EP3638760A1 - Waschbares substrat auf pflanzenbasis, das thermisch mit biobasierten fasern verbunden ist - Google Patents
Waschbares substrat auf pflanzenbasis, das thermisch mit biobasierten fasern verbunden istInfo
- Publication number
- EP3638760A1 EP3638760A1 EP18735022.8A EP18735022A EP3638760A1 EP 3638760 A1 EP3638760 A1 EP 3638760A1 EP 18735022 A EP18735022 A EP 18735022A EP 3638760 A1 EP3638760 A1 EP 3638760A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- nonwoven fabric
- wipe
- pla
- individualized bast
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/049—Cleaning or scouring pads; Wipes
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- 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
- D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
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- 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
- D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
- D04H1/4258—Regenerated cellulose series
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- 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
- D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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- 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
- D04H1/44—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/48—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
- D04H1/488—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation in combination with bonding agents
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- 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
- D04H1/44—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/48—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
- D04H1/49—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation entanglement by fluid jet in combination with another consolidation means
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- 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
- D04H1/542—Adhesive fibres
- D04H1/55—Polyesters
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- 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
- D04H1/58—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- 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
- D04H1/58—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/60—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently
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- 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
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
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- 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
- D04H3/013—Regenerated cellulose series
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- 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
- D04H3/015—Natural yarns or filaments
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- 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
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/11—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by fluid jet
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- 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
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
- D04H3/115—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by applying or inserting filamentary binding elements
Definitions
- aspects of the present invention are directed generally to nonwovens. More specifically, aspects of the present invention are related to biobased nonwovens.
- biobased product was defined by the United States Department of Agriculture (USD A) Secretary in the Farm Security and Rural Investment Act of 2002 as a commercial or industrial product (other than food or feed) that is composed, in whole or in significant part, of biological products, renewable domestic agricultural materials (including plant, animal, and marine materials), forestry materials, or an intermediate feedstock.
- agricultural resources that make up many biobased products include, for example, soybeans, corn, kenaf, flax, jute, and numerous other types of crops.
- Natural bast fibers are biobased fibers found in the stalks of the flax, hemp, jute, ramie, nettle, Spanish broom, and kenaf plants, to name only a few.
- native state bast fibers are 1 to 4 meters in length. These long native state fibers are comprised of bundles of individual fibers which are straight and have a length between 20 and 100 mm. The bundled individual fibers are glued together by a class of plant resins called pectins.
- Bast fibers can be used to create a variety of products, including nonwoven substrates and wet and dry wipers. To prove that nonwovens and wipers will sufficiently biodegrade, they can be tested against various standards, such as ASTM International D6400 and/or D6868 test standards, and/or certifications, such as the Biodegradable Products Institute ® (BPI ® ) certification. Brawny Industrial ® FLAX Cloths (Georgia- Pacific Consumer Products LP, Atlanta, Georgia) are examples of flax -based wipers that are certified by the BPI ® to be a BPI ® Compostable Product, as well as to meet the ASTM International D6400 and/or D6868 test standards. [0005] Various methods can be used to form biobased wipers from natural fibers.
- hydroentangled wipers are strong and absorbent, they may not withstand mechanical laudering and therefore may not be suitable for reuse. While hydroentangled fibers create strong bonds between the fibers, which provide strength to the substrates, the bonds may still be weakened by mechanical agitation in water, for example in laundry and dishwashing machines used to clean the nonwovens.
- a nonwoven fabric includes an entangled web of individualized bast fibers and polylactic acid (PLA) fibers. At least a portion of the bast fibers and a portion of the PLA fibers are thermally bonded together.
- PLA polylactic acid
- a nonwoven fabric includes an entangled web of individualized bast fibers, polylactic acid (PLA) fibers, and cellulose fibers. At least a portion of the PLA fibers are thermally bonded to the bast fibers and at least a portion of the PLA fibers are thermally bonded to the cellulose fibers.
- PLA polylactic acid
- a method of making a nonwoven fabric includes forming a web of individualized bast fibers and polylactic acid (PLA) fibers. The method further includes entangling the individualized bast fibers and the PLA fibers. The method includes heating to thermally bond at least a portion of the individualized bast fibers with at least a portion of the PLA fibers.
- PLA polylactic acid
- FIG. 1 is a graph of cross direction (CD) wet strength as a function of a series of wet agitation cycles according to aspects of the invention.
- FIG. 2A is an image of a 100% flax nonwoven after one wet agitation cycle.
- FIG. 2B is an image of a flax/viscose nonwoven after one wet agitation cycle.
- FIG. 3 A is an image of a flax/polylactic acid (PLA) nonwoven after wet agitation and drying according to aspects of the invention.
- PLA flax/polylactic acid
- FIG. 3B is an image of a flax/viscose/PLA nonwoven after wet agitation and drying according to aspects of the invention.
- exemplary is used herein to mean “serving as an example, instance or illustration.” Any embodiment or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments or designs.
- the terms "at least one” and “one or more” are understood to include any integer number greater than or equal to one, i.e. one, two, three, four, etc.
- the terms "a plurality” are understood to include any integer number greater than or equal to two, i.e. two, three, four, five, etc.
- references in the specification to "one aspect,” “an aspect,” “an example aspect,” etc., indicate that the aspect described can include a particular feature or characteristic, but every embodiment may or may not include the particular structure or characteristic. Moreover, such phrases are not necessarily referring to the same aspect. Further, when a particular structure or characteristic is described in connection with an aspect, it is submitted that it is within the knowledge of one skilled in the art to affect such structure or characteristic in connection with other aspects whether or not explicitly described.
- biobased means complying with the United States Department of Agriculture (USD A) Secretary in the Farm Security and Rural Investment Act of 2002 as being composed, in whole or in significant part, of biological products, renewable domestic agricultural materials (including plant, animal, and marine materials), forestry materials, or an intermediate feedstock. Biobased products are certified by the USDA.
- plant-based fiber means produced by and extracted from a plant as opposed to as opposed to man-made fibers formed from cellulose.
- nonwoven means a substrate or fabric having a structure of individual fibers or threads which are randomly interlaid, but not in an identifiable manner as in the case of a knitted or woven fabric.
- wiper means a dry wiper or a wet wiper that has been impregnated with a wetting solution.
- a wiper includes one or more plies of a nonwoven substrate, for example, one, two, three, or more plies.
- Dry tensile strengths are measured with a standard Instron test device (Instron Corporation, Canton,
- the tensile tester may be configured in various ways, for example using 3 or 1 inch wide strips of tissue or towel, conditioned in an atmosphere of 23°C ⁇ 1°C. (73.4°F ⁇ 1°F) at 50% relative humidity for 2 hours. The tensile test is run at a crosshead speed of 12.0 inch/min. The sample is clamped into the two jaws, and the test separation of the jaws is initiated. Following sample breakage, the dry tensile strength is recorded.
- substrate strength comes from inter-fiber friction amongst entangled fibers, wet agitation, such as during washing in a washing machine or dishwasher, and/or drying can cause the fibers to disentangle and the substrate to fall apart.
- thermo bonding component to fuse the fibers together and impart strength to the nonwoven substrate will allow the fibers to sufficiently maintain inter fiber bonding during wet agitation and/or drying processes.
- nonwoven substrates that use conventional thermal bonding fibers such as polyethylene
- PET terephthalate
- PPE polyphenylene ether
- nonwoven fabrics and methods of making nonwoven fabrics that incorporate a biobased thermal bonding component that allows the fibers to sufficiently maintain inter fiber bonds during wet agitation and drying (or heating) processes.
- the biobased thermal bonding fibers are 100% biobased and certified by the USDA.
- the biobased thermal bonding fibers include polylactic acid (PLA) according to some aspects of the invention.
- PLA polylactic acid
- the biobased fibers thermal bonding fibers are completely biodegradable in approved composting facilities.
- the biobased thermal bonding fibers are incorporated into a biobased nonwoven fabric, which is thermally bonded.
- the resulting nonwoven fabrics are dry wipers according to some aspects of the present invention.
- the nonwoven fabrics are also wet wipers impregnated with a wetting solution according to other aspects of the present invention.
- the nonwoven fabrics described herein are thermally bonded to provide a strong, 100% biobased product that can withstand wet agitation and drying processes, yet maintain USDA certification.
- the thermally bonded biobased nonwoven fabrics and wipers have improved wet durability, compared to non-thermally bonded biobased products, and are a USDA certified product that can be used in a variety of cleaning and maintenance applications.
- the nonwoven fabrics and wipers are
- a nonwoven fabric is 100% biobased.
- the nonwoven fabric includes bast fibers, which are plant-based fibers.
- the bast fiber is a flax fiber, a hemp fiber, a jute fiber, a ramie fiber, a nettle fiber, a Spanish broom fiber, a kenaf plant fiber, or any combination thereof.
- the bast fibers are flax fibers.
- the amount of bast fibers incorporated into the nonwoven fabric is tailored, depending on the nonwoven fabric application.
- the nonwoven fabric includes a majority (more than 50 weight % (wt.%) bast fibers.
- the bast fibers are present in a range between about 60 wt.% to about 92 wt.% based on the total weight of the nonwoven fabric.
- the bast fibers of the nonwoven fabric are present in a range between about 70 wt.% to about 80 wt.% based on the total weight of the nonwoven fabric.
- the bast fibers of the nonwoven fabric are present in a range between about 70 wt.% to about 90 wt.% based on the total weight of the nonwoven fabric.
- the amount of bast fibers in the nonwoven fabric is about or in any range between about 50, 55, 60, 65, 70, 75, 80, 85, 90, and 92 wt.% based on the total weight of the nonwoven fabric.
- the bast fibers are relatively long, having a mean length of about 25 mm (1 inch) to about 150 mm (6 inches) in some aspects. In other aspects, the bast fibers have a mean length in a range from about 25 mm (1 inch) to about 50 mm (2 inches). In other aspects, the bast fibers have a mean length of at least 6 mm. In some aspects, the bast fibers have a mean length of about 6 mm to about 55 mm.
- the bast fibers have a mean length about or in any range from about 6, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150 mm.
- the bast fibers of the nonwoven fabric are individualized bast fibers.
- Individualized bast fibers utilized in this invention are typically straight and are substantially pectin-free according to one or more aspects.
- conventional "individualized" bast fibers may be only subjected to mechanical
- Naturally occurring bundled bast fibers are chemically treated to remove the pectin holding the bundles together and to separate the naturally occurring fibers into individual bast fibers.
- Pectin acts as natural glue which holds the individual bast fibers in the bundle.
- Naturally occurring bundled bast fibers first are chemically treated to substantially remove pectin and form substantially pectin-free, individualized bast fibers. Enzymatic treatment is a non-limiting example of a chemical treatment that can be used to substantially remove pectin.
- the individualized bast fibers are substantially pectin-free.
- individualized bast fibers have less than 10% by weight of the pectin content of the naturally occurring fibers from which the substantially pectin-free fibers are derived.
- individualized bast fibers have less than 15% by weight of the pectin content of the naturally occurring fibers from which the substantially pectin- free fibers are derived.
- individualized bast fibers have less than 20%) by weight of the pectin content of the naturally occurring fibers from which the substantially pectin-free fibers are derived.
- individualized bast fibers have less than 0.1%> by weight, less than 0.15% by weight, or less than 0.20%> by weight, of the pectin content of the naturally occurring fibers from which the
- substantially pectin-free fibers are derived.
- the nonwoven fabric includes polylactic acid (PLA) fibers, which are also plant-based fibers.
- PLA fibers are 100%> biobased and certified by the USDA.
- the PLA fibers are derived from natural and sustainable raw materials, for example, corn plants and beet plants.
- suitable PLA fibers are commercially available from Far Easter New Century Corporation, Taipei, Taiwan.
- the PLA fibers function as the thermal bonding component in the nonwoven fabric, which allows the nonwoven fabric to be thermally bonded. At least a portion of the PLA fibers are thermally bonded to at least a portion of the individualized bast fibers in the nonwoven fabric. When other fibers are included in the nonwoven fabric, such as cellulose fibers (e.g., regenerated cellulose fibers), at least a portion of the PLA fibers also will be thermally bonded to the cellulose fibers.
- the PLA fibers have a melting point of about 120°C to about 170°C. In other aspects, the PLA fibers have a melting point of about 130°C to about 135°C.
- the PLA fibers have a melting point of about 130°C. Yet, in some aspects, the PLA fibers have a melting point about or in any range from about 120, 130, 135, 140, 145, 150, 155, 160, 165, and 170°C.
- the PLA fibers are bi-component fibers and/or have more than one melting point, or a range of melting points.
- the PLA fibers include a low melting point sheath and higher melting PLA core.
- the denier and mean length of the PLA fibers make them favorable for use as a thermal bonding component in the nonwoven fabric.
- the PLA fibers according to aspects of the invention, have a mean fiber length of about 45 mm to about 55 mm. In other aspects, the PLA fibers have a mean length of about 3 mm to about 55 mm. In some aspects, the PLA fibers have a mean length of about 3 mm (1/8 inch) to about 25 mm (1 inch). Yet, in one or more aspects, the PLA fibers have a mean length about or in any range from about 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, and 55 mm.
- the denier of the PLA fibers is about 3.6 to about 4.4 in some aspects. In other aspects, the denier of the PLA fibers is about 1.5 to about 4.4.
- the amount of PLA fibers incorporated into the nonwoven fabric is tailored, depending on the nonwoven fabric application.
- the PLA fibers are present in a range between about 8 wt.% to about 30 wt.% based on the total weight of the nonwoven fabric.
- the PLA fibers of the nonwoven fabric are present in a range between about 15 wt.% to about 25 wt.% based on the total weight of the nonwoven fabric.
- the PLA fibers of the nonwoven fabric are present in a range between about 8 wt.% to about 15 wt.% based on the total weight of the nonwoven fabric.
- the amount of PLA fibers in the nonwoven fabric is about or in any range between about 8, 10, 12, 15, 17, 20, 22, 25, 27, and 30 wt.% based on the total weight of the nonwoven fabric.
- the nonwoven fabric includes only bast fibers and PLA fibers. In other aspects, the nonwoven fabric includes bast fibers, PLA fibers, and cellulose fibers, which can be natural cellulose fibers or regenerated/reconstituted cellulose fibers.
- Regenerated/reconstituted cellulose fibers are man-made fibers formed from cellulose.
- regenerated cellulose include, but are not limited to, rayon, lyocell, (e.g., TENCEL®), Viscose®, or any combination thereof.
- TENCEL® and Viscose® are commercially available from Lenzing Aktiengesellschaft, Lenzing, Austria.
- Wood pulp fibers, or papermaking fibers are examples of natural cellulose fibers.
- the cellulose fibers can be chemically pulped or mechanically pulped, bleached or unbleached, virgin or recycled, high yield or low yield, and the like.
- the cellulose fibers are present in a range between about 1 wt.% and about 40 wt.% based on the total weight of the nonwoven fabric. In one aspect, the cellulose fibers of the nonwoven fabric are present in a range between about 5 wt.% to about 30 wt.% based on the total weight of the nonwoven fabric. In another aspect, the cellulose fibers of the nonwoven fabric are present in a range between about 10 wt.% to about 20 wt.% based on the total weight of the nonwoven fabric. In other aspects, the amount of cellulose fibers in the nonwoven fabric is about or in any range between about 1, 5, 10, 15, 20, 25, 30, 35, and 40 wt.% based on the total weight of the nonwoven fabric.
- the nonwoven fabric includes any other biobased fibers according to some embodiments.
- the fibers are combined and formed into a fiber web.
- the web includes individualized bast fibers and PLA fibers according to some aspects.
- the web includes individualized bast fibers, PLA fibers, and cellulose fibers, such as regenerated cellulose fibers.
- Air-laying processes are used to form the fiber web according to some aspects of the invention. Dry-laying processes are used to form the fiber web according to other aspects of the invention. In the air-laying processes (also called air-laid processes or air- forming processes), only airflow, gravity, and centrifugal force are used to deposit a stream of fibers onto a moving forming wire. Air-laid processes are described in, for example, PCT International Publication No. WO 03/099886 and U.S. Patent Nos.
- carding an air-laid process
- the mechanical process of carding is described in, for example, U.S. Patent No. 797,749, which is incorporated herein in its entirety by reference.
- the carding process includes an airstream component to randomize the orientation of the staple fibers when they are collected on the forming wire.
- the fiber webs are formed by classical, wet- laid papermaking processes according to some aspects of the invention.
- the fiber webs are made using any one of various, commonly practiced dispersant techniques to disperse a uniform furnish of fibers onto a foraminous screen of a conventional papermaking machine.
- the fibers are then subjected to entanglement (such as hydroentanglement or needlepunch, for example) to produce a nonwoven fabric in which the fibers are interlaced (entangled) with one another.
- entanglement such as hydroentanglement or needlepunch, for example
- hydroentanglement hydroentangling
- needlepunch is used to form the nonwoven fabric.
- Hydroentanglement processes are known in the art. Non-limiting examples of the hydroentangling process are described in Canadian Patent No. 841,938, U.S. Patent No. 3,485,706, and U.S. Patent No. 5,958, 186. U.S. Patent Nos. 3,485,706 and 5,958, 186, respectively, are incorporated herein in their entirety. Hydroentangling involves forming a dry-laid fiber web (or webs) and thereafter entangling the fibers by employing very fine water jets under high pressure. For example, a plurality of rows of waterjets is directed towards the fiber web which is disposed on a moving support, such as a wire (mesh). The level of bonding is determined by the energy imparted to the web by the
- hydroentangling jets The hydroentangling energy necessary to entangle the fibers depends on many factors, including the desired level of bonding, basis weights, specific fibers utilized, and other factors.
- the entangled web is then dried.
- Entangling by needle punch refers to a bonding process in which the subsequent material uses oscillating barbed needles to mechanically entangle and interlock the fibers of a web.
- the method includes entangling the individualized bast fibers and PLA fibers, and optionally, cellulose fibers and/or other biobased fibers when included.
- the entangled fiber web is heated to bond the entangled fiber web.
- the heating process is thermal bonding according to an exemplary aspect.
- the heating process is through air bonding according to other aspects.
- Thermal bonding is also referred to as calendar bonding, point bonding, thermal point bonding, or pattern bonding, and is used to bond the entangled fiber web to form the thermally bonded nonwoven fabric.
- thermal bonding is used to incorporate a pattern into the fabric. Thermal bonding is described in PCT International Publication No. WO/2005/025865, which is incorporated herein in its entirety by reference.
- thermal bonding the entangled fiber web is bonded under pressure by heating the entangled fiber web.
- the web can be heated by passing through a nip of heated calendar rolls under pressure, which can be embossed with a pattern that transfers to the surface of the fiber web.
- the calendar rolls are heated to a temperature that is about the melting point of the PLA fibers. In some aspects, the calendar rolls are heated to a temperature of about 120°C to about 170°C. In other aspects, the calendar rolls are heated to a temperature of about 130°C to about 135°C. Yet, in other aspects, the calendar rolls are heated to a temperature about or in any range from about 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, and 170°C.
- the entangled fiber web is heated at a temperature of about 120 to about 170°C. In other aspects, the entangled fiber web is heated to a temperature of about 130 to about 135°C. Still yet, in other aspects, the entangled fiber web is heated to a temperature about or in any range from about 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, and 170°C.
- Heating such as thermal bonding, thermally bonds at least a portion of the PLA fibers with at least a portion of the individualized bast fibers.
- other fibers such as cellulose fibers (e.g., regenerated cellulose fibers)
- at least a portion of the PLA fibers are also thermally bonded to the cellulose fibers.
- the nonwoven fabric After heating the entangled web by thermal bonding, the nonwoven fabric is strong enough to withstand wet mechanical agitation and drying processes, making it suitable for use as a wet wiper or dry wiper in a variety of applications.
- the CD wet tensile strength of a nonwoven is measured according to the Payne Sponge Method, which is described above. Compared to nonwoven substrates without PLA, the thermally bonded nonwoven substrates described herein have a significantly higher CD wet tensile strength.
- the nonwoven substrate has a CD wet tensile strength of at least 1,000 grams/inch (g/in). In other aspects, the nonwoven substrate has a CD wet tensile strength of about 1,000 g/in to about 1,400 g/in.
- the nonwoven substrate has a CD wet tensile strength of about 1,000 to about 1,200 g/in. Still yet, in other aspects, the nonwoven substrate has a CD wet tensile strength of at least 500 g/in. In some aspects, the nonwoven substrate has a CD wet tensile strength of about 500 to about 1,400 g/in. [0058]
- the basis weight of the nonwoven substrate depends on the specific application intended. In some aspects, the basis weight of the nonwoven substrate is about 40 to about 100 grams/m 2 (gsm). In other aspects, the basis weight of the nonwoven substrate is about 40 to about 60 gsm.
- the nonwoven fabric of the present invention can be incorporated into a variety of products.
- Non-limiting examples of products include wipers (or wipes), such as wet wipers, dry wipers, or impregnated wipers, which include personal care wipers, cleaning wipers, industrial wipers, and dusting wipers.
- Personal care wipers can be impregnated with, e.g., emollients, humectants, fragrances, and the like.
- Household cleaning wipers or hard surface cleaning wipers can be impregnated with, e.g., surfactants (for example, quaternary amines), peroxides, chlorine, solvents, chelating agents, antimicrobials, fragrances, and the like. Dusting wipers can be impregnated with, e.g., oils.
- surfactants for example, quaternary amines
- peroxides chlorine
- solvents solvents
- chelating agents antimicrobials
- fragrances e.g., and the like.
- Dusting wipers can be impregnated with, e.g., oils.
- the nonwoven fabric is incorporated into a launderable reusable industrial wiper, such as a launderable shop rag, or a food service towel.
- a launderable reusable industrial wiper such as a launderable shop rag, or a food service towel.
- the thermally bonded wiper fibers are sufficiently bonded to withstand the agitation of a laundry washing machine or water-jet force of a commercial dish washer.
- Non-limiting examples of wipers include baby wipes, cosmetic wipes, perinea wipes, disposable washcloths, household cleaning wipes, such as kitchen wipes, bath wipes, or hard surface wipes, disinfecting and germ removal wipes, specialty cleaning wipes, such as glass wipes, mirror wipes, leather wipes, electronics wipes, lens wipes, and polishing wipes, medical cleaning wipes, disinfecting wipes, and the like.
- Additional examples of products include sorbents, medical supplies, such as surgical drapes, gowns, and wound care products, personal protective products for industrial applications, such as protective coveralls, sleeve protectors, and the like, protective coverings for automotive applications, and protective coverings for marine applications.
- the nonwoven fabric can be incorporated into absorbent cores, liners, outer-covers, or other components of personal care articles, such as diapers (baby or adult), training pants, feminine care articles (pads and tampons) and nursing pads. Further, the nonwoven fabric can be incorporated into fluid filtration products, such air filters, water filters, and oil filters, home furnishings, such as furniture backing, thermal and acoustic insulation products, agricultural application products, landscaping application products, and geotextile application products. A variety of wetting compositions, formed from one or more of the above-described components, can be used with the wipers of the present invention.
- Cells 2 and 3 included flax fibers, viscose fibers, and PLA fibers.
- Cell 5 only included flax fibers and PLA fibers.
- Cells 1 and 4 were controls and did not include PLA fibers. The fibers were hydroentangled, and samples with PLA fibers were heated.
- the flax fibers used had a mean length of about 6-25 mm.
- the viscose fibers were about 1.5 denier and about 38 mm in length.
- the PLA fibers were about 4.0 denier, about 50 mm in length.
- the PLA fibers had a minimum melting point of 170°C.
- the PLA fibers were heated to 170°C to thermally bond them to the flax fibers.
- the PLA fibers in cell 3 had a minimum melting temperature of 120°C and were heated to 120°C to thermally bond them to the flax fibers.
- the hydroentangled wipers were tested for physical properties, hand feel, compostability, and washability. To assess the strength of the samples and the ability to withstand mechanical agitation, the samples were washed and dried and subjected to a series of wash cycles in a washing machine. Figure 1 and Table 3 show the CD wet strength (g/in) of the samples before washing, and up to 5 cycles of washing. The samples were dried in a residential clothes dryer between washing cycles.
- FIG. 1 shows an image of the sheet from cell 4 (100% flax) after one cycle of washing.
- Figure 2B shows an image of the sheet from cell 1 (flax/viscose) after one cycle of washing.
- FIG. 3 A shows an image of the sheet from cell 5 (flax/PLA) after five cycles of washing and drying.
- Figure 3B shows an image of the sheet from cell 3 (flax/viscose/PLA) after five cycles of washing and drying.
- Table 4 shows % PLA after extracting the hydroentangled substrates with chloroform.
- Table 5 shows physical properties of the hydroentangled substrates, including wet and dry tensile strengths and wet and dry ball burst measurements.
- Ball burst measurements were performed to assess the puncture strength of the substrates, which was indicative of thermal bonding in the z-direction.
- a ball burst fixture was used from MTS Systems Corporation, Stoughton, Massachusetts.
- An Instron tensile tester also was used from Instron Corporation, Canton, Massachusetts.
- Dry and wet ball burst measurements were performed by following INDA Wiper Ball Burst Test Method WSP 110.5 R4(12). The method measures the out-of-plane force to break a nonwoven sample using a 1-inch diameter polished steel ball probe.
- the probe is attached to a load cell in an Instron tensile test apparatus.
- the nonwoven sample is clamped securely in a horizontal orientation below the probe. During the test, the probe moves vertically downward to contact and eventually penetrate the nonwoven sheet. The force to break the sample is reported. Sheets may be tested dry or wet.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Nonwoven Fabrics (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US201762520511P | 2017-06-15 | 2017-06-15 | |
PCT/US2018/035523 WO2018231540A1 (en) | 2017-06-15 | 2018-06-01 | A launderable plant-based substrate that is thermally bonded with biobased fibers |
Publications (1)
Publication Number | Publication Date |
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EP3638760A1 true EP3638760A1 (de) | 2020-04-22 |
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ID=62779009
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Application Number | Title | Priority Date | Filing Date |
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EP18735022.8A Pending EP3638760A1 (de) | 2017-06-15 | 2018-06-01 | Waschbares substrat auf pflanzenbasis, das thermisch mit biobasierten fasern verbunden ist |
Country Status (9)
Country | Link |
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US (1) | US20200224344A1 (de) |
EP (1) | EP3638760A1 (de) |
JP (1) | JP7149959B2 (de) |
KR (1) | KR102511462B1 (de) |
CN (1) | CN110536957A (de) |
CA (1) | CA3060221A1 (de) |
IL (1) | IL271204B2 (de) |
MX (1) | MX2019012207A (de) |
WO (1) | WO2018231540A1 (de) |
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KR102256522B1 (ko) * | 2019-05-27 | 2021-05-26 | (주)부성텍스텍 | 흡차음재 및 이의 제조방법 |
DE102020116399A1 (de) * | 2020-06-22 | 2021-12-23 | McAirlaid's Vliesstoffe GmbH | Verfahren zur Herstellung einer Faserstoffbahn mit Polylactid-Fasern |
EP4166705A1 (de) * | 2021-10-18 | 2023-04-19 | Suominen Oyj | Verfahren zur herstellung von vliesstoff und vliesstoff |
CN114086313B (zh) * | 2021-11-24 | 2023-04-18 | 广州绿熙川新材料有限公司 | 一种植物纤维性革基布及其制作方法 |
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CA841938A (en) | 1970-05-19 | E.I. Du Pont De Nemours And Company | Process for producing a nonwoven web | |
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GB1518284A (en) | 1974-10-31 | 1978-07-19 | Kroyer K K K | Apparatus for the deposition of a uniform layer of dry fibres on a foraminous forming surface |
US4200488A (en) | 1975-02-20 | 1980-04-29 | International Paper Company | Viscous dispersion for forming wet-laid, non-woven fabrics |
US4081319A (en) | 1976-04-06 | 1978-03-28 | The Dexter Corporation | Continuous papermaking process |
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SE503606C2 (sv) | 1994-10-24 | 1996-07-15 | Moelnlycke Ab | Nonwovenmaterial innehållande en blandning av massafibrer och långa hydrofila växtfibrer samt förfarande för framställning av nonwovenmaterialet |
JPH09205827A (ja) * | 1996-02-05 | 1997-08-12 | Toyobo Co Ltd | 生分解性播種シート |
JP3352022B2 (ja) * | 1998-03-27 | 2002-12-03 | ユニチカ株式会社 | バインダー繊維を用いてなる高温雰囲気下での耐へたり性に優れる固綿 |
US7772138B2 (en) | 2002-05-21 | 2010-08-10 | Kimberly-Clark Worldwide, Inc. | Ion sensitive, water-dispersible polymers, a method of making same and items using same |
JP4048965B2 (ja) * | 2003-01-31 | 2008-02-20 | トヨタ自動車株式会社 | 生分解性樹脂からなる繊維複合材 |
US7932196B2 (en) | 2003-08-22 | 2011-04-26 | Kimberly-Clark Worldwide, Inc. | Microporous stretch thinned film/nonwoven laminates and limited use or disposable product applications |
US8695151B2 (en) * | 2004-12-28 | 2014-04-15 | Wooster Brush Company | Covers for paint rollers |
CA2654599C (en) | 2006-06-08 | 2014-06-10 | National Research Council Of Canada | Extraction of hemp fibers |
CN102220674B (zh) * | 2011-04-27 | 2012-10-03 | 嘉兴学院 | 一种半耐久性家纺用苎麻无纺材料及其生产方法 |
JP6011343B2 (ja) * | 2011-11-14 | 2016-10-19 | 東レ株式会社 | プレス成型用不織布及びその製造方法並びに成型体の製造方法 |
CN103306051A (zh) * | 2012-03-06 | 2013-09-18 | 安吉振兴布业有限公司 | 一种包装用薄型黄麻纤维无纺布及其制造方法 |
KR101401332B1 (ko) * | 2012-05-17 | 2014-06-02 | 한국생산기술연구원 | 케나프 단일성분으로 이루어진 부직포, 그를 이용한 혼합 부직포 및 그의 제조방법 |
EP2971313B1 (de) * | 2013-03-15 | 2018-07-18 | GPCP IP Holdings LLC | Vliesstoffe aus kurzen individualisierten bastfasern und daraus hergestellte produkte |
MX367539B (es) * | 2013-03-15 | 2019-08-26 | Gpcp Ip Holdings Llc | Sustrato de limpieza dispersable en agua. |
US20170051443A1 (en) * | 2014-04-28 | 2017-02-23 | 3M Innovative Properties Company | Self-bonded cellulosic nonwoven web and method for making |
-
2018
- 2018-06-01 JP JP2019558524A patent/JP7149959B2/ja active Active
- 2018-06-01 MX MX2019012207A patent/MX2019012207A/es unknown
- 2018-06-01 CA CA3060221A patent/CA3060221A1/en active Pending
- 2018-06-01 US US16/623,117 patent/US20200224344A1/en not_active Abandoned
- 2018-06-01 EP EP18735022.8A patent/EP3638760A1/de active Pending
- 2018-06-01 KR KR1020197029890A patent/KR102511462B1/ko active IP Right Grant
- 2018-06-01 CN CN201880025303.5A patent/CN110536957A/zh active Pending
- 2018-06-01 WO PCT/US2018/035523 patent/WO2018231540A1/en unknown
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US20200224344A1 (en) | 2020-07-16 |
KR20200019845A (ko) | 2020-02-25 |
CA3060221A1 (en) | 2018-12-20 |
MX2019012207A (es) | 2020-01-13 |
KR102511462B1 (ko) | 2023-03-20 |
JP2020523489A (ja) | 2020-08-06 |
IL271204B2 (en) | 2023-06-01 |
IL271204A (en) | 2020-01-30 |
JP7149959B2 (ja) | 2022-10-07 |
CN110536957A (zh) | 2019-12-03 |
WO2018231540A1 (en) | 2018-12-20 |
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