WO2004059050A1 - 熱融着生複合繊維 - Google Patents
熱融着生複合繊維 Download PDFInfo
- Publication number
- WO2004059050A1 WO2004059050A1 PCT/JP2003/016367 JP0316367W WO2004059050A1 WO 2004059050 A1 WO2004059050 A1 WO 2004059050A1 JP 0316367 W JP0316367 W JP 0316367W WO 2004059050 A1 WO2004059050 A1 WO 2004059050A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heat
- resin component
- conjugate fiber
- nonwoven fabric
- fiber
- Prior art date
Links
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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
- Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
- Y10T442/638—Side-by-side multicomponent strand or fiber material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
- Y10T442/641—Sheath-core multicomponent strand or fiber material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/69—Autogenously bonded nonwoven fabric
Definitions
- the present invention relates to a heat-fusible conjugate fiber.
- the present invention also relates to a bulky nonwoven fabric.
- a crystalline polymer is used as a core component, and a polymer having a softening point at least 40 ° C lower than the softening point of the polymer is used as a sheath component, and the weight ratio of the sheath component is 5 to 75%.
- a method for producing a conjugate fiber is disclosed in which a conjugate spinning is performed in a core-sheath shape so as to obtain a spun yarn at a speed of 320 to 980 m / min. According to the above publication, the conjugate fiber obtained by this method has a reduced heat shrinkage.
- a three-dimensionally crimped heat-fusible material having a first component made of crystalline polypropylene and a second component made of polyethylene Using composite fibers has been proposed (see Japanese Patent Application Laid-Open No. 8-64041). Also, for the purpose of obtaining a nonwoven fabric having an excellent texture, it has been proposed to use a heat-fusible conjugate fiber having an irregular fiber cross-section and having branch points extending in a strand shape. (See Japanese Patent Application Laid-Open No. 11-323663).
- the present invention has achieved the above object by providing a heat-fusible conjugate fiber produced by a high-speed melt spinning method.
- the heat-fusible conjugate fiber comprises a first resin component having an orientation index of 40% or more and a second resin component having a melting point or softening point lower than the melting point of the first resin component and having an orientation index of 25% or less. It consists of a resin component.
- the second resin component exists at least partially on the fiber surface continuously in the length direction.
- the present invention also provides a nonwoven fabric produced by using a web containing the heat-fusible conjugate fiber and formed by a card method, and heat-sealing intersections of the fibers in the web.
- the present invention includes a heat-fusible conjugate fiber composed of two components having different melting points, and is formed by heat-sealing the intersection of the fibers, and has a specific volume of 95 cm 3 / g or more and a unit area of intensity 0.1 8 per amount (N / 2 5 mm) / (g / m 2) or more, which provides a further units per thickness Parukusofu Tonesu is 0.1 4 N / mm or less is bulky nonwoven It is.
- FIG. 1 is a schematic diagram showing an apparatus used for a high-speed melt spinning method.
- FIG. 2 is a schematic view showing a fusion point forming apparatus.
- FIG. 3 is a schematic diagram showing a tensile tester used for measuring the fusion point strength.
- the present invention relates to a heat-fusible conjugate fiber having a low heat shrinkage ratio, exhibiting a high fusion strength at a low calorific value, and having good force web formability.
- the present invention also relates to a bulky and high-strength nonwoven fabric.
- the bicomponent fiber of the present invention is a bicomponent fiber comprising a first resin component and a second resin component having a lower melting point or softening point than the melting point of the first resin component, wherein the second resin component is At least a part of the fiber surface is continuous in the length direction.
- the form of the conjugate fiber includes various forms such as a core-sheath type and a side-by-side type, and the conjugate fiber of the present invention may take any form.
- the conjugate fiber of the present invention is preferably a concentric or eccentric core-sheath type, particularly preferably a concentric core-sheath type.
- the heat-fusible conjugate fiber of the present invention is produced by a high-speed melt spinning method. As shown in Fig. 1, the high-speed melt spinning method is a spinning apparatus equipped with two systems of extruders 1, 2 comprising an extruder 1A, 2A and a gear pump 1B, 2B, and a spinneret 3.
- the resin components melted and measured by the extruders 1A and 2A and the gear pumps 1B and 2B are combined in the spinneret 3 and discharged from the nozzle.
- the shape of the spinneret 3 is appropriately selected according to the form of the target conjugate fiber.
- a winding device 4 is provided directly below the spinneret 3, and the molten resin discharged from the nozzle is taken at a predetermined speed. Take-off speed of spun yarn in high-speed melt spinning The degree is generally greater than 2000 m / min. There is no particular upper limit for the pick-up speed, and it is now possible to pick up at speeds exceeding 100 m.
- the first resin component in the conjugate fiber of the present invention is a component that maintains the strength of the conjugate fiber
- the second resin component is a component that exhibits heat-fusibility.
- the first resin component has an orientation index of 40% or more, particularly 50% or more, while the second resin component has an orientation index of 25% or less, particularly 20% or less. It has become.
- the orientation index is an index of the degree of orientation of the polymer chains of the resin constituting the fiber.
- orientation index of the (1) resin component is less than 40%, the crystallization of the first resin component is not sufficiently performed, and the strength that can withstand practical use cannot be exhibited.
- orientation index of the second resin component is more than 25%, the heat-fusibility is not sufficiently exhibited, and it is difficult to form a high-strength fusion point with a low heat value (low temperature). is there.
- two types of resins having different melting points may be used to form fibers by the high-speed melt spinning method.
- the orientation index of the first resin component and the second resin component is as follows when the value of the birefringence of the resin in the conjugate fiber is A and the value of the intrinsic birefringence of the resin is B. It is expressed by equation (1).
- Intrinsic birefringence refers to the birefringence when the polymer chains of the resin are completely oriented, and the value is, for example, “Plastic material in molding” First edition It is described in Appendix, Typical Plastic Materials Used for Molding (Edited by the Japan Society of Plastics and Molding, Sigma Publishing, published on February 10, 1998).
- the birefringence of a conjugate fiber is measured under a polarized light parallel and perpendicular to the fiber axis with a polarizing plate attached to an interference microscope.
- As the immersion liquid use a standard refraction liquid manufactured by Cargi11e.
- the refractive index of the immersion liquid is measured with an Abbe refractometer.
- the refractive index in the direction parallel to and perpendicular to the fiber axis is determined by the calculation method described in the following literature, and the birefringence, which is the difference between the two, is calculated.
- the composite fiber of the present invention is obtained after spinning. It is preferable that the heat treatment or the crimping treatment is performed and the stretching treatment is not performed. Thereby, the conjugate fiber of the present invention has a low degree of heat shrinkage. Specifically, the heat shrinkage at a temperature 10 ° C higher than the melting point or softening point of the second resin component is 5% or less, particularly 1% or less, and particularly as low as 0.5% or less. Become.
- the conjugate fiber of the present invention when used, for example, as a constituent fiber of a nonwoven fabric, the resulting nonwoven fabric is bulky and has high strength (this will be further described later).
- the lower the value of the heat shrinkage the more preferable and ideally it is 0.
- the heat shrinkage may be a negative value, that is, the fibers may be elongated by heating.
- a negative heat shrinkage works in a favorable direction from the viewpoint of obtaining a bulky nonwoven fabric. Heat shrink When the percentage is negative, the upper limit (that is, the upper limit on the negative side) is -20%, especially about 110%, which means that the control of the formation of the non-woven fabric and the impression of the appearance Preferred from the point.
- the reason for measuring the heat shrinkage at the above-mentioned temperature is that, when a non-woven fabric is manufactured by heat-sealing the intersections of the fibers, the non-woven fabric is at or above the melting point or softening point of the second resin component and 10 ° C from them. This is because it is usually manufactured at a temperature as high as C.
- the heat shrinkage is measured by the following method. Using a thermo-mechanical analyzer TMA-50 (manufactured by Shimadzu Corporation), parallel fibers are mounted at a chuck distance of 10 mm, and a constant load of 0.025 m NZ te X is applied. In this condition, the temperature is raised at a rate of 10 ° C / min.
- the change in the shrinkage of the fiber is measured, and the shrinkage at a temperature higher by 10 ° C. than the melting point or softening point of the second resin component is read to be regarded as the heat shrinkage.
- Appropriate conditions for the heat treatment performed after the spinning are selected according to the types of the first and second resin components constituting the conjugate fiber of the present invention.
- the conjugate fiber of the present invention is a core-sheath type
- the core component is polypropylene and the sheath component is high-density polyethylene
- the heating temperature is 50 to 120 ° C, particularly 70 to 100 ° C. ° C
- the heating time is preferably 10 to 500 seconds, particularly preferably 20 to 2 0 seconds.
- Examples of the heating method include blowing hot air and irradiating infrared rays.
- mechanical crimping is simple. There are two-dimensional and three-dimensional modes in mechanical crimping, and in the present invention, any mode of crimping may be performed.
- Mechanical crimping can be hot. In that case, the heat treatment and the crimping treatment are performed simultaneously.
- the fiber may be slightly stretched, but such stretching is not included in the stretching process according to the present invention.
- the drawing treatment refers to a drawing operation usually performed on an undrawn yarn at a draw ratio of about 2 to 6 times.
- the form of the composite fiber of the present invention is as described above, and is typically a core-sheath type.
- the first resin component constitutes the core and the second resin component constitutes the sheath from the viewpoint that the heat shrinkage of the composite fiber of the present invention can be kept low.
- the types of the first resin component and the second resin component and any resin having a fiber-forming ability may be used.
- the melting point difference between the two resin components or the difference between the melting point of the first resin component and the softening point of the second resin component is 10 ° C or more, especially 20 ° C or more, This is preferable because the nonwoven fabric can be easily manufactured.
- the composite fiber is of a core-sheath type
- a resin having a higher melting point of the core component than a melting point or softening point of the sheath component is used.
- the first resin component is polypropylene (PP)
- the second resin component is high-density polyethylene (HDPE). ), Low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene propylene copolymer, and polystyrene.
- a polyester resin such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) is used as the first resin component
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- examples of the resin component there may be mentioned polypropylene (PP), copolymerized polyester and the like.
- the first resin component include polyamide polymers and copolymers of two or more of the above-mentioned first resin components.
- the second resin component include the second resin described above. Copolymers of two or more types of resin components are also included. These are appropriately combined. Of these combinations, it is preferred to use polypropylene (PP) high density polyethylene (HDPE). The reason for this is that the difference in melting point between the two resin components is in the range of 20 to 40 ° C., so that the nonwoven fabric can be easily produced.
- PP polypropylene
- HDPE high density polyethylene
- the specific gravity of the fiber is low, a nonwoven fabric that is lightweight and has excellent cost and can be incinerated and discarded with a low calorie is obtained because it is The method for measuring the melting points of the first resin component and the second resin component will be described in detail in Examples described later.
- the temperature at which the flow of the molecules of the second resin component starts is set as the temperature of the fusion point strength described in detail in Examples described later.
- the softening point is the temperature at which the second resin component fuses to such an extent that the fusion point strength of the fiber can be measured.
- the ratio (weight ratio) of the first resin component to the second resin component in the conjugate fiber of the present invention is 10: 90 to 90: 10%, particularly 30: 70 to 70: 30%. It is preferable that Within this range, the mechanical properties of the fiber will be sufficient and the fiber will be practically usable. In addition, the amount of the fusion component is sufficient, and the fusion between the fibers is sufficient. An appropriate value is selected for the thickness of the conjugate fiber of the present invention according to the specific use of the conjugate fiber. When the conjugate fiber of the present invention is used, for example, as a constituent fiber of a non-woven fabric, it is 1.0 to LO dtex, particularly 1.7 to 8. It is preferable in terms of card machine passability, productivity, cost and the like.
- the nonwoven fabric of the present invention contains heat-fusible conjugate fibers composed of two components having different melting points, and is formed by heat-sealing the intersections of the fibers.
- the nonwoven fabric of the present invention has a distinctive feature that differs from conventional nonwoven fabrics in its bulk and high strength.
- the nonwoven fabric of the present invention has a specific volume serving as a measure of bulkiness of 95 cm 3 Zg or more, preferably 110 cm 3 Zg or more, and more preferably 120 cm 3 / g. g or more.
- the specific volume can be increased even with a conventional nonwoven fabric. However, such nonwovens had to be of low strength.
- the nonwoven fabric of the present invention Although it has a large specific volume, it has high strength. Specifically, the nonwoven fabric of the present invention, the strength per unit basis weight of 0. 1 8 (N / 2 5 mm) / (g / m 2) or more, preferably 0 ⁇ 1 9 (N / 2 5 mm ) / (g / m 2) or more, still more preferably of high strength of 0. 2 0 (N / 2 5 mm) / (g / m 2) on or more.
- the strength per unit basis weight is sufficient if the above value is satisfied in the width direction (CD) of the nonwoven fabric. It is preferable to satisfy the above values in both the machine direction (MD) and the CD.
- the strength of the nonwoven fabric is generally higher in the MD than in the CD, it can be said that if the strength per unit basis weight satisfies the above-mentioned value in the CD, the above-mentioned value is necessarily satisfied also in the MD.
- the upper limits of the specific volume and the strength per square meter there are no particular restrictions on the upper limits of the specific volume and the strength per square meter, and the larger the better, the better.
- the upper limit of the specific volume is about 250 cm 3 / g, sufficiently satisfactory results can be obtained when the nonwoven fabric of the present invention is used for various uses.
- the nonwoven fabric of the present invention preferably has a bulk softness per unit thickness of 0.1 A NZ mm or less, particularly 0.12 N / mm or less, particularly 0.10 N / mm or less. That is, the nonwoven fabric of the present invention preferably has low bulk softness. This imparts drape to the nonwoven fabric and improves the texture. It is sufficient for the Balta softness per unit thickness to satisfy the above value in the machine direction (MD) of the nonwoven fabric. It is preferable that the above values be satisfied in both the MD and the width direction (CD).
- MD machine direction
- CD width direction
- nonwoven fabrics generally have higher balta softness in MD than in CD, if bulk softness per unit thickness satisfies the above-mentioned value in MD, it is inevitable that CD also satisfies the above-mentioned value in MD. I can say.
- Barthasov tone per unit thickness There is no particular limitation on the lower limit of the service, the smaller the better. If the lower limit of the balta softness per unit thickness is about 0.05 NZ mm, satisfactory results can be obtained when the nonwoven fabric of the present invention is used for various applications. A method of measuring the Balta softness per unit thickness will be described in detail in Examples described later.
- the low-stretching treatment refers to a case where the stretching treatment is performed less than twice. It has also been found effective to use undrawn conjugate fibers having a low heat shrinkage.
- unstretched conjugate fibers having a heat shrinkage of 5% or less, particularly 1% or less, especially 0.5% or less at a temperature 10 ° C higher than the melting point or softening point of the second resin component should be used. Is effective. Further, it is also effective to use undrawn conjugate fibers having a low orientation index of the second resin component, for example, those having an orientation index of 25% or less, particularly 20% or less.
- the non-stretched or low-stretched heat-fusible conjugate fiber for example, two types of resins having different melting points are used, and a fiber is formed by the high-speed melt spinning method at a spinning speed of 200 m / min or more. It can be obtained by doing so.
- the fiber can also be obtained by adjusting the orientation index of the core and the sheath by a combination of the resin of the core and the sheath, and then forming the fiber by ordinary melt spinning and performing a non-drawing treatment or a low drawing treatment. Furthermore, even if the combination of the core and the sheath resin is the same, after adjusting the orientation index of the core and the sheath by changing the molecular weight of each resin, the fiber is formed by ordinary melt spinning, and the unstretched or low-stretched fiber is formed. It can also be obtained by stretching.
- the nonwoven fabric of the present invention is preferably manufactured using a web containing undrawn conjugate fibers and formed by a card method, and heat-sealing the intersections of the fibers in the web.
- Such non-woven fabric has its specific volume and This is because the strength becomes higher.
- the nonwoven fabric of the present invention contains at least 30% by weight, particularly at least 50% by weight, of the unstretched conjugate fiber from the viewpoint of sufficiently exhibiting the properties of the conjugate fiber.
- the nonwoven fabric may be composed of 100% of the undrawn conjugate fiber.
- the fiber other than the undrawn conjugate fiber examples include, for example, a combination of the same resin as the undrawn conjugate fiber, a conjugate fiber obtained by a usual spinning and drawing process, or a polyester, polyolefin, or polyamide. Fibers of a single component made of a polymer of the base type, regenerated fibers such as rayon, cellulosic fibers, and natural fibers such as cotton are used. In the case of producing a web by a card method, it is preferable to use undrawn conjugate fibers in the form of short fibers of about 30 to 70 mm from the viewpoint of the passing property of a card machine and the formability of a card web. The resulting card web is heat treated to thermally fuse the fiber intersections in the web.
- the heat treatment include blowing hot air and pinching with a hot embossing roll. From the viewpoint that the texture of the obtained nonwoven fabric is improved, it is preferable to perform blowing of hot air (air through method).
- the temperature of the heat treatment is higher than the melting point or softening point of one resin component and lower than the melting point of the other resin component.
- the above-mentioned heat-fusible conjugate fiber of the present invention is used as the undrawn conjugate fiber, it can be further compared with a conventional nonwoven fabric made of the same type of conjugate fiber obtained by a usual method. A bulky and higher strength nonwoven fabric is obtained. The reason is as follows. First, the reason for the bulkiness is as follows.
- the composite fiber of the present invention has a low heat shrinkage. Therefore, when the card web is subjected to the heat treatment, the composite fibers are unlikely to shrink, and as a result, the fibers can be fused together in the state of the bulky card web before the heat treatment. Component fibers shrink When this occurs, the thickness of the card web decreases, and the bulk decreases.
- the second resin component of the conjugate fiber of the present invention has a low orientation index as described above, the use of a core-sheath type conjugate fiber having the second resin component as a sheath component,
- the strength of the fusion point can be maintained at a high value with a small amount of heat, that is, at a lower temperature than before and / or with a smaller amount of hot air than before. Being able to process at a lower temperature than before reduces the heat shrinkage of the composite fiber. Being able to process with a smaller amount of hot air than in the past will prevent a reduction in web bulk due to wind pressure.
- the nonwoven fabric can be manufactured under conditions that do not further reduce the bulk, even under the heat treatment conditions.
- the reason for the high strength is as follows.
- the advantages of the conjugate fiber of the present invention are that the heat shrinkage is low and the orientation index of the second resin component (fused component) is low. If shrinkage of the conjugate fiber does not easily occur during heat treatment of the card web, the fusion point becomes difficult to move, and as a result, a decrease in the strength of the fusion point is prevented. When the constituent fibers shrink, the fusion point moves and the strength decreases. Further, as described above, since the orientation index of the fusion component is low, the intensity of the fusion point can be maintained at a high value even with a smaller amount of heat than in the past.
- the influence of the temperature of the heat treatment is small, and the strength of the fusion point can be maintained at a high value in a wide range from a low temperature to a high temperature.
- the strength at the fusion point is higher than the strength at the fusion point of the same type of composite fiber obtained by an ordinary method.
- the fusion component of the conjugate fiber is uniformly aggregated at the fusion point, and the shape of the fusion point is substantially constant. As a result, the variation in the strength of the fusion point is reduced. As a result, it is possible to maintain the strength of the fusion points of the fibers constituting the nonwoven fabric at a high value and to reduce the variation.
- the strength of a nonwoven fabric obtained by fusing fibers with each other by blowing hot air greatly depends on the strength of a fusion point. That is, in order to obtain a high-strength nonwoven fabric, it is necessary to maintain the strength of the fiber fusion point at a high value. In addition, if the strength of the fusion point varies, the nonwoven fabric will be destroyed from the weak fusion point, and the strength of the nonwoven fabric will not be high.
- a high-strength nonwoven fabric can be obtained because the fusion point strength is high and the variation is small as described above. Furthermore, since the influence of the temperature of the heat treatment is small, the mechanical properties of the obtained nonwoven fabric can be made uniform.
- the nonwoven fabric of the present invention can be applied to various fields utilizing its bulk and high strength.
- disposable hygiene articles such as disposable diapers and sanitary napkins, topsheets, second sheets (sheets placed between the topsheet and the absorber), backsheets, leakproof sheets, or personal cleaning sheets It is suitably used as a sheet for skin care, a wiper for an object, and the like.
- second sheets sheets placed between the topsheet and the absorber
- backsheets sheets placed between the topsheet and the absorber
- leakproof sheets or personal cleaning sheets
- personal cleaning sheets It is suitably used as a sheet for skin care, a wiper for an object, and the like.
- the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to such embodiments.
- a thermal analysis of the finely cut fiber sample (sample mass: 2 mg) was performed at a heating rate of 10 ° C / min, and the melting peak of each resin was measured. The temperature was taken as the melting point of the resin.
- the fusing point forming apparatus shown in FIG. 2 was used.
- the fusing point forming device is a heating furnace 10 It consists of a thread hanging frame 1 1.
- the heating furnace 10 is a hollow rectangular parallelepiped having a heater (not shown) in the bottom surface, and only one side surface is open. This heater is connected to a temperature controller (not shown), which can control the atmosphere temperature in the furnace to a set temperature.
- the yarn suspension frame 11 has pulleys 12 attached at the four corners, single yarns 13 and 13 are crossed diagonally, and the single yarns 13 and 13 contact each other at the intersection. I have.
- the angle between the single yarns 13 and 13 is 90 degrees.
- each yarn attach a weight (not shown) with 5.88 mN / tex (1/15 gf / denier).
- the yarn suspension frame 11 can be slid into and out of the heating furnace 10 through an open side surface of the heating furnace 10, and heats the single yarn 13 for a predetermined time at a predetermined temperature. The intersection can be fused. After heating at a predetermined temperature for a predetermined time to fuse the single yarns 13 at the fusion point, they are removed from the frame 11 and attached to the tensile tester 14 shown in Fig. 3 as shown in the same figure. You. Specifically, the individual yarns 13 are attached to the upper and lower chucks 15 and 15 so that they are at 45 degrees to the tensile direction, and the fusion point is performed at a tensile speed of 10 mmZmin.
- the composite fibers obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were used as short fibers having a fiber length of 51 mm, and the short fibers were subjected to two-dimensional mechanical crimping.
- a card web was manufactured using the short fibers as a raw material.
- Hot air having a wind speed of 0.5 m / s was blown onto the card web at 135 ° C for 30 seconds by an air-through method to thermally fuse the intersections of the fibers. In this way, an air-through nonwoven fabric was obtained.
- the above-described measurement of the fusion point strength is adhesion at ambient temperature
- the fan is blown with hot air, so the temperature and time are the same. It should be noted that these are not the same conditions.
- the bulk of the obtained nonwoven fabric was evaluated by the following method, and the breaking strength was measured. Table 2 shows the results.
- a 12 cm x 12 cm plate is placed on the measuring table, and the position of the upper surface of the plate in this state is set as the reference point A for measurement.
- the plate is removed, a nonwoven fabric test piece to be measured is placed on a measuring table, and the plate is placed thereon.
- the position of the upper surface of the plate in this state is B. From the difference between A and B, determine the thickness of the non-woven test piece to be measured.
- the weight of the plate can be variously changed depending on the purpose of measurement, but here, the measurement was performed using a plate weighing 54 g.
- a laser displacement meter manufactured by Keyence Corporation, CCD laser displacement sensor LK-080 is used as the measuring device.
- a dial gauge type thickness gauge may be used.
- a thickness gauge it is necessary to adjust the pressure applied to the nonwoven fabric test piece.
- the thickness of the nonwoven fabric measured by the above method largely depends on the basis weight of the nonwoven fabric. Therefore, the specific volume (cm 3 / g) calculated from the thickness and the grammage is adopted as an index of the bulkiness.
- the method of measuring the basis weight is arbitrary, but it is calculated from the dimensions of the measured test piece by measuring the weight of the test piece itself whose thickness is to be measured.
- the composite fibers of the examples have a low heat shrinkage and a high fusion point strength. Further, it can be seen that the nonwoven fabric of each example is bulky and shows high strength. (Example 5 and Comparative Examples 7 and 8)
- Example 5 Using the fibers obtained in Example 5 and Comparative Example 7, an air-through nonwoven fabric was obtained in the same procedure as in Example 3.
- the manufacturing conditions are as shown in Table 4.
- the specific volume and the strength per unit weight of the obtained nonwoven fabric were measured by the above-described method, and the Balta softness was measured by the following method.
- the texture of the nonwoven fabric was determined by a sensory test using five monitors, and evaluated as follows. Table 4 shows the results.
- a sample was prepared by cutting the nonwoven fabric to 3 O mm on the MD and 15 O mm on the CD, and using this sample, a cylinder 45 mm in diameter and 30 mm in height was made.
- the repulsive force when compressing in the vertical direction at a speed of 10 mm / min was measured, and the value of the repulsive force was defined as the value of the bulk softness to the MD.
- Balta softness on CD was obtained by preparing a sample prepared by cutting a nonwoven fabric into a CD of 30 mm and a MD of 15 Omm, and performing the same measurement. Balta softness measured by this method is large in the thickness of the nonwoven fabric. It depends. Therefore, the bulk softness is divided by the thickness of the nonwoven fabric measured in the evaluation of the bulkiness described above, and the obtained value is used as the index of the drapability of the nonwoven fabric as the baltasoftness per unit thickness.
- Comparative Example 9 shown in Table 4 was used as a reference product, and three points were used. The touch of the nonwoven fabric was determined based on the following criteria, and an average score was calculated.
- Example 6 132 0.5 10 38.0 122.4 0.80 0.20 0 09 0 06 4.8 Comparative Example 9 132 0.5 10 36.2 0.92 0.17 0 24 0 12 3. 0 (reference) Comparative example 1 0 132 0.5 0.5 10 39.0 0 91 0.13 0 12 0 08 5.0
- Example 7 136 0.5 0.5 10 32.5 204.6 0 68 0.24 0 08 0 05 4.0 Comparative Example 1 1 136 0. 5 10 36. 7 0.86 0. 20 0 23 0 17 2.8 Comparative Example 1 2 136 0. 5 10 36. 9 1.10 0.
- Example 9 140 0.5 0.5 10 36. 6 0.80 80 0.20 09 0 07 4.0 Comparative example 1 5 140 0.5 10 42.6 87.9 0 84 0.19 0 35 0 20 1.8 Comparative example 1 6 140 0.5 0.5 10 35.26 o o 5. 0 1 20 0.24 0 40 0 23 1.0 ot
- the heat-fusible conjugate fiber of the present invention has a low heat shrinkage and a high fusion point strength. Further, the formability of the card web is good.
- the nonwoven fabric of the present invention is bulky and shows high strength even when the heat treatment temperature is lower than that of the conventional nonwoven fabric.
- the nonwoven fabric of the present invention has excellent drapability and good texture.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03780942.3A EP1577426B1 (en) | 2002-12-24 | 2003-12-19 | Heat fusible conjugate fiber |
AU2003289457A AU2003289457A1 (en) | 2002-12-24 | 2003-12-19 | Hot-melt conjugate fiber |
US10/540,474 US7968481B2 (en) | 2002-12-24 | 2003-12-19 | Hot-melt conjugate fiber |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-371283 | 2002-12-24 | ||
JP2002371283 | 2002-12-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004059050A1 true WO2004059050A1 (ja) | 2004-07-15 |
Family
ID=32677194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/016367 WO2004059050A1 (ja) | 2002-12-24 | 2003-12-19 | 熱融着生複合繊維 |
Country Status (5)
Country | Link |
---|---|
US (1) | US7968481B2 (ja) |
EP (1) | EP1577426B1 (ja) |
CN (1) | CN100339520C (ja) |
AU (1) | AU2003289457A1 (ja) |
WO (1) | WO2004059050A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007066599A1 (ja) * | 2005-12-07 | 2007-06-14 | Kao Corporation | 熱伸長性繊維 |
CN101379232B (zh) * | 2006-02-06 | 2014-08-06 | 帝人纤维株式会社 | 热粘合性复合纤维及其制造方法 |
CN112323258A (zh) * | 2020-10-10 | 2021-02-05 | 佛山市裕丰无纺布有限公司 | 一种热风蓬松布制造工艺 |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BRPI0508770A (pt) * | 2004-03-23 | 2007-08-28 | Solutia Inc | fibra eletrocondutora de multicomponentes, método para preparar uma fibra eletrocondutora de multicomponentes estirada uma fibra eletrocondutora de dois componentes estirada |
EP2022878B1 (en) | 2006-05-31 | 2014-10-15 | Kao Corporation | Stretch nonwoven fabric |
CA2708403C (en) | 2007-12-14 | 2016-04-12 | Schlumberger Canada Limited | Proppants and uses thereof |
CN101903616A (zh) * | 2007-12-14 | 2010-12-01 | 普拉德研究及开发股份有限公司 | 接触和/或处理地下地层的方法 |
US8353344B2 (en) * | 2007-12-14 | 2013-01-15 | 3M Innovative Properties Company | Fiber aggregate |
WO2009079310A1 (en) * | 2007-12-14 | 2009-06-25 | 3M Innovative Properties Company | Multi-component fibers |
WO2009079234A2 (en) | 2007-12-14 | 2009-06-25 | Schlumberger Canada Limited | Methods of treating subterranean wells using changeable additives |
WO2009079235A2 (en) * | 2007-12-14 | 2009-06-25 | 3M Innovative Properties Company | Fracturing fluid compositions comprising solid epoxy particles and methods of use |
WO2010075248A1 (en) | 2008-12-23 | 2010-07-01 | 3M Innovative Properties Company | Curable fiber and compositions comprising the same; method of trating a subterranean formation |
CN103993428B (zh) * | 2008-12-25 | 2017-10-24 | 花王株式会社 | 无纺布的制造方法 |
JP5842353B2 (ja) * | 2010-04-13 | 2016-01-13 | Jnc株式会社 | 嵩高性不織布 |
US11598031B2 (en) | 2011-07-07 | 2023-03-07 | 3M Innovative Properties Company | Article including multi-component fibers and hollow ceramic microspheres and methods of making and using the same |
KR101963791B1 (ko) * | 2011-10-05 | 2019-07-31 | 다우 글로벌 테크놀로지스 엘엘씨 | 이성분 섬유 및 그로부터 제조된 직물 |
JP6021566B2 (ja) | 2012-09-28 | 2016-11-09 | ユニ・チャーム株式会社 | 吸収性物品 |
JP6112816B2 (ja) | 2012-09-28 | 2017-04-12 | ユニ・チャーム株式会社 | 吸収性物品 |
CN103866485B (zh) * | 2012-12-11 | 2017-07-28 | 东丽纤维研究所(中国)有限公司 | 一种热粘合无纺布及其生产方法和用途 |
BR112018010582A2 (pt) * | 2015-11-25 | 2018-11-27 | Procter & Gamble | não tecido e artigos absorventes o contendo |
BE1023505B1 (nl) * | 2016-03-24 | 2017-04-11 | Beaulieu International Group | Non-woven-structuur met vezels die gekatalyseerd zijn door een metalloceenkatalysator |
CN110637117B (zh) * | 2017-06-05 | 2021-10-26 | 东洋纺株式会社 | 无纺布 |
CN109943980B (zh) * | 2017-12-20 | 2021-02-23 | 财团法人纺织产业综合研究所 | 无纺布结构与其制作方法 |
CN110894622B (zh) * | 2019-11-06 | 2022-01-28 | 青岛大学 | 粘结强度可控的类橘瓣形结构复合纤维及其制备工艺 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5438214B1 (ja) * | 1971-02-16 | 1979-11-20 | ||
US4269888A (en) * | 1972-11-25 | 1981-05-26 | Chisso Corporation | Heat-adhesive composite fibers and process for producing same |
JPS62184173A (ja) * | 1986-02-03 | 1987-08-12 | チッソ株式会社 | 弾性不織布およびその製造方法 |
JPS6440618A (en) * | 1987-08-03 | 1989-02-10 | Asahi Chemical Ind | Fiber for nonwoven fabric and production thereof |
JP2003119625A (ja) * | 2001-08-09 | 2003-04-23 | Ube Nitto Kasei Co Ltd | 不織布用繊維と不織布及びこれらの製造方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5237097B2 (ja) * | 1973-12-28 | 1977-09-20 | ||
JPS5823951A (ja) * | 1981-07-31 | 1983-02-12 | チッソ株式会社 | 嵩高不織布の製造方法 |
CN1066502A (zh) | 1991-05-04 | 1992-11-25 | 徐进华 | 筒杆式流体衡器 |
US5780155A (en) * | 1994-08-11 | 1998-07-14 | Chisso Corporation | Melt-adhesive composite fibers, process for producing the same, and fused fabric or surface material obtained therefrom |
JP3569972B2 (ja) | 1994-08-11 | 2004-09-29 | チッソ株式会社 | 熱融着性複合繊維および熱融着不織布 |
JPH09273060A (ja) * | 1996-04-03 | 1997-10-21 | Oji Paper Co Ltd | 複合長繊維不織布及びその製造方法 |
JP3658884B2 (ja) * | 1996-09-11 | 2005-06-08 | チッソ株式会社 | 複合長繊維不織布の製造方法 |
US5733825A (en) * | 1996-11-27 | 1998-03-31 | Minnesota Mining And Manufacturing Company | Undrawn tough durably melt-bondable macrodenier thermoplastic multicomponent filaments |
JP3844390B2 (ja) | 1997-11-26 | 2006-11-08 | 三井化学株式会社 | 不織布積層体 |
JP3900680B2 (ja) | 1998-05-19 | 2007-04-04 | チッソ株式会社 | 熱接着性複合繊維、これを用いた不織布及び吸収性物品 |
JP4206570B2 (ja) | 1999-04-23 | 2009-01-14 | チッソ株式会社 | 不織布およびそれを用いた吸収性物品 |
TW584680B (en) * | 1999-05-28 | 2004-04-21 | Inventa Fischer Ag | Device for intermingling, relaxing, and/or thermosetting of filament yarn in a melt spinning process, as well as associated processes and the filament yarn manufactured therewith |
-
2003
- 2003-12-19 US US10/540,474 patent/US7968481B2/en not_active Expired - Fee Related
- 2003-12-19 AU AU2003289457A patent/AU2003289457A1/en not_active Abandoned
- 2003-12-19 WO PCT/JP2003/016367 patent/WO2004059050A1/ja active Application Filing
- 2003-12-19 EP EP03780942.3A patent/EP1577426B1/en not_active Expired - Fee Related
- 2003-12-19 CN CNB2003801074784A patent/CN100339520C/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5438214B1 (ja) * | 1971-02-16 | 1979-11-20 | ||
US4269888A (en) * | 1972-11-25 | 1981-05-26 | Chisso Corporation | Heat-adhesive composite fibers and process for producing same |
JPS62184173A (ja) * | 1986-02-03 | 1987-08-12 | チッソ株式会社 | 弾性不織布およびその製造方法 |
JPS6440618A (en) * | 1987-08-03 | 1989-02-10 | Asahi Chemical Ind | Fiber for nonwoven fabric and production thereof |
JP2003119625A (ja) * | 2001-08-09 | 2003-04-23 | Ube Nitto Kasei Co Ltd | 不織布用繊維と不織布及びこれらの製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1577426A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007066599A1 (ja) * | 2005-12-07 | 2007-06-14 | Kao Corporation | 熱伸長性繊維 |
JP2007182662A (ja) * | 2005-12-07 | 2007-07-19 | Kao Corp | 熱伸長性繊維 |
KR101308640B1 (ko) * | 2005-12-07 | 2013-09-23 | 가오 가부시키가이샤 | 열 신장성 섬유 |
US8968859B2 (en) | 2005-12-07 | 2015-03-03 | Kao Corporation | Heat extensible fiber |
CN101379232B (zh) * | 2006-02-06 | 2014-08-06 | 帝人纤维株式会社 | 热粘合性复合纤维及其制造方法 |
CN112323258A (zh) * | 2020-10-10 | 2021-02-05 | 佛山市裕丰无纺布有限公司 | 一种热风蓬松布制造工艺 |
CN112323258B (zh) * | 2020-10-10 | 2023-12-19 | 佛山市裕丰无纺布有限公司 | 一种热风蓬松布制造工艺 |
Also Published As
Publication number | Publication date |
---|---|
AU2003289457A1 (en) | 2004-07-22 |
CN1732294A (zh) | 2006-02-08 |
CN100339520C (zh) | 2007-09-26 |
US7968481B2 (en) | 2011-06-28 |
EP1577426A1 (en) | 2005-09-21 |
EP1577426A4 (en) | 2006-07-05 |
EP1577426B1 (en) | 2016-06-01 |
US20060063457A1 (en) | 2006-03-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2004059050A1 (ja) | 熱融着生複合繊維 | |
JP4785700B2 (ja) | 不織布の製造方法 | |
JP3989468B2 (ja) | 立体賦形不織布 | |
JP4948127B2 (ja) | 熱伸長性繊維 | |
JP3016361B2 (ja) | 一方向伸縮性不織布及びその製造方法 | |
JP4068171B2 (ja) | 積層不織布およびその製造方法 | |
JP4535984B2 (ja) | 凹凸構造体の製造方法 | |
JP3955650B2 (ja) | 積層不織布およびその製造方法 | |
JP4975091B2 (ja) | 不織布 | |
JP3760599B2 (ja) | 積層不織布及びそれを用いた吸収性物品 | |
JP3736014B2 (ja) | 積層不織布 | |
JP5948214B2 (ja) | 熱伸長性繊維及びそれを用いた不織布 | |
JP4131852B2 (ja) | 熱融着性複合繊維 | |
JP2010235131A (ja) | 通気性成形体 | |
JP4318594B2 (ja) | 不織布 | |
JP5276305B2 (ja) | 混繊長繊維不織布 | |
JP2020147857A (ja) | 熱接着性複合繊維および不織布 | |
JP5548041B2 (ja) | 不織布 | |
JP5190441B2 (ja) | 不織布 | |
KR20040013756A (ko) | 복합 장섬유 부직포 및 이의 제조방법 | |
JP5548040B2 (ja) | 不織布 | |
JP7059850B2 (ja) | 積層不織布 | |
JP2020139244A (ja) | 積層不織布 | |
JP3135050B2 (ja) | 伸縮性ポリエステル系不織布及びその製造方法 | |
JP2020139245A (ja) | 積層不織布 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2006063457 Country of ref document: US Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10540474 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20038A74784 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003780942 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2003780942 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 10540474 Country of ref document: US |