m/min such that the filaments were not bonded to each other. By a 0.4 m wide head box a fibre dispersion containing pulp fibres and staple fibres or alternatively without staple fibres was laid onto the unbonded web of spunlaid filaments and the excess water was drained and sucked off. The unbonded spunlaid filaments and wetlaid short fibres were then mixed and bonded together by hydroentanglement with three manifolds at a hydroentangling energy of about 300-350 kWh/ton. The hydroentanglement was done from the wetlaid side and the pulp and staple fibres were thus moved into and mixed intensively with the spunlaid filament web. Finally, the hydroentangled nonwoven composite material was dewatered and then dried using a through-air drum drier. - Only the examples showing a projected coverage between 1.3-1.6 and a content of continuous filaments of about 15-40 weight % fall within the scope of the claims.
- The Taber resistance values refer to the pulp side of the composite nonwoven material.
Table 1 Projected coverage Filament titre dtex Taber value (with staple fibres) Taber value (without staple fibres) 0.9 6.9 3 2 1.1 4.7 4 4 1.33 3.2 5 4 1.5 2.5 5 4 1.7 1.9 1 1 2.1 1.3 1 1 - As is evident from Table 1, the strength of the pulp side is optimised at a projected coverage between 1.3 and 1.5 corresponding to filament titre of 3.2 and 2.5 dtex (g/10 000 m), respectively. At higher projected coverage of 1.7 or more represented by projected coverages 1.7 and 2.1 corresponding to filament titres of 1.9 and 1.3 dtex, respectively, the integration or mixing of fibres and filaments in the material was not good, resulting in very poor surface strength on the pulp side of the material. At the lower projected coverage of 0.9 corresponding to a filament tire of 6.9 dtex, the structure of the filament web became too open to hold the pulp and the surface strength of the pulp side became poor.
- The Taber abrasion resistance is measured by Taber test equipment 5151 with two rubber wheel CS-10. Such equipment is well known to the skilled man and need not be described in detail. The testing is performed by mounting a circular test sample of the nonwoven material on a rotatable disk on the Taber test equipment. In the test, the test sample is subjected to the pressure of the two rubber wheel running on the top surface of the test sample. Depending on the basis weight of the test sample the disk is rotated with a different number of revolutions, the number of revolutions increasing with increased basis weight of the test sample. The Taber value of a tested sample is determined by visual comparison with a scale, i.e. five reference samples having Taber values 1-5, where 1 defines a very poor abrasion resistance and 3 defines an acceptable abrasion resistance.
- In Table 2 there is shown Taber values for three nonwoven materials, manufactured as described above, having different basis weight and content of continuous filaments. The continuous filaments are spunbond filaments of polypropylene and the short fibres are pulp fibres. The Taber value in the table represents the average of two identical test samples.
Table 2 Sample
Grammage/spunlaid content (g/m2)/ %Projected coverage Taber revolutions Taber value 50/40% 0.85 30 1 "-" 1.13 "-" 2 "-" 1.34 "-" 3 "-" 1.47 "-" 3.5 "-" 1.5 "-" 3.5 "-" 1.54 "-" 3.5 "-" 1.8 "-" 2 65/25% 0.76 100 1.5 "-" 1 "-" 2.5 "-" 1.18 "-" 3 "-" 1.3 "-" 4 "-" 1.4 "-" 4.5 "-" 1.8 "-" 4 "-" 2.16 "-" 2 80/25% 0.9 200 1.5 "-" 1.13 "-" 3 "-" 1.25 "-" 4 "-" 1.47 "-" 5 "-" 1.55 "-" 5 "-" 1.63 "-" 4 "-" 1.9 "-" 2 - From Table 2 one can conclude that if the projected coverage lies between 1.1 and 1.6 well integrated composite nonwovens can be provided for nonwovens with a basis weight of 80 g/m2 or more. For nonwovens having a lower basis weight the projected coverage shall be at least 1.2 in order for an acceptable material to be provided. In the interval of 1.3-1.6 acceptable nonwovens are provided even for nonwovens with a low basis weight and high content of continuous filaments. Thus, when constructing nonwoven materials according to the invention the ideal projected coverage lie between 1.3-1.6
- The examples below shows how important it is to select the correct filament titre to obtain the ideal projected coverage as basis weight and/or spunlaid content is varied in a wetlaid-spunlaid composite.
- For three different basis weights, 50, 80 and 100 gsm, filament titre is shown as function of spunlaid content and coverage in Tables 3-5.
- Calculation is made as follows:
-
-
- The total length of the filaments within the unit area is obtained by dividing the total weight of spunlaid filaments with the average filament titre (Titre) in dtex as shown in equation (3) below. The weight of the spunlaid filament web is obtained by myltiplying the basis weight of the spunlaid filament (BWS) web in g/m2 with the unit area (A). The filament titre in dtex is the weight of the filaments corresponding 10 000 m, i.e. g/10 000m.
-
-
-
-
-
-
-
- The specific gravity for polypropylene is around 900 kg/m3 for polyester around 1350 kg/m3.
- In Tables 2-4 below the filament titre for the ideal projected coverage range i.e. between 1.3 and 1.5 For wetlaid-spunlaid composite materials is shown. The filament titre of the outer range when the spunlaid web will become to open or to dense for making an acceptable spunlaid-wetlaid composite material is also shown for spunlaid projected coverages corresponding to 1.1 and 1.7.
Table 3. Filament titre in dtex as function of spunlaid content and coverage for a 50 g/m2 wetlaid-spunlaid composite material. SL Content Spunlaid Coverage [%] 1.1 1.3 1.6 1.7 40 4.68dtex 3.35dtex 2.21dex 1.96dtex 30 2.63dtex 1.88dtex 1.24dex 1.10dtex 20 1.17dtex 0.84dtex 0.55dex 0.49dtex Table 4. Filament titre in dtex as function of spunlaid content and coverage for a 80 g/m2 wetlaid-spunlaid composite material. SL Content Spunlaid Coverage [%] 1.1 1.3 1.6 1.7 30 6.73dtex 4.82dtex 3.18dtex 2.82dex 25 4.68dtex 3.35dtex 2.21dtex 1.96dtex 20 2.99dex 2.14dtex 1.41dtex 1.25dtex 15 1.68dtex 1.21dtex 0.80dtex 0.70dtex Table 4. Filament titre in dtex as function of spunlaid content and coverage for a 100 g/m2 wettaid-spunlaid composite material SL Content Spunlaid Coverage [%] 1.1 1.3 1.6 1.7 30 10.52dtex 7.53dtex 4.97dtex 4.41dtex 25 7.31dtex 5.23dex 3.45dtex 3.06dtex 20 4.68dtex 3.35dtex 2.21dtex 1.96dtex 15 2.63dtex 1.88dtex 1.24dtex 1.10dtex - As the filament titre in the Tables are compared it is clear that for spunlaid-wetlaid composites with high basis weights and/or high spunlaid contents a coarser titre of the spunlaid filaments has to be used to obtain the ideal spunlaid projected coverage. When spunlaid-wetlaid composites with low basis weight and/or low spunlaid contents are made a lower titre of the spunlaid filaments has to be used to obtain the ideal spunlaid projected coverage.
- The results in the Tables also show that as spunlaid content in the materials is changed with a relatively small percentage, a major adjustment of the filament titre has to be made to keep the spunlaid projected coverage at the same level. In a similar manner a relatively small change of the total basis weight of the material require a relatively large adjustment of the filament titre to be able to hit the ideal spunlaid projected coverage.
- Since the projected coverage is the product of filament length and average diameter of the filaments, the ideal projected coverage can be obtained by varying the filament length/m2, i.e. the velocity by which the filaments are laid on the transport web 1, or the diameter of the filaments. It is thus relatively easy for a skilled man to adapt the process parameters within the given limits.
Claims (9)
- A nonwoven composite material consisting of a mixture containing continuous spunlaid filaments and short fibres, characterised in that no thermobonds between continuous filaments are present in the material, the continuous filaments being substantially mechanically bonded to each other due to entangling of fibres and filaments and that the continuous filaments in the material have a projected coverage between 1.3-1.6, said projected coverage being the sum of projected surface area of all filaments in one unit area, the content of continuous filaments in the material is about 15-40 weight%
- The nonwoven composite material according to Claim 1, wherein that the short fibres comprises natural fibres and/or synthetic staple fibres.
- The nonwoven composite material according to Claim 2, wherein the short fibres comprise at least 60 weight% of cellulose fibres, preferably at least 70 weight%, more preferably at least 75 weight% and most preferably at least 85 weight%.
- The nonwoven composite material according to Claim 3, wherein the short fibres comprise 85-95 weight% of cellulose fibres, preferably about 90 weight%.
- The nonwoven composite material according to any one of Claims 1-4, wherein the content of continuous filaments in the material is about 25-40 weight%.
- The nonwoven composite material according to any one of Claims 1-5, wherein the basis weight of the material is 40-100 g/m2, preferably 50-80 g/m2.
- The nonwoven composite according to any one of Claims 1-6, wherein the short fibres are wetlaid fibres.
- A method of manufacturing a nonwoven material characterised by the steps of laying a web of unbonded continuous spunlaid filaments (4) onto a transport web (1) and choosing the velocity by which the filaments are laid onto the transport web (1) and the diameter of the filaments so that the web (4) of unbonded continuous filaments has a projected coverage of between 1.3-1.6, said projected coverage being the sum of projected surface area of all filaments in one unit area, wetlaying or airlaying a layer of short fibres (6) onto the web of unbonded continuous filaments (4) in such amount that the content of continuous filaments in the material is about 15-40 weight%, hydroentangling the layers consisting of continuous filaments and short fibres to form a composite nonwoven material and thereafter drying the material,.
- The method according to any one of Claim 8, wherein the energy supply at the hydroentangling is at the most about 500 kWh/ton, preferably about 300-400 kWh/ton and most preferably about 350 kWh/ton.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL04800360T PL1694895T3 (en) | 2003-12-18 | 2004-11-19 | A composite nonwoven material containing continuous filaments and short fibres |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE0303413A SE0303413D0 (en) | 2003-12-18 | 2003-12-18 | a composite nonwoven material containing continuous filaments and short fibers |
| PCT/SE2004/001698 WO2005059218A1 (en) | 2003-12-18 | 2004-11-19 | A composite nonwoven material containing continuous filaments and short fibres |
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| Publication Number | Publication Date |
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| EP1694895A1 EP1694895A1 (en) | 2006-08-30 |
| EP1694895B1 true EP1694895B1 (en) | 2010-04-21 |
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| EP (1) | EP1694895B1 (en) |
| CN (1) | CN1894455B (en) |
| AT (1) | ATE465289T1 (en) |
| AU (1) | AU2004299772B2 (en) |
| BR (1) | BRPI0417452A (en) |
| DE (1) | DE602004026774D1 (en) |
| ES (1) | ES2343687T3 (en) |
| MX (1) | MXPA06006089A (en) |
| PL (1) | PL1694895T3 (en) |
| RU (1) | RU2363786C2 (en) |
| SE (1) | SE0303413D0 (en) |
| WO (1) | WO2005059218A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2005331321B2 (en) | 2005-04-29 | 2011-04-28 | Sca Hygiene Products Ab | Hydroentangled integrated composite nonwoven material |
| WO2009031951A1 (en) | 2007-09-03 | 2009-03-12 | Sca Hygiene Products Ab | Laminate having improved wiping properties and a method for producing the laminate |
| WO2012150902A1 (en) * | 2011-05-04 | 2012-11-08 | Sca Hygiene Products Ab | Method of producing a hydroentangled nonwoven material |
| MX337119B (en) * | 2012-05-03 | 2016-02-12 | Sca Hygiene Prod Ab | Method of producing a hydroentangled nonwoven material. |
| WO2014104955A1 (en) * | 2012-12-27 | 2014-07-03 | Sca Hygiene Products Ab | Hydroformed composite nonwoven |
| CN103007632B (en) * | 2012-12-31 | 2015-10-28 | 上海博格工业用布有限公司 | Efficient low-resistance non-woven filter material and preparation method |
| CN104911820A (en) * | 2015-04-13 | 2015-09-16 | 武汉纺织大学 | Filament yarn bonding type honeycomb structure high-elastic vertical cotton and preparation method thereof |
| CN104818582A (en) * | 2015-04-13 | 2015-08-05 | 武汉纺织大学 | High-elastic antibacterial vertical cotton with filament adhesion type honeycomb structure and preparation method thereof |
| SI3239378T1 (en) * | 2016-04-29 | 2019-06-28 | Reifenhaeuser Gmbh & Co. Kg Maschinenfabrik | Device and method for the manufacture of material from continuous filaments |
| CA3034510C (en) * | 2016-09-01 | 2021-01-26 | Essity Hygiene And Health Aktiebolag | Process for producing nonwoven |
| CA3034508C (en) | 2016-09-01 | 2022-03-29 | Essity Hygiene And Health Aktiebolag | Process and apparatus for wetlaying nonwovens |
| CN112160077B (en) * | 2020-08-24 | 2022-07-05 | 中国农业科学院麻类研究所 | Low-cost plant fiber membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3493462A (en) * | 1962-07-06 | 1970-02-03 | Du Pont | Nonpatterned,nonwoven fabric |
| US4442161A (en) * | 1982-11-04 | 1984-04-10 | E. I. Du Pont De Nemours And Company | Woodpulp-polyester spunlaced fabrics |
| US4808467A (en) * | 1987-09-15 | 1989-02-28 | James River Corporation Of Virginia | High strength hydroentangled nonwoven fabric |
| US5026587A (en) * | 1989-10-13 | 1991-06-25 | The James River Corporation | Wiping fabric |
| CA2048905C (en) * | 1990-12-21 | 1998-08-11 | Cherie H. Everhart | High pulp content nonwoven composite fabric |
| DE69314202T2 (en) * | 1992-03-12 | 1998-05-14 | Oji Paper Co | Process for producing a wiping nonwoven |
| SE503272C2 (en) * | 1994-08-22 | 1996-04-29 | Moelnlycke Ab | Nonwoven material prepared by hydroentangling a fiber web and method for making such nonwoven material |
| SE9703886L (en) * | 1997-10-24 | 1999-04-25 | Sca Hygiene Paper Ab | Method of making a nonwoven material and made according to the method |
| FR2794776B1 (en) * | 1999-06-10 | 2001-10-05 | Icbt Perfojet Sa | PROCESS FOR THE PRODUCTION OF A NONWOVEN MATERIAL, INSTALLATION FOR ITS IMPLEMENTATION AND NONWOVEN THUS OBTAINED |
| CA2425947A1 (en) * | 2000-11-10 | 2002-05-16 | Kimberly-Clark Worldwide, Inc. | Hydroentangled nonwoven composite structures containing recycled synthetic fibrous materials |
| SE518035C2 (en) * | 2000-12-18 | 2002-08-20 | Sca Hygiene Prod Ab | Method of making a nonwoven material |
-
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- 2003-12-18 SE SE0303413A patent/SE0303413D0/en unknown
-
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- 2004-11-19 BR BRPI0417452-6A patent/BRPI0417452A/en not_active Application Discontinuation
- 2004-11-19 DE DE602004026774T patent/DE602004026774D1/en not_active Expired - Lifetime
- 2004-11-19 AU AU2004299772A patent/AU2004299772B2/en not_active Ceased
- 2004-11-19 CN CN2004800377676A patent/CN1894455B/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| ATE465289T1 (en) | 2010-05-15 |
| AU2004299772B2 (en) | 2009-10-29 |
| EP1694895A1 (en) | 2006-08-30 |
| CN1894455A (en) | 2007-01-10 |
| BRPI0417452A (en) | 2007-05-22 |
| PL1694895T3 (en) | 2010-09-30 |
| DE602004026774D1 (en) | 2010-06-02 |
| RU2363786C2 (en) | 2009-08-10 |
| WO2005059218A1 (en) | 2005-06-30 |
| CN1894455B (en) | 2010-11-10 |
| SE0303413D0 (en) | 2003-12-18 |
| MXPA06006089A (en) | 2006-08-11 |
| ES2343687T3 (en) | 2010-08-06 |
| RU2006121473A (en) | 2007-12-27 |
| AU2004299772A1 (en) | 2005-06-30 |
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