EP3212846B1 - Schnell fibrillierende lyocellfasern und deren verwendung - Google Patents

Schnell fibrillierende lyocellfasern und deren verwendung Download PDF

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Publication number
EP3212846B1
EP3212846B1 EP15744462.1A EP15744462A EP3212846B1 EP 3212846 B1 EP3212846 B1 EP 3212846B1 EP 15744462 A EP15744462 A EP 15744462A EP 3212846 B1 EP3212846 B1 EP 3212846B1
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EP
European Patent Office
Prior art keywords
fibers
lyocell
lyocell fibers
fibrillation
fibrillated
Prior art date
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Active
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EP15744462.1A
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German (de)
English (en)
French (fr)
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EP3212846A1 (de
Inventor
Johann Männer
Rudolf Aigner
Jim GANNON
Matt Riley
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Lenzing AG
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Lenzing AG
Chemiefaser Lenzing AG
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Priority to PL15744462T priority Critical patent/PL3212846T3/pl
Publication of EP3212846A1 publication Critical patent/EP3212846A1/de
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/02—Synthetic cellulose fibres
    • D21H13/08—Synthetic cellulose fibres from regenerated cellulose
    • 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
    • D04H1/492—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 by fluid jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B1/00—Cleaning by methods involving the use of tools
    • B08B1/10—Cleaning by methods involving the use of tools characterised by the type of cleaning tool
    • B08B1/14—Wipes; Absorbent members, e.g. swabs or sponges
    • B08B1/143—Wipes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/423—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by fibrillation of films or filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • 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
    • 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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • 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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838—Ultrafine fibres, e.g. microfibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance

Definitions

  • the present invention relates to fibrillated lyocell fibers having a fibrillation quotient Q of 20 or greater and having a content of microfibers with a fineness of less than 14 mesh and a diameter of less than 2 microns at least 50%, and their use for producing a wipe, the pulp and 5 to 20% by weight of fibrillated lyocell fibers.
  • the US 6042769 discloses a method of increasing the fibrillation tendency of lyocell fibers by a treatment which reduces the degree of polymerization of the cellulose by at least 200 units.
  • the fiber thus obtained should be used mainly in nonwovens and paper.
  • the treatment is preferably carried out with a bleaching agent, in particular with sodium hypochlorite.
  • the treatment with an acid, preferably a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid is possible.
  • this process has not been implemented commercially until today.
  • regenerated cellulose fibers such as viscose and lyocell in nonwovens
  • refiners which are known from papermaking
  • lyocell fibers are fibrillated and used as cellulose microfibers in admixture with paper pulp in so-called wet-laying processes (also referred to in the art as "wet-laid processes")
  • wet-laid processes also referred to in the art as "wet-laid processes”.
  • wipes or wipes and paper structures for, for example, tissues US 8187422 in that the incorporation of fibrillated lyocell microfibers into paper pulp enables the properties of disposable cellulosic wipes to be optimized accordingly.
  • the cleaning behavior should be correspondingly improved by this admixture.
  • the optimized property profile should be improved by an increased opacity (light scattering) and porosity, distinguished by the improvement of the soft grip. The higher porosity is said to result in a higher absorbency of water and oil, resulting in improved cleaning performance.
  • the US 8187422 does not describe exactly how the lyocell microfibers used are made. It merely indicates that conventional lyocell staple fibers, as used, for example, for the production of textiles, can be fibrillated in a disk refiner or similar aggregate in an aqueous medium at low solids content.
  • the according to the US 8187422 used lyocell microfibers were purchased in an already fibrillated state from a supplier. They have a fibrillation degree of CSF ⁇ 175ml and a diameter of ⁇ 2 ⁇ m. 40% of the fibers should have a fineness of finer than 14mesh.
  • the in the US 8187422 Disposable wipes disclosed contain between 25 and 75% of the Lyocell microfibers so prepared.
  • the object of this prior art was to provide fibers for use in wipes, which can be fibrillated for a cost-effective and on the other hand in a lower proportion in wipes nor the same mechanical properties of the wipes, such as high strength allow.
  • fibrillated lyocell fibers which are characterized in that they have a Fibrillation quotient Q of 20 or greater and their content of microfibers with a fineness of less than 14 mesh and a diameter of less than 2 microns is at least 50%.
  • Fibrillated lyocell fibers in the context of the present invention does not mean a total amount of completely identical fibers, but a mixture of fibers of basically the same nature, wherein in the mixture fibers of different fineness (measured in mesh ) and different diameters.
  • t CSF200 is the time (in minutes) required in the CSF check to achieve a CSF value of 200.
  • Q the time (in minutes) required in the CSF check to achieve a CSF value of 200.
  • the larger Q is, the less time is needed at constant fibrillation conditions to achieve the same degree of fibrillation.
  • a Q value of up to 400 can be achieved.
  • Another object of the present invention is a wipe containing pulp and 5 to 20% by weight of fibrillated lyocell fibers and wherein the fibrillated lyocell fibers have a fibrillation quotient Q of 20 or greater.
  • the pulp is a paper pulp.
  • the fast-fibrillating lyocell fibers could be prepared by acid treatment of conventional lyocell fibers.
  • This acid treatment can be carried out according to the invention by using a fiber cable extruded from spinnerets in a known manner with a single fiber titer of for example between 1.0 and 6.0 dtex with dilute mineral acid, for example hydrochloric, sulfuric or nitric acid, with a concentration for example, between 0.5 and 5% at room temperature in a container at a liquor ratio of for example, impregnated 1:10 and then pressed to a certain residual moisture of, for example, 200%.
  • the impregnated fiber cable is then exposed to water vapor at overpressure in a suitable device, then washed free of acid and dried.
  • the fiber cable is cut to a staple length of 5 mm and subjected to the CSF test (Canadian Standard Freeness according to TAPPI Standard T227 om-94).
  • the fiber cable is cut to produce the wipes according to the invention in staple fibers suitable cut length, for example 4 to 6 mm.
  • the fibrillation can then take place in a comminution unit customary in the paper industry, for example a grinding unit, a refiner, a disintegrator or a hydrapulper. It is carried out there until the desired degree of fibrillation is reached.
  • the effect of acid treatment and consequent reduction of CSF can be influenced by varying the treatment parameters. For longer treatment duration in the overpressure steam, the same effect can be achieved with lower acid concentrations and vice versa. Similarly, with lower or higher steaming temperatures, the CSF value can be affected.
  • the fast-fibrillating lyocell fibers according to the invention can be used according to the invention for the production of a wide variety of products, such as wipes, in particular disposable wipes, papers, in particular filter papers and papers for technical applications, such as batteries.
  • wipes in particular disposable wipes
  • filters papers and papers for technical applications, such as batteries.
  • wipes according to the invention can be prepared by basically known processes from the fibers and pulp according to the invention.
  • the solidification takes place by water needling.
  • the present invention also relates to the use of the inventive fibers described above for producing a wipe, wherein the wipe comprises pulp and 5 to 20 wt .-% fibrillated lyocell fibers.
  • the pulp is preferably a paper pulp.
  • Fast fibrillating lyocell fibers are produced as follows: A lyocell fiber strand having a single fiber titer of 1.7 dtex is impregnated with dilute sulfuric acid at room temperature and a liquor ratio of 1:10 and pressed to about 200% humidity. The impregnated fiber strand is subjected to steam in a laboratory damper for about 10 minutes under pressure, then washed free of acid with water and dried. The dry fiber strand is cut to 5mm staple length and subjected to the CSF test.
  • Fig. 1 shows the decrease of the CSF value with increasing comminution time in the measuring device. It can be clearly seen that the acid-treated fibers fibrillate much faster than the untreated. For the commercial production of fibrillated lyocell fibers, this means a considerably lower expenditure of time and energy than when using untreated lyocell fibers.
  • Table 1 shows the t CSF200 values determined for the various samples and the Q values calculated from them. Tab. 1: sample t CSF200 [min] Q [min -1 ] A 15.5 12.9 B 3.5 57.1
  • Example 2 The same fiber samples were compared as in Example 1: Each 1% aqueous fiber suspensions of both fiber samples A and B were ground in a laboratory refiner of the type Andritz R1L at a power of 500W, both the energy consumption in kWh / to and the duration to reach a degree of milling of CSF 200 (Canadian Standard of Freeness Test in accordance with TAPPI Standard T227 om-94). The fibrillating lyocell fiber could be processed in less than 80% of the energy consumption compared to the standard lyocell fiber in only 50% of the milling time (see Table 2). Tab. 2: sample Grinding time [min] Energy consumption [kWh / to] A 5 400 B 2.5 65
  • Fig. 2 shows an SEM image of the leaf from the suspension of sample B.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Artificial Filaments (AREA)
EP15744462.1A 2014-10-29 2015-05-29 Schnell fibrillierende lyocellfasern und deren verwendung Active EP3212846B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15744462T PL3212846T3 (pl) 2014-10-29 2015-05-29 Szybko fibrylujące włókna lyocell i ich zastosowanie

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA793/2014A AT515693B1 (de) 2014-10-29 2014-10-29 Schnell fibrillierende Lyocellfasern und deren Verwendung
PCT/AT2015/000082 WO2016065377A1 (de) 2014-10-29 2015-05-29 Schnell fibrillierende lyocellfasern und deren verwendung

Publications (2)

Publication Number Publication Date
EP3212846A1 EP3212846A1 (de) 2017-09-06
EP3212846B1 true EP3212846B1 (de) 2019-04-17

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EP15744462.1A Active EP3212846B1 (de) 2014-10-29 2015-05-29 Schnell fibrillierende lyocellfasern und deren verwendung

Country Status (10)

Country Link
US (1) US10570565B2 (pl)
EP (1) EP3212846B1 (pl)
JP (1) JP6931786B2 (pl)
KR (1) KR102444057B1 (pl)
CN (1) CN107109735B (pl)
AT (1) AT515693B1 (pl)
ES (1) ES2733229T3 (pl)
PL (1) PL3212846T3 (pl)
TR (1) TR201909640T4 (pl)
WO (1) WO2016065377A1 (pl)

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AT515693B1 (de) * 2014-10-29 2015-11-15 Chemiefaser Lenzing Ag Schnell fibrillierende Lyocellfasern und deren Verwendung
AT517303B1 (de) 2015-06-11 2018-02-15 Chemiefaser Lenzing Ag Verwendung cellulosischer Fasern zur Herstellung eines Vliesstoffes
EP3536829A1 (en) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Lyocell fiber with viscose like properties
EP3536851A1 (en) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Lyocell fiber with increased tendency to fibrillate
EP3536832A1 (en) 2018-03-06 2019-09-11 Lenzing Aktiengesellschaft Lyocell fiber with improved disintegration properties
ES2964861T3 (es) * 2018-07-31 2024-04-09 Chemiefaser Lenzing Ag Tela no tejida, uso de la tela no tejida y toallita de limpieza, toallita para secar y mascarilla que contiene la tela no tejida
CN111139596B (zh) * 2018-11-02 2023-04-11 东丽纤维研究所（中国）有限公司 一种水刺无纺布
WO2021144854A1 (ja) * 2020-01-14 2021-07-22 旭化成株式会社 フィブリル化している再生セルロース繊維及びそれを用いた布帛
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TR201909640T4 (tr) 2019-07-22
AT515693B1 (de) 2015-11-15
WO2016065377A1 (de) 2016-05-06
KR20170077158A (ko) 2017-07-05
US20170241079A1 (en) 2017-08-24
PL3212846T3 (pl) 2019-10-31
CN107109735B (zh) 2022-09-02
ES2733229T3 (es) 2019-11-28
KR102444057B1 (ko) 2022-09-15
US10570565B2 (en) 2020-02-25
EP3212846A1 (de) 2017-09-06
CN107109735A (zh) 2017-08-29
JP2017534390A (ja) 2017-11-24
AT515693A4 (de) 2015-11-15
JP6931786B2 (ja) 2021-09-08

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