WO2008062328A1 - Strand composite having latent elasticity - Google Patents
Strand composite having latent elasticity Download PDFInfo
- Publication number
- WO2008062328A1 WO2008062328A1 PCT/IB2007/053952 IB2007053952W WO2008062328A1 WO 2008062328 A1 WO2008062328 A1 WO 2008062328A1 IB 2007053952 W IB2007053952 W IB 2007053952W WO 2008062328 A1 WO2008062328 A1 WO 2008062328A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composite
- styrene
- strand layer
- elastic strand
- ethylene
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- 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
- D04H13/00—Other non-woven fabrics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/15577—Apparatus or processes for manufacturing
- A61F13/15585—Apparatus or processes for manufacturing of babies' napkins, e.g. diapers
- A61F13/15593—Apparatus or processes for manufacturing of babies' napkins, e.g. diapers having elastic ribbons fixed thereto; Devices for applying the ribbons
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/45—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape
- A61F13/49—Absorbent articles specially adapted to be worn around the waist, e.g. diapers
- A61F13/49007—Form-fitting, self-adjusting disposable diapers
- A61F13/49009—Form-fitting, self-adjusting disposable diapers with elastic means
- A61F13/4902—Form-fitting, self-adjusting disposable diapers with elastic means characterised by the elastic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/04—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a layer being specifically extensible by reason of its structure or arrangement, e.g. by reason of the chemical nature of the fibres or filaments
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
-
- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- 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]
- Y10T442/601—Nonwoven fabric has an elastic quality
- Y10T442/602—Nonwoven fabric comprises an elastic strand or fiber material
Definitions
- a nonwoven composite having latent elasticity comprises an elastic strand layer laminated to a nonwoven web facing.
- the elastic strand layer comprises a plurality of elastic strands and is formed from at least one thermoplastic elastomer and at least one semi-crystalline polyolefin.
- the semi-crystalline polyolefin constitutes from about 40 wt.% to about 95 wt.% of the elastic strand layer and the thermoplastic elastomer constitutes from about 5 wt.% to about 60 wt.% of the elastic strand layer.
- the composite exhibits a percent strain of about 50% or less when subjected to a load of 2000 grams-force per 3 inches wide in the machine direction prior to heat activation.
- Spunbond fibers may sometimes have diameters less than about 40 microns, and are often between about 5 to about 20 microns.
- machine direction generally refers to the direction in which a material is produced.
- cross-machine direction or “CD” refers to the direction perpendicular to the machine direction. Dimensions measured in the cross-machine direction are referred to as “width” dimension, while dimensions measured in the machine direction are referred to as “length” dimensions.
- the terms “extensible” or “extensibility” generally refers to a material that stretches or extends in the direction of an applied force by at least about 50% of its relaxed length or width.
- An extensible material does not necessarily have recovery properties.
- an elastomeric material is an extensible material having recovery properties.
- a meltblown web may be extensible, but not have recovery properties, and thus, be an extensible, non- elastic material.
- set refers to retained elongation in a material sample following the elongation and recovery, i.e., after the material has been stretched and allowed to relax during a cycle test.
- percent set is the measure of the amount of the material stretched from its original length after being cycled (the immediate deformation following the cycle test). The percent set is where the retraction curve of a cycle crosses the elongation axis. The remaining strain after the removal of the applied stress is measured as the percent set.
- the sample size is 3 inches by 6 inches, with a jaw facing height of 1 inch and width of 3 inches, and a constant rate of extension of 300 mm/min.
- the specimen is clamped in, for example, a Sintech 2/S tester with a Renew MTS mongoose box (control) and using TESTWORKS 4.07b software (Sintech Corp, of Cary, NC).
- the test is conducted under ambient conditions.
- the "hysteresis value" of a sample may be determined by first elongating the sample ("load up") and then allowing the sample to retract (“load down”). The hysteresis value is the loss of energy during this cyclic loading.
- the present invention is directed to a nonwoven composite that exhibits latent elastic properties.
- the composite is formed from an elastic strand layer laminated to a nonwoven web facing.
- Latent elasticity may be imparted to the elastic strand layer through the combination of a thermoplastic elastomer and a polyolefin capable of forming semi-crystalline domains among the elastomeric chains. More specifically, the elastic strand layer may be stretched in one or more directions to orient the elastomer chains. Without intending to be limited by theory, the present inventors believe that the oriented state of the chains may be held in place by the relatively stiff semi-crystalline domains of the polyolefin.
- the elastic strands may be substantially continuous in length so that they are in the form of filaments.
- Such filaments may be produced using any of a variety of known techniques, such as by extruding an elastomeric polymeric composition from a die having a series of extrusion capillaries arranged in a row.
- meltblown dies may be suitable for forming the filaments, except that the high velocity gas streams used in fiber attenuation are generally not employed. Rather, the molten polymer extrudate is pumped from the die capillaries and allowed to extend away from the die under the impetus of gravity.
- other elastic filaments may also be employed in the present invention, such as the spandex-type materials available under the designation "LYCRA®" from Invista North America of Wilmington, Delaware.
- the monoalkenyl arene blocks may include styrene and its analogues and homologues, such as o-methyl styrene; p-methyl styrene; p-tert-butyl styrene; 1 ,3 dimethyl styrene p-methyl styrene; etc., as well as other monoalkenyl polycyclic aromatic compounds, such as vinyl naphthalene; vinyl anthrycene; and so forth.
- Preferred monoalkenyl arenes are styrene and p-methyl styrene.
- the amount of monoalkenyl arene (e.g., polystyrene) blocks may vary, but typically constitute from about 8 wt.% to about 55 wt.%, in some embodiments from about 10 wt.% to about 35 wt.%, and in some embodiments, from about 25 wt.% to about 35 wt.% of the copolymer.
- Suitable block copolymers may contain monoalkenyl arene endblocks having a number average molecular weight from about 5,000 to about 35,000 and saturated conjugated diene midblocks having a number average molecular weight from about 20,000 to about 170,000.
- the total number average molecular weight of the block polymer may be from about 30,000 to about 250,000.
- styrene-olefin block copolymers examples include styrene-(ethylene-butylene), styrene- (ethylene-propylene), styrene-(ethylene-butylene)-styrene, styrene-(ethylene- propylene)-styrene, styrene-(ethylene-butylene)-styrene-(ethylene-butylene), styrene-(ethylene-propylene)-styrene-(ethylene-propylene), and styrene-ethylene- (ethylene-propylene)-styrene.
- copolymers include the S-I-S and S-B-S elastomeric copolymers available from Dexco Polymers of Houston, Texas under the trade designation VECTOR®.
- polymers composed of an A-B-A-B tetrablock copolymer such as discussed in U.S. Patent No. 5,332,613 to Taylor, et al., which is incorporated herein in its entirety by reference thereto for all purposes.
- An example of such a tetrablock copolymer is a styrene- poly(ethylene-propylene)-styrene-poly(ethylene-propylene) (“S-EP-S-EP”) block copolymer.
- Particularly desired ⁇ - olefin comonomers are 1-butene, 1-hexene and 1-octene.
- the ethylene content of such copolymers may be from about 60 mole% to about 99 mole%, in some embodiments from about 80 mole% to about 98.5 mole%, and in some embodiments, from about 87 mole% to about 97.5 mole%.
- the ⁇ -olefin content may likewise range from about 1 mole% to about 40 mole%, in some embodiments from about 1.5 mole% to about 15 mole%, and in some embodiments, from about 2.5 mole% to about 13 mole%.
- Suitable propylene polymers are commercially available under the designations VISTAMAXXTM from ExxonMobil Chemical Co. of Houston, Texas; FINATM (e.g., 8573) from Atofina Chemicals of Feluy, Belgium; TAFMERTM available from Mitsui Petrochemical Industries; and VERSIFYTM available from Dow Chemical Co. of Midland, Michigan.
- Other examples of suitable propylene polymers are described in U.S. Patent No. 6,500,563 to Datta, et al.; 5,539,056 to
- olefin polymers may be formed using a free radical or a coordination catalyst (e.g., Ziegler-Natta).
- a coordination catalyst e.g., Ziegler-Natta
- the olefin polymer is formed from a single-site coordination catalyst, such as a metallocene catalyst.
- a metallocene catalyst Such a catalyst system produces ethylene copolymers in which the comonomer is randomly distributed within a molecular chain and uniformly distributed across the different molecular weight fractions.
- Metallocene- catalyzed polyolefins are described, for instance, in U.S. Patent. Nos.
- metallocene catalysts include bis(n-butylcyclopentadienyl)titanium dichloride, bis(n- butylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)scandium chloride, bis(indenyl)zirconium dichloride, bis(methylcyclopentadienyl)titanium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl(cyclopentadienyl,-1 -flourenyl)zirconium dichloride, molybdocene dichloride, nickelocene, niobocene dichloride, ruthenocene, titanocene dichloride, zirconocene chloride
- Metallocene catalysts typically have a narrow molecular weight range.
- metallocene-catalyzed polymers may have polydispersity numbers (Mw/Mn) of below 4, controlled short chain branching distribution, and controlled isotacticity.
- the melt flow index (Ml) of the semi-crystalline polyolefins may generally vary, but is typically in the range of about 0.1 grams per 10 minutes to about 100 grams per 10 minutes, in some embodiments from about 0.5 grams per 10 minutes to about 30 grams per 10 minutes, and in some embodiments, about 1 to about 10 grams per 10 minutes, determined at 190 0 C.
- the melt flow index is the weight of the polymer (in grams) that may be forced through an extrusion rheometer orifice (0.0825-inch diameter) when subjected to a force of 2.16 kilograms in 10 minutes at 190°C, and may be determined in accordance with
- thermoplastic elastomers and semi-crystalline polyolefins are selectively controlled in accordance with the present invention to achieve a balance between the mechanical and thermal properties of the elastic strand layer.
- the ratio of the amount of the thermoplastic elastomer(s) to the amount of the semi-crystalline polyolefin(s) may range from about 0.5 to about 15, in some embodiments from about 1 to about 10, and in some embodiments, from about 1 to about 5.
- the thermoplastic elastomer(s) may constitute from about 40 wt.% to about 95 wt.%, in some embodiments from about 45 wt.% to about 90 wt.%, and in some embodiments, from about 50 wt.% to about 75 wt.% of the elastic strand layer.
- the semi-crystalline polyolefin(s) may constitute from about 5 wt.% to about 60 wt.%, in some embodiments from about 10 wt.% to about 55 wt.%, and in some embodiments, from about 15 wt.% to about 50 wt.% of the elastic strand layer. It should of course be understood that other polymers may also be employed in the elastic strand layer. When utilized, however, the other polymers typically constitute about 10 wt.% or less, and in some embodiments, about 5 wt.% or less of the material.
- the elastic strand layer may also employ other additives as is known in the art.
- a tackifying resin may nevertheless be employed in some embodiments to facilitate subsequent bonding of the strand layer to a nonwoven web facing.
- One suitable class of tackifying resins includes hydrogenated hydrocarbon resins, such as REGALREZTM hydrocarbon resins available from Eastman Chemical.
- Other suitable tackifying resins may be described in U.S. Patent No. 4,787,699.
- the tackifying resin may be present in an amount from about 0.001 wt.% to about 35 wt.%, in some embodiments, from about 0.005 wt.% to about 30 wt.%, and in some embodiments, from 0.01 wt.% to about 25 wt.% of the elastic strand layer.
- the elastic strand layer may also contain other additives as is known in the art, such as melt stabilizers, processing stabilizers, heat stabilizers, light stabilizers, antioxidants, heat aging stabilizers, whitening agents, antiblocking agents, bonding agents, viscosity modifiers, etc.
- Viscosity modifiers may also be employed, such as polyethylene wax (e.g., EPOLENETM C-10 from Eastman Chemical).
- Phosphite stabilizers e.g., IRGAFOS available from Ciba Specialty Chemicals of Terrytown, N.Y. and DOVERPHOS available from Dover Chemical Corp. of Dover, Ohio
- melt stabilizers e.g., IRGAFOS available from Ciba Specialty Chemicals of Terrytown, N.Y. and DOVERPHOS available from Dover Chemical Corp. of Dover, Ohio
- hindered amine stabilizers e.g., CHIMASSORB available from Ciba Specialty Chemicals
- CHIMASSORB available from Ciba Specialty Chemicals
- hindered phenols are commonly used as an antioxidant in the production of fibers and films.
- Some suitable hindered phenols include those available from Ciba Specialty Chemicals of under the trade name "Irganox®", such as Irganox® 1076, 1010, or E 201.
- bonding agents may also be added to facilitate bonding to additional materials (e.g., nonwoven web).
- additives e.g., antioxidant, stabilizer, etc.
- additives may each be present in an amount from about 0.001 wt.% to about 40 wt.%, in some embodiments, from about 0.005 wt.% to about 35 wt.%, and in some embodiments, from 0.01 wt.% to about 25 wt.% of the elastic strand layer.
- the elastic strand layer may be in the form of a single layer of strands or a laminate containing the strands.
- the polymer content of the elastic strands and/or other components of the layer may be selected to provide the desired degree of latent elasticity to the composite.
- the elastic strands may be formed from a blend of a thermoplastic elastomer and semi-crystalline polyolefin.
- the thermoplastic elastomer(s) may constitute from about 40 wt.% to about 95 wt.%, in some embodiments from about 45 wt.% to about 90 wt.%, and in some embodiments, from about 50 wt.% to about 75 wt.% of the strands.
- the semi-crystalline polyolefin(s) may constitute from about 5 wt.% to about 60 wt.%, in some embodiments from about 10 wt.% to about 55 wt.%, and in some embodiments, from about 15 wt.% to about 50 wt.% of the strands.
- the elastic strand layer is a laminate that includes multiple layers.
- the laminate may contain strands laminated to a meltblown web to help secure the strands to a facing so that they are less likely to loosen during use. Examples of such laminates are described in more detail, for instance, in U.S. Patent No. 5,385,775 to Wright and U.S. Patent Application Publication No. 2005/0170729 to Stadelman. et al.. which are incorporated herein in their entirety by reference thereto for all purposes.
- the strands and the meltblown web may contain a thermoplastic elastomer, semi- crystalline polyolefin, or combinations thereof.
- the strands contain a thermoplastic elastomer and the meltblown web contains a semi- crystalline polyolefin.
- the thermoplastic elastomer(s) may constitute about 70 wt.% or more, in some embodiments about 80 wt.% or more, and in some embodiments, about 90 wt.% or more of the strands
- the semi- crystalline polyolefin(s) may constitute about 70 wt.% or more, in some embodiments about 80 wt.% or more, and in some embodiments, about 90 wt.% or more of the meltblown web.
- the relatively stiff semi-crystalline domains of the meltblown web may hold the elastomeric chains of the strands in an oriented state (when stretched).
- the semi- crystalline domains may be softened and release oriented chains to impart latent elasticity to the composite.
- the basis weight (or add-on level) of the strands is greater than the meltblown web to optimize the elasticity of the composite.
- too high of a strand basis weight relative to the meltblown web basis weight may result in a composite lacking the desired latency characteristics.
- the ratio of the strand basis weight to the meltblown web basis weight is typically from about 1.2 to about 5.0, in some embodiments from about 1.5 to about 4.0, and in some embodiments, from about 2.0 to about 3.5.
- the basis weight of the meltblown layer may range from about 0.1 to about 30 gram per square meter ("gsm"), in some embodiments about 0.5 to about 20 gsm, and in some embodiments, from about 1 to about 15 gsm.
- the basis weight of the strands may range from about 1 to about 75 gsm, in some embodiments from about 4 to about 60 gsm, and in some embodiments, from about 5 to about 40 gsm.
- the elastic strand layer of the present invention exhibits good latent stretch properties for use in a wide variety of applications.
- One measurement that is indicative of the latent stretch properties of the material is the heat shrinkage performance, which is a measure of recoverable deformation upon activation.
- a very high level of heat shrinkage may be achieved in the present invention, such as about 40% or more, in some embodiments about 50% or more, and in some embodiments, about 60% or more.
- heat shrinkage is determined by heating the material in water at 160°F for 30 seconds to 1 minute.
- shrinkage may be determined using ASTM D2838-02.
- a nonwoven web facing is generally employed in the present invention to reduce the coefficient of friction and enhance the cloth-like feel of the composite surface.
- Exemplary polymers for use in forming nonwoven web facings may include, for instance, polyolefins, e.g., polyethylene, polypropylene, polybutylene, etc.; polytetrafluoroethylene; polyesters, e.g., polyethylene terephthalate and so forth; polyvinyl acetate; polyvinyl chloride acetate; polyvinyl butyral; acrylic resins, e.g., polyacrylate, polymethylacrylate, polymethylmethacrylate, and so forth; polyamides, e.g., nylon; polyvinyl chloride; polyvinylidene chloride; polystyrene; polyvinyl alcohol; polyurethanes; polylactic acid; copolymers thereof; and so forth.
- biodegradable polymers such as those described above, may also be employed.
- Synthetic or natural cellulosic polymers may also be used, including but not limited to, cellulosic esters; cellulosic ethers; cellulosic nitrates; cellulosic acetates; cellulosic acetate butyrates; ethyl cellulose; regenerated celluloses, such as viscose, rayon, and so forth.
- the polymer(s) may also contain other additives, such as processing aids or treatment compositions to impart desired properties to the fibers, residual amounts of solvents, pigments or colorants, and so forth.
- Monocomponent and/or multicomponent fibers may be used to form the nonwoven web facing.
- Monocomponent fibers are generally formed from a polymer or blend of polymers extruded from a single extruder.
- Multicomponent fibers are generally formed from two or more polymers (e.g., bicomponent fibers) extruded from separate extruders.
- the polymers may be arranged in substantially constantly positioned distinct zones across the cross-section of the fibers.
- the components may be arranged in any desired configuration, such as sheath-core, side-by-side, pie, island-in-the-sea, three island, bull's eye, or various other arrangements known in the art.
- Various methods for forming multicomponent fibers are described in U.S. Patent Nos.
- Multicomponent fibers having various irregular shapes may also be formed, such as described in U.S. Patent. Nos.
- the fibers are sent through a combing or carding unit that further breaks apart and aligns the fibers in the machine direction so as to form a machine direction-oriented fibrous nonwoven web.
- the carded web may then be bonded using known techniques to form a bonded carded nonwoven web.
- a nonwoven web facing may also contain an additional fibrous component such that it is considered a composite.
- a nonwoven web may be entangled with another fibrous component using any of a variety of entanglement techniques known in the art (e.g., hydraulic, air, mechanical, etc.).
- the nonwoven web is integrally entangled with cellulosic fibers using hydraulic entanglement.
- a typical hydraulic entangling process utilizes high pressure jet streams of water to entangle fibers to form a highly entangled consolidated fibrous structure, e.g., a nonwoven web. Hydraulically entangled nonwoven webs of staple length and continuous fibers are disclosed, for example, in U.S. Patent Nos.
- Hydraulically entangled composite nonwoven webs of a continuous fiber nonwoven web and a pulp layer are disclosed, for example, in U.S. Patent Nos. 5,284,703 to Everhart, et al. and 6,315,864 to Anderson, et al., which are incorporated herein in their entirety by reference thereto for all purposes.
- the fibrous component of the composite may contain any desired amount of the resulting substrate.
- the fibrous component may contain greater than about 50% by weight of the composite, and in some embodiments, from about 60% to about 90% by weight of the composite.
- the nonwoven web may contain less than about 50% by weight of the composite, and in some embodiments, from about 10% to about 40% by weight of the composite.
- the basis weight of the nonwoven web facing may generally vary, such as from about 5 grams per square meter ("gsm") to 120 gsm, in some embodiments from about 8 gsm to about 70 gsm, and in some embodiments, from about 10 gsm to about 35 gsm. When multiple nonwoven web facings, such materials may have the same or different basis weights.
- the elastic strand layer is initially stretched in one or more directions to orient the chains of the thermoplastic elastomer(s). Thereafter, the stretched material is relaxed to a certain degree and bonded to a nonwoven web facing. Because the elastic strand layer is in a relaxed stated during lamination, the nonwoven web facing does not gather to a significant extent. Thus, despite the fact that the composite contains an elastomeric polymer, its elastic properties are initially limited by the presence of the relatively inelastic nonwoven web facing. Upon heat activation, however, the semi-crystalline domains of the polyolefin may soften and release the chains from their oriented configuration.
- a first extrusion apparatus 20 is fed with the raw materials (e.g., thermoplastic elastomer) used to form the continuous filaments.
- the materials may be dry mixed together (i.e., without a solvent) or alternatively blended with a solvent.
- the materials are dispersively mixed in the melt and compounded using any known technique, such as batch and/or continuous compounding techniques that employ, for example, a Banbury mixer, Farrel continuous mixer, single screw extruder, twin screw extruder, etc.
- the first extrusion apparatus 20 extrudes the raw materials in the form of filaments 31 onto a forming surface 30 (e.g., a foraminous belt) moving clockwise about rolls 40.
- a vacuum may also help hold the filaments 31 against the forming surface 30.
- meltblown fibers 36 are also extruded from an extrusion apparatus 45 on top of the continuous filaments 31 to form a laminated elastic strand layer 50.
- the elastic strand layer 50 is stretched in one or more directions.
- the elastic strand layer 50 is stretched in the machine direction by passing through a first set of rolls 46 traveling at a speed that is slower than a second set of rolls 47. While four rolls are illustrated in Fig. 1 , it should be understood that the number of rolls may be higher or lower, depending on the level of stretch that is desired and the degrees of stretching between each roll.
- various parameters of the stretching operation may be selectively controlled, including the stretch ratio, stretching temperature, and so forth.
- the elastic strand layer is stretched in the machine direction at a ratio of from about 2.0 to about 8.0, in some embodiments from about 3.0 to about 7.0, and in some embodiments, from about 3.5 to about 6.0.
- the stretch ratio may be determined by dividing the length of the stretched material by its length before stretching.
- the stretch ratio may also be approximately the same as the draw ratio, which may be determined by dividing the linear speed of the strand layer upon stretching (e.g., speed of the nip rolls) by the linear speed at which the strand layer is formed (e.g., speed of forming surface).
- the stretch ratio is determined by dividing the linear speed of the second set of rolls 47 by the linear speed of the forming surface 30.
- the orientation temperature profile is also chosen to deliver the desired shrink mechanical properties, such as shrink tension and shrink percentage. More specifically, the orientation temperature is less than the melting temperature of the semi-crystalline polyolefin.
- the elastic strand layer may be stretched at a temperature from about 15 0 C to about 50 0 C, in some embodiments from about 25°C to about 4O 0 C, and in some embodiments, from about 30°C to about 4O 0 C.
- the elastic strand layer is "cold drawn", i.e., stretched without the application of external heat (e.g., heated rolls), to improve latent elasticity.
- a nonwoven web facing is also employed for laminating to the elastic strand layer 50.
- a nonwoven web facing 33 may simply be unwound from a supply roll 22 as shown in Fig. 1.
- the nonwoven web facing 33 may be formed in-line, such as by dispensing polymer filaments from a pair of spinnerettes onto a conveyor assembly.
- the facing 33 may be compressed to form inter-filament bonding using a pair of nip rolls (not shown).
- the nonwoven web facing 33 is directed to a nip defined between rolls 58 for laminating to the elastic strand layer 50.
- a second nonwoven web facing 35 is also employed that originates from a supply roll 62.
- the latent character of the elastic strand layer of the present invention may be enhanced by allowing it to relax prior to lamination to a nonwoven web facing.
- the elastic strand layer is allowed to relax about 10% or more, in some embodiments from about 15% to about 60%, and in some embodiments, from about 20% to about 50% in the machine direction.
- the aforementioned "relaxation percentage" may be determined by subtracting the relaxed length of the strand layer by the stretched length of the layer, dividing this difference by the stretched length; and then multiplying the quotient by 100.
- the stretched and relaxed lengths of the layers may be determined from the speed of rolls used during stretching and lamination. In the illustrated embodiment, for example, the relaxation percentage is determined by subtracting the linear speed of the nip rolls 58 from the linear speed of the rolls 47, dividing this difference by the linear speed of the rolls 47, and then multiplying the quotient by 100.
- the elastic strand layer 50 may be utilized to bond to the nonwoven web facings 33 and 35, including adhesive bonding; thermal bonding; ultrasonic bonding; microwave bonding; extrusion coating; and so forth.
- one or both of the rolls 58 apply a pressure to the strand layer 50 and facings 33 and 35 to thermally bond the materials together.
- the rolls 58 may be smooth and/or contain a plurality of raised bonding elements.
- the elastic strand layer may itself act as an adhesive to facilitate bonding with the nonwoven web facings 33 and 35.
- adhesives may also be employed, such as Rextac 2730 and 2723 available from Huntsman Polymers of Houston, Texas, as well as adhesives available from Bostik Findley, Inc, of Wauwatosa, Wisconsin.
- the type and basis weight of the adhesive used will be determined on the elastic attributes desired in the final composite and end use. For instance, the basis weight of the adhesive may be from about 1.0 to about 3.0 gsm.
- the adhesive may be applied to the nonwoven web facings and/or the elastic strand layer prior to lamination using any known technique, such as slot or melt spray adhesive systems.
- the resulting composite 32 is wound and stored on a take-up roll 60.
- the composite 32 may be allowed to slightly retract prior to winding on to the take-up roll 60. This may be achieved by using a slower linear velocity for the roll 60. More preferably, however, the composite 32 is kept under tension, such as by using the same linear velocity for the roll 60 as the speed of one or more of the nip rolls 58.
- the composite may optionally be mechanically stretched in the cross- machine and/or machine directions to enhance extensibility.
- the composite may be coursed through two or more rolls that have grooves in the CD and/or MD directions.
- Such grooved satellite/anvil roll arrangements are described in U.S. Patent Application Publication Nos. 2004/0110442 to Rhim, et aL. and 2006/0151914 to Gerndt, et al., which are incorporated herein in their entirety by reference thereto for all purposes.
- the laminate may be coursed through two or more rolls that have grooves in the CD and/or MD directions.
- the grooved rolls may be constructed of steel or other hard material (such as a hard rubber).
- heat may be applied by any suitable method known in the art, such as heated air, infrared heaters, heated nipped rolls, or partial wrapping of the laminate around one or more heated rolls or steam canisters, etc. Heat may also be applied to the grooved rolls themselves.
- other grooved roll arrangement are equally suitable, such as two grooved rolls positioned immediately adjacent to one another.
- other techniques may also be used to mechanically stretch the composite in one or more directions. For example, the composite may be passed through a tenter frame that stretches the composite.
- tenter frames are well known in the art and described, for instance, in U.S. Patent Application Publication No. 2004/0121687 to Morman, et al.
- the composite may also be necked. Suitable techniques necking techniques are described in U.S. Patent Nos. 5,336,545, 5,226,992, 4,981 ,747 and 4,965,122 to Morman, as well as U.S. Patent Application Publication No. 2004/0121687 to Morman, et al., all of which are incorporated herein in their entirety by reference thereto for all purposes.
- Fig. 1 depicts filaments formed in a "horizontal" extrusion process, it should be understood that other methods are equally contemplated by the present invention.
- the filaments may be formed using a "vertical" extrusion process, such as described in U.S. Patent Application Publication No. 2002/0104608 to Welch, et al., which is incorporated herein in its entirety by reference thereto for all purposes.
- a vertical filament laminate (VFL) is shown. As depicted, the method employs a vertically arranged apparatus that includes an extruder 110 for extruding continuous molten filaments 105 downward from a die onto a chilled positioning roll 120. As the filaments travel over the surface of the roll 120, they are cooled and solidified.
- the chilled roll 120 may, for instance, have a temperature of about 4O 0 F to about 80 0 F.
- the die of the extruder 110 may be positioned with respect to the chilled roll 120 so that the continuous filaments meet the roll at a predetermined angle 130.
- An angled, or canted, orientation provides an opportunity for the filaments to emerge from the die at a right angle to the roll tangent point resulting in improved spinning, more efficient energy transfer, and generally longer die life.
- the angle 130 between the die exit of the extruder 110 and the vertical axis (or the horizontal axis of the first roll, depending on which angle is measured) may be as little as a few degrees or as much as 90°.
- the optimum angle may vary as a function of extrudate exit velocity, roll speed, vertical distance from the die to the roll, and horizontal distance from the die centerline to the top dead center of the roll.
- the series of stretch rolls 140 may include one or more individual stretch rolls, and suitably at least two stretch rolls 145 and 160 as shown in Fig. 2.
- the stretch rolls 145 and 160 rotate at a speed greater than a speed at which the chill roll 120 rotates, thereby stretching the filaments 105.
- each successive roll rotates at a speed greater than the speed of the previous roll.
- the filaments 105 are then allowed to relax prior to entering a nip formed between rolls 165.
- Nonwoven web facings 155 and 185 are unwound from supply rolls 154 and 184, respectively, and also supplied to the nip for lamination to the filaments 105.
- the resulting composite 132 is wound and stored on a take-up roll 160 as described above.
- composites may be formed according to the present invention that are relatively inelastic prior to heat activation.
- One parameter that is indicative of the dimensional stability of the composite prior to heat activation is the percent strain that it undergoes at a load of 2000 grams-force per 3 inches wide (sample width) according to the "stretch to stop" test, which is described in more detail below.
- the composite typically has a percent strain of about 50% or less in the machine direction, in some embodiments about 40% or less in the machine direction, and in some embodiments, about 25% or less in the machine direction prior to heat activation.
- the composite After heat shrinkage, the composite typically has a percent strain of about 50% or more in the machine direction, in some embodiments about 75% or more in the machine direction, and in some embodiments, from about 100% to about 200% in the machine direction. Furthermore, the potential shrinkage of the composite may be about 40% or more, in some embodiments about 50% or more, and in some embodiments, about 60% or more.
- the composite may be more easily processed into an end product because it is less elastic prior to activation, and thus more dimensionally stable.
- a latent elastic composite may be incorporated into an absorbent article.
- the latent elastic composite may be activated through the application of heat, such as during the curing process for an adhesive used to attach together various components of the product.
- the latent elastic composite has a greater dimensional stability prior to activation than highly elastic materials, enhanced processing efficiencies may be realized.
- the composite need not be maintained in a mechanically stretched condition during attachment to other components of the product. This allows for greater freedom in the location and manner in which the adhesive is applied.
- the latent elastic composite of the present invention may be used in a wide variety of applications.
- the elastic composite may be used in an absorbent article.
- An "absorbent article” generally refers to any article capable of absorbing water or other fluids. Examples of some absorbent articles include, but are not limited to, personal care absorbent articles, such as diapers, training pants, absorbent underpants, incontinence articles, feminine hygiene products (e.g., sanitary napkins), swim wear, baby wipes, and so forth; medical absorbent articles, such as garments, fenestration materials, underpads, bedpads, bandages, absorbent drapes, and medical wipes; food service wipers; clothing articles; and so forth.
- absorbent articles include a substantially liquid-impermeable layer (e.g., outer cover), a liquid- permeable layer (e.g., bodyside liner, surge layer, etc.), and an absorbent core.
- the elastic strand layer of the present invention may be used in providing elastic waist, leg cuff/gasketing, stretchable ear, side panel or stretchable outer cover applications.
- the backsheet 270 extends outwardly beyond the terminal marginal edges of the liquid retention structure 280 to form side margins and end margins of the diaper 250.
- the topsheet 275 is generally coextensive with the backsheet 270 but may optionally cover an area that is larger or smaller than the area of the backsheet 270, as desired.
- the various regions and/or components of the diaper 201 may be assembled together using any known attachment mechanism, such as adhesive, ultrasonic, thermal bonds, etc.
- Suitable adhesives may include, for instance, hot melt adhesives, pressure-sensitive adhesives, and so forth. When utilized, the adhesive may be applied as a uniform layer, a patterned layer, a sprayed pattern, or any of separate lines, swirls or dots.
- the materials were tested using a cyclical testing procedure to determine load loss and percent set.
- 2-cycle testing was utilized to 100% defined elongation.
- the sample size was 3 inches (7.6 centimeters) in the cross-machine direction by 6 inches in the machine direction.
- the Grip size was 3 inches (7.6 centimeters) in width.
- the grip separation was 4 inches.
- the samples were loaded such that the machine direction of the sample was in the vertical direction. A preload of approximately 20 to 30 grams was set.
- the test pulled the sample to 100% elongation at a speed of 20 inches (50.8 centimeters) per minute, and then immediately (without pause) returned to the zero at a speed of 20 inches (50.8 centimeters) per minute.
- the testing was done on a Sintech Corp. constant rate of extension tester 2/S with a Renew MTS mongoose box (controller) using TESTWORKS 4.07b software (Sintech Corp, of Cary, NC). The tests were conducted under ambient conditions. Results are generally reported as an average of three specimens and may be performed with the specimen in the cross direction (CD) and/or the machine direction (MD).
- EXAMPLE 1 Six samples (Nos. 1-6) of a continuous filament/meltblown laminate were initially formed using the "horizontal" method shown in Fig. 1. The filaments were formed from 100 wt.% KRATON® MD6673 (Kraton Polymers, LLC of Houston Texas). KRATON® MD6673 contains 68 wt.% of a styrene-ethylene-butyiene- styrene block copolymer (KRATON® MD6937), 20 wt.% REGALREZTM 1126 (Eastman Chemical) and 12 wt.% EPOLENETM C-10 polyethylene wax (Eastman Chemical).
- KRATON® MD6673 contains 68 wt.% of a styrene-ethylene-butyiene- styrene block copolymer (KRATON® MD6937), 20 wt.% REGALREZTM 1126 (Eastman Chemical) and 12 wt.% EPOLENETM C-10 polyethylene wax (Eastman Chemical).
- a 1.5" Killion extruder was used to extrude the parallel continuous filaments and a 3" Beloit extruder was used to produce the meltblown fibers.
- the extruder temperatures were set at 500 0 F and 420 0 F for the 1.5" and 3" extruders, respectively.
- the filament die had 12 holes per inch, each hole having a diameter of 0.9 millimeters.
- the filaments were first laid down on a foraminous wire and then the meltblown fibers were formed on top of the filaments.
- the filament/meltblown structure was removed from the forming wire at a speed of 20 feet per minute and then passed through S-wrap rollers operating at a speed of 100 feet per minute, thereby stretching the structure at a stretch ratio of about 5.0 in the machine direction.
- the extruder temperatures were set at 500 0 F and 420°F for the 1.5" and 3" extruders, respectively.
- the filament die had 12 holes per inch, each hole having a diameter of 0.9 millimeters.
- the filaments were first laid down on a foraminous wire and then the meltblown fibers were formed on top of the filaments.
- the filament/meltblown structure was removed from the forming wire at a speed of 20 feet per minute and then passed through S-wrap rollers operating at a speed of 100 feet per minute, thereby stretching the structure at a stretch ratio of about 5.0 in the machine direction.
- the samples were then passed through two smooth calender rolls and thermally bonded to a polypropylene spunbond facing having a basis weight of approximately 13.6 grams per square meter.
Landscapes
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Nonwoven Fabrics (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0718941-9A BRPI0718941B1 (en) | 2006-11-22 | 2007-09-28 | DENTAL ELASTICITY FILTED COMPOSITE |
KR1020097010381A KR101511390B1 (en) | 2006-11-22 | 2007-09-28 | Strand composite having latent elasticity |
MX2009005301A MX2009005301A (en) | 2006-11-22 | 2007-09-28 | Strand composite having latent elasticity. |
AU2007323084A AU2007323084B2 (en) | 2006-11-22 | 2007-09-28 | Strand composite having latent elasticity |
EP20070826581 EP2076384B1 (en) | 2006-11-22 | 2007-09-28 | Strand composite having latent elasticity |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/603,954 | 2006-11-22 | ||
US11/603,954 US7938921B2 (en) | 2006-11-22 | 2006-11-22 | Strand composite having latent elasticity |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008062328A1 true WO2008062328A1 (en) | 2008-05-29 |
Family
ID=38982812
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2007/053952 WO2008062328A1 (en) | 2006-11-22 | 2007-09-28 | Strand composite having latent elasticity |
Country Status (7)
Country | Link |
---|---|
US (1) | US7938921B2 (en) |
EP (1) | EP2076384B1 (en) |
KR (1) | KR101511390B1 (en) |
AU (1) | AU2007323084B2 (en) |
BR (1) | BRPI0718941B1 (en) |
MX (1) | MX2009005301A (en) |
WO (1) | WO2008062328A1 (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8709191B2 (en) | 2008-05-15 | 2014-04-29 | Kimberly-Clark Worldwide, Inc. | Latent elastic composite formed from a multi-layered film |
EP2416956B1 (en) * | 2009-04-08 | 2016-01-06 | The Procter and Gamble Company | Stretchable laminates of nonwoven web(s) and elastic film |
CA2806308A1 (en) * | 2009-04-08 | 2010-10-14 | The Procter & Gamble Company | Stretchable laminates of nonwoven web(s) and elastic film |
CN102387917B (en) * | 2009-04-08 | 2016-03-09 | 宝洁公司 | Non-woven webs and elastic film can stretch laminate |
JP5373183B2 (en) * | 2009-04-08 | 2013-12-18 | ザ プロクター アンド ギャンブル カンパニー | Non-woven web (s) and elastic laminate of elastic film |
US20110152808A1 (en) * | 2009-12-21 | 2011-06-23 | Jackson David M | Resilient absorbent coform nonwoven web |
US9260808B2 (en) | 2009-12-21 | 2016-02-16 | Kimberly-Clark Worldwide, Inc. | Flexible coform nonwoven web |
US20120053547A1 (en) * | 2010-08-31 | 2012-03-01 | Karyn Clare Schroeder | Absorbent Composite With A Resilient Coform Layer |
AU2011241903B2 (en) * | 2010-04-16 | 2015-12-17 | Kimberly-Clark Worldwide, Inc. | Absorbent composite with a resilient coform layer |
US20120066855A1 (en) * | 2010-09-17 | 2012-03-22 | Schmidt Michael A | Coform nonwoven web having multiple textures |
EP2720862B1 (en) | 2011-06-17 | 2016-08-24 | Fiberweb, Inc. | Vapor permeable, substantially water impermeable multilayer article |
WO2012177376A1 (en) * | 2011-06-21 | 2012-12-27 | Exxonmobil Chemical Patents Inc. | Elastic nonwoven materials comprising propylene-based and ethylene-based polymers |
US10369769B2 (en) | 2011-06-23 | 2019-08-06 | Fiberweb, Inc. | Vapor-permeable, substantially water-impermeable multilayer article |
DK2723568T3 (en) | 2011-06-23 | 2017-10-23 | Fiberweb Llc | Vapor permeable, essentially all water impermeable, multilayer |
US9765459B2 (en) | 2011-06-24 | 2017-09-19 | Fiberweb, Llc | Vapor-permeable, substantially water-impermeable multilayer article |
US20130309439A1 (en) | 2012-05-21 | 2013-11-21 | Kimberly-Clark Worldwide, Inc. | Fibrous Nonwoven Web with Uniform, Directionally-Oriented Projections and a Process and Apparatus for Making the Same |
US9251792B2 (en) * | 2012-06-15 | 2016-02-02 | Sri International | Multi-sample conversational voice verification |
GB2529358A (en) | 2013-06-20 | 2016-02-17 | Procter & Gamble | Absorbent articles with activation-friendly laminates |
US10259165B2 (en) | 2015-04-01 | 2019-04-16 | Aurizon Ultrasonics, LLC | Apparatus for fabricating an elastic nonwoven material |
CN110636823A (en) | 2017-05-17 | 2019-12-31 | 贝瑞全球有限公司 | Elastic nonwoven lamination process and apparatus |
US20210388548A1 (en) * | 2018-10-25 | 2021-12-16 | Mitsui Chemicals, Inc. | Multilayer nonwoven fabric, stretchable multilayer nonwoven fabric, fiber product, absorbent article, and sanitary mask |
CN113825631A (en) | 2019-03-22 | 2021-12-21 | 杜凯恩Ias有限责任公司 | Apparatus for making elastic nonwoven material |
WO2023085277A1 (en) * | 2021-11-09 | 2023-05-19 | 東洋紡エムシー株式会社 | Long-fiber nonwoven fabric laminate, and bag-like object using same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5385775A (en) | 1991-12-09 | 1995-01-31 | Kimberly-Clark Corporation | Composite elastic material including an anisotropic elastic fibrous web and process to make the same |
WO2003031151A1 (en) * | 2001-10-09 | 2003-04-17 | Kimberly-Clark Worldwide, Inc. | Method of producing latent elastic, cross-direction-oriented films |
US20050043460A1 (en) * | 2003-08-22 | 2005-02-24 | Kimberly-Clark Worldwide, Inc. | Microporous breathable elastic films, methods of making same, and limited use or disposable product applications |
US20060246803A1 (en) * | 2005-04-29 | 2006-11-02 | Smith Charles A | Latent elastic articles and methods of making thereof |
WO2007070146A1 (en) * | 2005-12-15 | 2007-06-21 | Kimberly-Clark Worldwide, Inc. | Latent elastic laminates and methods of making latent elastic laminates |
Family Cites Families (135)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3338992A (en) * | 1959-12-15 | 1967-08-29 | Du Pont | Process for forming non-woven filamentary structures from fiber-forming synthetic organic polymers |
NL130678C (en) * | 1960-07-15 | 1900-01-01 | ||
USRE28688E (en) * | 1960-10-31 | 1976-01-20 | Raychem Corporation | Solid heat-flowable dispersed phase in a crosslinked elastomer |
US3502763A (en) * | 1962-02-03 | 1970-03-24 | Freudenberg Carl Kg | Process of producing non-woven fabric fleece |
US3354506A (en) | 1962-04-30 | 1967-11-28 | Union Carbide Corp | Apparatus for melt extrusion of multi-wall plastic tubing |
US3502538A (en) * | 1964-08-17 | 1970-03-24 | Du Pont | Bonded nonwoven sheets with a defined distribution of bond strengths |
US3341394A (en) | 1966-12-21 | 1967-09-12 | Du Pont | Sheets of randomly distributed continuous filaments |
US3494821A (en) * | 1967-01-06 | 1970-02-10 | Du Pont | Patterned nonwoven fabric of hydraulically entangled textile fibers and reinforcing fibers |
US3542615A (en) | 1967-06-16 | 1970-11-24 | Monsanto Co | Process for producing a nylon non-woven fabric |
US3849241A (en) | 1968-12-23 | 1974-11-19 | Exxon Research Engineering Co | Non-woven mats by melt blowing |
US3801429A (en) * | 1969-06-06 | 1974-04-02 | Dow Chemical Co | Multilayer plastic articles |
DE1939528A1 (en) * | 1969-08-02 | 1971-02-11 | Barmag Barmer Maschf | Device for the continuous production of multilayer blown films |
DE2048006B2 (en) * | 1969-10-01 | 1980-10-30 | Asahi Kasei Kogyo K.K., Osaka (Japan) | Method and device for producing a wide nonwoven web |
DE1950669C3 (en) | 1969-10-08 | 1982-05-13 | Metallgesellschaft Ag, 6000 Frankfurt | Process for the manufacture of nonwovens |
US3639917A (en) * | 1970-04-07 | 1972-02-08 | Raychem Corp | Heat recoverable article |
US3912565A (en) | 1972-01-24 | 1975-10-14 | Fmc Corp | Method of preparing shirred, elastic, flexible articles |
GB1453447A (en) * | 1972-09-06 | 1976-10-20 | Kimberly Clark Co | Nonwoven thermoplastic fabric |
GB1550955A (en) * | 1975-12-29 | 1979-08-22 | Johnson & Johnson | Textile fabric and method of manufacturing the same |
US4323534A (en) * | 1979-12-17 | 1982-04-06 | The Procter & Gamble Company | Extrusion process for thermoplastic resin composition for fabric fibers with exceptional strength and good elasticity |
US4340563A (en) * | 1980-05-05 | 1982-07-20 | Kimberly-Clark Corporation | Method for forming nonwoven webs |
US4374888A (en) * | 1981-09-25 | 1983-02-22 | Kimberly-Clark Corporation | Nonwoven laminate for recreation fabric |
US4527990A (en) * | 1982-09-30 | 1985-07-09 | Kimberly-Clark Corporation | Elasticized garment and method for its manufacture |
US4937299A (en) * | 1983-06-06 | 1990-06-26 | Exxon Research & Engineering Company | Process and catalyst for producing reactor blend polyolefins |
US4795668A (en) * | 1983-10-11 | 1989-01-03 | Minnesota Mining And Manufacturing Company | Bicomponent fibers and webs made therefrom |
US4543154A (en) | 1983-11-04 | 1985-09-24 | The Procter & Gamble Company | Method for severing a laminated web containing a dimensionally heat unstable layer to produce non-linear shirred edges |
US4640859A (en) * | 1983-12-27 | 1987-02-03 | Minnesota Mining And Manufacturing Company | Inelastic, heat-elasticizable sheet material for diapers |
US4552795A (en) | 1983-12-27 | 1985-11-12 | Minnesota Mining And Manufacturing Co. | Inelastic, heat-elasticizable sheet material |
US5176668A (en) * | 1984-04-13 | 1993-01-05 | Kimberly-Clark Corporation | Absorbent structure designed for absorbing body fluids |
US4816094A (en) * | 1984-05-01 | 1989-03-28 | Kimberly-Clark Corporation | Method of producing a heat shrinkable elastomer and articles utilizing the elastomer |
US4663106A (en) * | 1984-05-01 | 1987-05-05 | Kimberly-Clark Corporation | Formation of elasticized portions of disposable garments and other articles |
CA1341430C (en) | 1984-07-02 | 2003-06-03 | Kenneth Maynard Enloe | Diapers with elasticized side pockets |
US4665306A (en) * | 1985-04-04 | 1987-05-12 | Kimberly-Clark Corporation | Apparatus for activating heat shrinkable ribbon on disposable garments and other articles |
US4640726A (en) * | 1985-06-27 | 1987-02-03 | Kimberly-Clark Corporation | Heat activation process and apparatus for heat shrinkable material |
US4663220A (en) * | 1985-07-30 | 1987-05-05 | Kimberly-Clark Corporation | Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers |
US4680450A (en) * | 1985-07-30 | 1987-07-14 | Kimberly-Clark Corporation | Apparatus for controlling the heating of composite materials |
US4720415A (en) * | 1985-07-30 | 1988-01-19 | Kimberly-Clark Corporation | Composite elastomeric material and process for making the same |
JPS6269822A (en) | 1985-09-19 | 1987-03-31 | Chisso Corp | Heat bondable conjugate fiber |
US4834738A (en) * | 1986-12-31 | 1989-05-30 | Kimberly-Clark Corporation | Disposable garment having elastic outer cover and integrated absorbent insert structure |
US4766029A (en) * | 1987-01-23 | 1988-08-23 | Kimberly-Clark Corporation | Semi-permeable nonwoven laminate |
US4787699A (en) | 1987-09-01 | 1988-11-29 | Hughes Aircraft Company | Fiber optic terminus |
US5162074A (en) | 1987-10-02 | 1992-11-10 | Basf Corporation | Method of making plural component fibers |
US4916005A (en) * | 1987-10-13 | 1990-04-10 | Kimberly-Clark Corporation | Diaper article with elasticized waist panel |
US4798603A (en) * | 1987-10-16 | 1989-01-17 | Kimberly-Clark Corporation | Absorbent article having a hydrophobic transport layer |
US4940464A (en) * | 1987-12-16 | 1990-07-10 | Kimberly-Clark Corporation | Disposable incontinence garment or training pant |
US4965122A (en) | 1988-09-23 | 1990-10-23 | Kimberly-Clark Corporation | Reversibly necked material |
US5226992A (en) * | 1988-09-23 | 1993-07-13 | Kimberly-Clark Corporation | Process for forming a composite elastic necked-bonded material |
US4981747A (en) * | 1988-09-23 | 1991-01-01 | Kimberly-Clark Corporation | Composite elastic material including a reversibly necked material |
US5003178A (en) * | 1988-11-14 | 1991-03-26 | Electron Vision Corporation | Large-area uniform electron source |
US5218071A (en) * | 1988-12-26 | 1993-06-08 | Mitsui Petrochemical Industries, Ltd. | Ethylene random copolymers |
US5069970A (en) | 1989-01-23 | 1991-12-03 | Allied-Signal Inc. | Fibers and filters containing said fibers |
JP2682130B2 (en) * | 1989-04-25 | 1997-11-26 | 三井石油化学工業株式会社 | Flexible long-fiber non-woven fabric |
US5501679A (en) * | 1989-11-17 | 1996-03-26 | Minnesota Mining And Manufacturing Company | Elastomeric laminates with microtextured skin layers |
ES2074172T3 (en) | 1989-11-17 | 1995-09-01 | Minnesota Mining & Mfg | ELASTOMER LAMINATES WITH MICROTEXTURED LEATHER LAYERS. |
US5057368A (en) | 1989-12-21 | 1991-10-15 | Allied-Signal | Filaments having trilobal or quadrilobal cross-sections |
US5169706A (en) | 1990-01-10 | 1992-12-08 | Kimberly-Clark Corporation | Low stress relaxation composite elastic material |
US5429856A (en) | 1990-03-30 | 1995-07-04 | Minnesota Mining And Manufacturing Company | Composite materials and process |
US5093422A (en) * | 1990-04-23 | 1992-03-03 | Shell Oil Company | Low stress relaxation extrudable elastomeric composition |
US5464688A (en) | 1990-06-18 | 1995-11-07 | Kimberly-Clark Corporation | Nonwoven web laminates with improved barrier properties |
US5213881A (en) * | 1990-06-18 | 1993-05-25 | Kimberly-Clark Corporation | Nonwoven web with improved barrier properties |
US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
US5140757A (en) * | 1990-10-09 | 1992-08-25 | Terada Stanley H | Elastic band heat activation system |
US5176672A (en) * | 1990-11-13 | 1993-01-05 | Kimberly-Clark Corporation | Pocket-like diaper or absorbent article |
CA2048905C (en) * | 1990-12-21 | 1998-08-11 | Cherie H. Everhart | High pulp content nonwoven composite fabric |
US5192606A (en) * | 1991-09-11 | 1993-03-09 | Kimberly-Clark Corporation | Absorbent article having a liner which exhibits improved softness and dryness, and provides for rapid uptake of liquid |
ZA92308B (en) * | 1991-09-11 | 1992-10-28 | Kimberly Clark Co | Thin absorbent article having rapid uptake of liquid |
US5277976A (en) * | 1991-10-07 | 1994-01-11 | Minnesota Mining And Manufacturing Company | Oriented profile fibers |
US5278272A (en) * | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
US5382400A (en) * | 1992-08-21 | 1995-01-17 | Kimberly-Clark Corporation | Nonwoven multicomponent polymeric fabric and method for making same |
US5336552A (en) * | 1992-08-26 | 1994-08-09 | Kimberly-Clark Corporation | Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and ethylene alkyl acrylate copolymer |
US5322728A (en) * | 1992-11-24 | 1994-06-21 | Exxon Chemical Patents, Inc. | Fibers of polyolefin polymers |
IT1256260B (en) * | 1992-12-30 | 1995-11-29 | Montecatini Tecnologie Srl | ATACTIC POLYPROPYLENE |
USH2096H1 (en) * | 1993-02-03 | 2004-01-06 | Exxon Chemical Patents, I | Thermoplastic elastomer copolymer films |
US5332613A (en) * | 1993-06-09 | 1994-07-26 | Kimberly-Clark Corporation | High performance elastomeric nonwoven fibrous webs |
US5472775A (en) | 1993-08-17 | 1995-12-05 | The Dow Chemical Company | Elastic materials and articles therefrom |
CA2120646A1 (en) | 1993-12-16 | 1995-06-17 | Kimberly-Clark Worldwide, Inc. | Dynamic fitting diaper |
US5399219A (en) * | 1994-02-23 | 1995-03-21 | Kimberly-Clark Corporation | Method for making a fastening system for a dynamic fitting diaper |
EP0672774B1 (en) * | 1994-03-04 | 1999-07-14 | Kimberly-Clark Worldwide, Inc. | Improved surge management fibrous nonwoven web for personal care absorbent articles and the like |
US5486166A (en) * | 1994-03-04 | 1996-01-23 | Kimberly-Clark Corporation | Fibrous nonwoven web surge layer for personal care absorbent articles and the like |
CA2125807A1 (en) * | 1994-03-14 | 1995-09-15 | Edward Heerman Ruscher | Apparatus and method for stretching an elastomeric material in a cross machine direction |
US5571619A (en) | 1994-05-24 | 1996-11-05 | Exxon Chemical Patents, Inc. | Fibers and oriented films of polypropylene higher α-olefin copolymers |
US5669896A (en) * | 1994-06-16 | 1997-09-23 | Kimberly-Clark Worldwide, Inc. | Absorbent garment comprising dual containment flaps |
US5540796A (en) * | 1994-08-03 | 1996-07-30 | Kimberly-Clark Corporation | Process for assembling elasticized ear portions |
CN1144574C (en) * | 1994-08-31 | 2004-04-07 | 金伯利-克拉克环球有限公司 | Thin absorbent article having wicking and crush resistant properties |
USH1808H (en) | 1994-11-17 | 1999-10-05 | Shell Oil Company | Extrudable styrenic block copolymer compositions containing a metallocene polyolefin |
US5539056A (en) * | 1995-01-31 | 1996-07-23 | Exxon Chemical Patents Inc. | Thermoplastic elastomers |
US5595618A (en) * | 1995-04-03 | 1997-01-21 | Kimberly-Clark Corporation | Assembly process for a laminated tape |
US5773374A (en) * | 1995-04-24 | 1998-06-30 | Wood; Leigh E. | Composite materials and process |
US5827259A (en) | 1995-10-25 | 1998-10-27 | Kimberly-Clark Worldwide, Inc. | Absorbent article with waist elastic and containment system |
US5766389A (en) * | 1995-12-29 | 1998-06-16 | Kimberly-Clark Worldwide, Inc. | Disposable absorbent article having a registered graphic and process for making |
US5885908A (en) * | 1996-10-04 | 1999-03-23 | Minnesota Mining And Manufacturing Co. | Anisotropic elastic films |
US6200669B1 (en) * | 1996-11-26 | 2001-03-13 | Kimberly-Clark Worldwide, Inc. | Entangled nonwoven fabrics and methods for forming the same |
US6111163A (en) * | 1996-12-27 | 2000-08-29 | Kimberly-Clark Worldwide, Inc. | Elastomeric film and method for making the same |
US6015764A (en) * | 1996-12-27 | 2000-01-18 | Kimberly-Clark Worldwide, Inc. | Microporous elastomeric film/nonwoven breathable laminate and method for making the same |
US6407492B1 (en) * | 1997-01-02 | 2002-06-18 | Advanced Electron Beams, Inc. | Electron beam accelerator |
US6436529B1 (en) * | 1997-01-21 | 2002-08-20 | 3M Innovative Properties Company | Elatomeric laminates and composites |
US5997981A (en) | 1997-09-15 | 1999-12-07 | Kimberly-Clark Worldwide, Inc. | Breathable barrier composite useful as an ideal loop fastener component |
US5932497A (en) * | 1997-09-15 | 1999-08-03 | Kimberly-Clark Worldwide, Inc. | Breathable elastic film and laminate |
US6090325A (en) * | 1997-09-24 | 2000-07-18 | Fina Technology, Inc. | Biaxially-oriented metallocene-based polypropylene films |
US6315864B2 (en) | 1997-10-30 | 2001-11-13 | Kimberly-Clark Worldwide, Inc. | Cloth-like base sheet and method for making the same |
US6060009A (en) * | 1998-02-18 | 2000-05-09 | 3M Innovative Properties Company | Method of laminate formation |
AR018359A1 (en) | 1998-05-18 | 2001-11-14 | Dow Global Technologies Inc | HEAT RESISTANT ARTICLE, CONFIGURED, IRRADIATED AND RETICULATED, FREE FROM A SILANAN RETICULATION AGENT |
US6709742B2 (en) * | 1998-05-18 | 2004-03-23 | Dow Global Technologies Inc. | Crosslinked elastic fibers |
CA2332558A1 (en) * | 1998-06-01 | 1999-12-09 | The Dow Chemical Company | Method of making washable, dryable elastic articles |
US6645190B1 (en) | 1999-11-22 | 2003-11-11 | Kimberly-Clark Worldwide, Inc. | Absorbent article with non-irritating refastenable seams |
US6761711B1 (en) * | 1998-12-18 | 2004-07-13 | Kimberly-Clark Worldwide, Inc. | Absorbent articles with refastenable side seams |
US6500563B1 (en) | 1999-05-13 | 2002-12-31 | Exxonmobil Chemical Patents Inc. | Elastic films including crystalline polymer and crystallizable polymers of propylene |
US6461457B1 (en) | 1999-06-30 | 2002-10-08 | Kimberly-Clark Worldwide, Inc. | Dimensionally stable, breathable, stretch-thinned, elastic films |
AU7371400A (en) * | 1999-09-17 | 2001-04-17 | Procter & Gamble Company, The | Radiation crosslinked elastomeric materials |
US6663611B2 (en) | 1999-09-28 | 2003-12-16 | Kimberly-Clark Worldwide, Inc. | Breathable diaper with low to moderately breathable inner laminate and more breathable outer cover |
US6479154B1 (en) | 1999-11-01 | 2002-11-12 | Kimberly-Clark Worldwide, Inc. | Coextruded, elastomeric breathable films, process for making same and articles made therefrom |
US6794024B1 (en) | 1999-11-01 | 2004-09-21 | Kimberly-Clark Worldwide, Inc. | Styrenic block copolymer breathable elastomeric films |
JP2003515619A (en) | 1999-11-01 | 2003-05-07 | キンバリー クラーク ワールドワイド インコーポレイテッド | Breathable elastomer film of styrenic block copolymer |
US6969441B2 (en) * | 2000-05-15 | 2005-11-29 | Kimberly-Clark Worldwide, Inc. | Method and apparatus for producing laminated articles |
US20020009940A1 (en) * | 2000-05-15 | 2002-01-24 | May Raymond Jeffrey | Targeted elastic laminate having zones of different polymer materials |
JP3974315B2 (en) | 2000-07-25 | 2007-09-12 | 三菱電機株式会社 | AC generator |
JP3658301B2 (en) * | 2000-08-31 | 2005-06-08 | ユニ・チャーム株式会社 | Method for producing composite sheet having elastic elasticity |
US6946413B2 (en) | 2000-12-29 | 2005-09-20 | Kimberly-Clark Worldwide, Inc. | Composite material with cloth-like feel |
DK1453994T3 (en) | 2001-11-06 | 2007-09-10 | Dow Global Technologies Inc | Isotactic propylene copolymer fibers, their preparation and use |
US6902796B2 (en) * | 2001-12-28 | 2005-06-07 | Kimberly-Clark Worldwide, Inc. | Elastic strand bonded laminate |
US6978486B2 (en) * | 2002-07-02 | 2005-12-27 | Kimberly-Clark Worldwide, Inc. | Garment including an elastomeric composite laminate |
US20040110442A1 (en) * | 2002-08-30 | 2004-06-10 | Hannong Rhim | Stretchable nonwoven materials with controlled retraction force and methods of making same |
US20060151914A1 (en) * | 2002-08-30 | 2006-07-13 | Gerndt Robert J | Device and process for treating flexible web by stretching between intermeshing forming surfaces |
US8389634B2 (en) * | 2002-10-02 | 2013-03-05 | Dow Global Technologies Llc | Polymer compositions comprising a low-viscosity, homogeneously branched ethylene α-olefin extender |
US7320948B2 (en) * | 2002-12-20 | 2008-01-22 | Kimberly-Clark Worldwide, Inc. | Extensible laminate having improved stretch properties and method for making same |
US7226880B2 (en) * | 2002-12-31 | 2007-06-05 | Kimberly-Clark Worldwide, Inc. | Breathable, extensible films made with two-component single resins |
US6916750B2 (en) * | 2003-03-24 | 2005-07-12 | Kimberly-Clark Worldwide, Inc. | High performance elastic laminates made from high molecular weight styrenic tetrablock copolymer |
US6964720B2 (en) | 2003-03-26 | 2005-11-15 | The Procter & Gamble Company | Elastomeric nonwoven laminates and process for producing same |
EP1656254B1 (en) | 2003-08-22 | 2012-02-01 | Kimberly-Clark Worldwide, Inc. | Microporous breathable elastic film laminates |
US7601657B2 (en) * | 2003-12-31 | 2009-10-13 | Kimberly-Clark Worldwide, Inc. | Single sided stretch bonded laminates, and methods of making same |
US20050245162A1 (en) | 2004-04-30 | 2005-11-03 | Kimberly-Clark Worldwide, Inc. | Multi-capable elastic laminate process |
US20060003658A1 (en) * | 2004-06-30 | 2006-01-05 | Hall Gregory K | Elastic clothlike meltblown materials, articles containing same, and methods of making same |
US7612001B2 (en) * | 2004-12-22 | 2009-11-03 | Kimberly-Clark Worldwide, Inc. | High performance elastic materials made using styrene block copolymers and mixtures |
US7651653B2 (en) * | 2004-12-22 | 2010-01-26 | Kimberly-Clark Worldwide, Inc. | Machine and cross-machine direction elastic materials and methods of making same |
US20060148358A1 (en) * | 2004-12-30 | 2006-07-06 | Hall Gregory K | Elastic laminate and process therefor |
US20060251858A1 (en) | 2005-05-06 | 2006-11-09 | Kimberly-Clark Worldwide, Inc. | Elastic, breathable barrier films and laminates |
-
2006
- 2006-11-22 US US11/603,954 patent/US7938921B2/en active Active
-
2007
- 2007-09-28 EP EP20070826581 patent/EP2076384B1/en active Active
- 2007-09-28 MX MX2009005301A patent/MX2009005301A/en active IP Right Grant
- 2007-09-28 BR BRPI0718941-9A patent/BRPI0718941B1/en active IP Right Grant
- 2007-09-28 AU AU2007323084A patent/AU2007323084B2/en active Active
- 2007-09-28 KR KR1020097010381A patent/KR101511390B1/en active IP Right Grant
- 2007-09-28 WO PCT/IB2007/053952 patent/WO2008062328A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5385775A (en) | 1991-12-09 | 1995-01-31 | Kimberly-Clark Corporation | Composite elastic material including an anisotropic elastic fibrous web and process to make the same |
WO2003031151A1 (en) * | 2001-10-09 | 2003-04-17 | Kimberly-Clark Worldwide, Inc. | Method of producing latent elastic, cross-direction-oriented films |
US20050043460A1 (en) * | 2003-08-22 | 2005-02-24 | Kimberly-Clark Worldwide, Inc. | Microporous breathable elastic films, methods of making same, and limited use or disposable product applications |
US20060246803A1 (en) * | 2005-04-29 | 2006-11-02 | Smith Charles A | Latent elastic articles and methods of making thereof |
WO2007070146A1 (en) * | 2005-12-15 | 2007-06-21 | Kimberly-Clark Worldwide, Inc. | Latent elastic laminates and methods of making latent elastic laminates |
Also Published As
Publication number | Publication date |
---|---|
BRPI0718941B1 (en) | 2018-07-24 |
AU2007323084B2 (en) | 2012-01-12 |
AU2007323084A1 (en) | 2008-05-29 |
KR20090082239A (en) | 2009-07-29 |
US7938921B2 (en) | 2011-05-10 |
US20080119103A1 (en) | 2008-05-22 |
EP2076384B1 (en) | 2013-07-03 |
MX2009005301A (en) | 2009-05-28 |
EP2076384A1 (en) | 2009-07-08 |
BRPI0718941A2 (en) | 2013-12-10 |
KR101511390B1 (en) | 2015-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7938921B2 (en) | Strand composite having latent elasticity | |
EP2076383B2 (en) | Nonwoven-film composite with latent elasticity | |
US9724248B2 (en) | Latent elastic composite formed from a multi-layered film | |
US7585382B2 (en) | Latent elastic nonwoven composite | |
US7910795B2 (en) | Absorbent article containing a crosslinked elastic film | |
AU2009265213B2 (en) | Elastic composite formed from multiple laminate structures | |
AU2007290942B2 (en) | Nonwoven composite containing an apertured elastic film | |
AU2011350922B2 (en) | Sheet materials containing S-B-S and S-I/B-S copolymers | |
KR20070107094A (en) | Cloth-like biaxial stretch nonwoven |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07826581 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007826581 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007323084 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2007323084 Country of ref document: AU Date of ref document: 20070928 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2009/005301 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020097010381 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: PI0718941 Country of ref document: BR Kind code of ref document: A2 Effective date: 20090522 |