EP3762536B1 - Lyocellfaser mit erhöhter neigung zur fibrillierung - Google Patents
Lyocellfaser mit erhöhter neigung zur fibrillierung Download PDFInfo
- Publication number
- EP3762536B1 EP3762536B1 EP19707837.1A EP19707837A EP3762536B1 EP 3762536 B1 EP3762536 B1 EP 3762536B1 EP 19707837 A EP19707837 A EP 19707837A EP 3762536 B1 EP3762536 B1 EP 3762536B1
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- EP
- European Patent Office
- Prior art keywords
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- lyocell
- pulp
- fibers
- lyocell fiber
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- 229920000433 Lyocell Polymers 0.000 title claims description 96
- 239000000835 fiber Substances 0.000 claims description 120
- 229920002488 Hemicellulose Polymers 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 41
- 229920002678 cellulose Polymers 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 31
- 239000001913 cellulose Substances 0.000 claims description 30
- 229920000057 Mannan Polymers 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 22
- 229920001221 xylan Polymers 0.000 claims description 19
- 150000004823 xylans Chemical class 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000009987 spinning Methods 0.000 claims description 16
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- 238000002203 pretreatment Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 48
- 230000002600 fibrillogenic effect Effects 0.000 description 48
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- 210000001519 tissue Anatomy 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 4
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- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 229920001503 Glucan Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001891 gel spinning Methods 0.000 description 2
- 150000002402 hexoses Chemical class 0.000 description 2
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- 238000000465 moulding Methods 0.000 description 2
- 150000002972 pentoses Chemical class 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QGGOCWIJGWDKHC-FSIIMWSLSA-N (2s,3s,4r,5r)-2,4,5-trihydroxy-3-methoxy-6-oxohexanoic acid Chemical group OC(=O)[C@@H](O)[C@@H](OC)[C@H](O)[C@@H](O)C=O QGGOCWIJGWDKHC-FSIIMWSLSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 description 1
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- ITJLNEXJUADEMK-UHFFFAOYSA-N Shirin Natural products CCC(C)(O)c1c(Cl)c(OC)c(C)c2OC(=O)c3c(C)c(Cl)c(O)c(Cl)c3Oc12 ITJLNEXJUADEMK-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 125000000089 arabinosyl group Chemical group C1([C@@H](O)[C@H](O)[C@H](O)CO1)* 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ATSGLBOJGVTHHC-UHFFFAOYSA-N bis(ethane-1,2-diamine)copper(2+) Chemical compound [Cu+2].NCCN.NCCN ATSGLBOJGVTHHC-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
-
- 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
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/013—Regenerated cellulose series
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
-
- 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
-
- 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
-
- 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
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/002—Tissue paper; Absorbent paper
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/08—Filter paper
Definitions
- the present invention relates to a lyocell fiber with increased tendency to fibrillate, a method for producing same as well as products comprising the lyocell fiber.
- Fibers of various types are employed for producing products such as wipes and tissues. Typically such fibers do show a high degree of fibrillation in order to enable uptake of other materials (during use or to provide functionalized wipes for example).
- fibers employed in this field are cellulose based fibers.
- fibrillated regenerated cellulose fibers milled in refiners, which are well known to experts, are used in blends with pulps. Products from this process can be used in numerous applications - e.g. in wipes for cleaning and wiping and tissues and technical applications.
- the fibrillated fibers generate increased stability and improved uptake for cleaning purposes and a decreased air permeability and porosity.
- US 8187422 describes a blend with fibrillated lyocell-microfibers and paper pulp to optimize cleaning performance of the final wipe product resulting in increased opacity and porosity and enhanced softness of the final product.
- lyocell fibers can be fibrillated in an aqueous medium with low solid content using a disk refiner or a similar device.
- a chemical pre-treatment is employed for such fibers as to fibrillate the fibers without any chemical pre-treatment would consume enormous amounts of energy and time.
- US 8187422 discloses that the already fibrillated fibers (obtained from an external supplier) are processed to produce disposable wipes containing 25-75% of these fibrillated fibers.
- US 6042769 shows an example of chemical treatments to enhance fibrillation tendency. It discloses chemical treatments to reduce the DP (degree of polymerization) by 200 units, thereby increasing fibrillation tendency.
- Chemical treatments mentioned in this patent refer to the use of bleaching reagents, such as sodium hypochlorite or mineral acids, such as hydrochloric acid, sulfuric acid or nitric acid. A commercialization of this procedure did not succeed up to now.
- US 9222222 discloses mixtures of lyocell fibers and low DP or standard DP cellulose pulp fibers with a CSF (Canadian Standard Freeness) of 250 ml or less, retaining the CSF values even after drying.
- the pulp fibers account for 10-75% of total weight of fibers in the mixture.
- the low DP pulp contains higher amounts of hemicelluloses, but is only added to the mixtures as a low DP pulp, without mentioning any relevance of the hemicellulose content.
- the fibrillation tendency is measured using the CSF-method (Canadian Standard of Freeness) according to TAPPI Standard T227 om-94.
- US 2015//0184338 A1 discloses compositions including Kraft pulp. These are described as having a low hemicellulose content.
- WO 99/47733 describes lyocell fibers and compositions for making same.
- WO 2011/079331 A1 , WO 01/81664 A1 , WO 2014/161018 A1 and WO 2016/197156 A1 disclose technical background information concerning cellulose fibers and compositions useful for preparing such fibers.
- WO 2016065377 describes a wipe containing 5-20 wt% of a fast fibrillating lyocell fiber produced by chemical treatments with mineral acids. This fiber is characterized by a very fast fibrillation. During refining this fast fibrillation is not always feasible. Whilst the standard lyocell fibers tend to fibrillate too slow, this fiber fibrillates too fast. In addition it has to be taken into consideration that chemical treatment induced fibrillation has detrimental effects on fiber properties. US 6706237 discloses that meltblown fibers obtained from hemicelluloses rich pulps show a decreased or reduced tendency to fibrillate. US 8420004 discloses another example of meltblown fibers for producing non-woven fabrics.
- Zhang et al (Polymer Engineering and Science, 2007, 47, 702-706 ) describe fibers with higher hemicellulose contents. The authors postulate that the fibers tend to show an enhanced fiber fibrillation resistance, lower crystallinity and better dyeability. They also postulate that the tensile strength only decreases insignificantly and that the fiber properties could be even increased further by higher hemicelluloses concentrations in the spinning dope.
- Zhang et al Journal of Applied Polymer Science, 2008, 107, 636-641
- Zhang et al Polymer Materials Science and Engineering, 2008, 24, 11, 99-102
- Zhang et al disclose the same figures as the paper by Zhang (Polymer Engineering and Science, 2007, 47, 702-706 )
- Zhang et al Chinese Synthetic Fiber Industry, 2008, 31, 2, 24-27
- compositions including treated Kraft pulp, having a low degree of polymerization, a high R18, and a low hemicellulose content. Additionally, methods of making the compositions are also described.
- WO 99/47733 A1 provides compositions for making lyocell fibers and such lyocell fibers.
- the compositions have a high hemicellulose content, a low lignin content and include cellulose that has a low average degree of polymerization. Further, processes for making such compositions are provided.
- the present inventors accordingly provide the fiber as defined in claim 1, the method for producing same as described in claim 11 as well as products containing same as defined in claim 16 as well as the use defined in claim 8.
- Preferred embodiments are described in the respective subclaims as well as in the specification.
- Figure 1 shows the fibrillation dynamics of a fiber in accordance with the present invention in comparison with a standard lyocell fiber and a lyocell fiber subjected to chemical fibrillation.
- the fiber in accordance with the present invention is a lyocell fiber with an increased tendency to fibrillate without requiring a chemical pre-treatment.
- a chemical pre-treatment step is for example described in AT 515693 B1 .
- the lyocell process is well known in the art and relates to a direct dissolution process of cellulose wood pulp or other cellulose-based feedstock in a polar solvent (for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids).
- a polar solvent for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids.
- NMMO N-methylmorpholine N-oxide
- ionic liquids for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids.
- the technology is used to produce a family of cellulose staple fibers (commercially available from Lenzing AG, Lenzing, Austria under the trademark TENCEL ® or TENCEL TM ) which are widely used in the textile and nonwoven industry.
- Other cellulose bodies from lyocell technology have also been produced.
- the solution of cellulose is extruded in a so called dry-wet-spinning process by means of a forming tool and the moulded solution is guided for example over an air gap into a precipitation bath, where the moulded body is obtained by precipitation of the cellulose.
- the molding is washed and optionally dried after further treatment steps.
- Such lyocell fibers are well known in the art and the general methodology to produce same is for example disclosed in US 4,246,221 and its analytics in the BISFA (The International Bureau for the Standardization of Man-Made Fibers) publication " Terminology of Man-Made Fibres", 2009 editi on. Both references are included herewith in their entirety by reference.
- BISFA The International Bureau for the Standardization of Man-Made Fibers
- lyocell fiber as employed herein defines a fiber obtained by this process, as it has been found that fibers in accordance with the present invention differ greatly from fibers for example obtained from a meltblown process, even if using a direct dissolution process of cellulose wood pulp or other cellulose-based feedstock in a polar solvent (for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids) in order to produce the starting material.
- a polar solvent for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids
- hemicelluloses refers to materials known to the skilled person which are present in wood and other cellulosic raw material such as annual plants, i.e. the raw material from which cellulose typically is obtained. Hemicelluloses are present in wood and other plants in form of branched short chain polysaccharides built up by pentoses and/or hexoses (C5 and / or C6-sugar units). The main building blocks are mannose, xylose, glucose, rhamnose and galactose. The back bone of the polysaccharides can consist of only one unit (f.e. xylan) or of two or more units (e.g. mannan).
- hemicelluloses as known by the skilled person and as employed herein comprises hemicelluloses in its native state, hemicelluloses degraded by ordinary processing and hemicelluloses chemically modified by special process steps (e. g. derivatization) as well as short chain celluloses and other short chain polysaccharides with a degree of polymerization (DP) of up to 500.
- DP degree of polymerization
- the pulps preferably employed in the present invention do show as outlined herein a high content of hemicelluloses. Compared with the standard low hemicellulose content pulp employed for the preparation of standard lyocell fibers the preferred pulps employed in accordance with the present invention do show also other differences, which are outlined below.
- the pulps as employed herein display a more fluffy appearance, which results after milling (during preparation of starting materials for the formation of spinning solutions for the lyocell process), in the presence of a high proportion of larger particles.
- the bulk density is much lower, compared with standard pulps having a low hemicellulose content.
- This low bulk density requires adaptions in the dosage parameters (f.e. dosage from at least 2 storage devices).
- the pulps employed in accordance with the present invention are more difficult to impregnate with NMMO. This can be seen by evaluating the impregnating behavior according to the Cobb evaluation.
- the pulp employed for the preparation of the lyocell products, preferably fibers, as described herein has a scan viscosity in the range of from 300-440 ml/g, especially 320-420 ml/g, more preferably 320 to 400 ml/g.
- the scan viscosity is determined in accordance with SCAN-CM 15:99 in a cupriethylenediamine solution, a methodology which is known to the skilled person and which can be carried out on commercially available devices, such as the device Auto PulpIVA PSLRheotek available from psl-rheotek.
- the scan viscosity is an important parameter influencing in particular processing of the pulp to prepare spinning solutions.
- lyocell process and lyocell technology relate to a direct dissolution process of cellulose wood pulp or other cellulose-based feedstock in a polar solvent (for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids).
- a polar solvent for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids.
- the technology is used to produce a family of cellulose staple fibers (commercially available from Lenzing AG, Lenzing, Austria under the trademark TENCEL ® or TENCEL TM ) which are widely used in the textile and nonwoven industry.
- Other cellulose bodies from lyocell technology have also been produced.
- the solution of cellulose is usually extruded in a so called dry-wet-spinning process by means of a forming tool and the moulded solution gets for example over an air gap into a precipitation bath, where the moulded body is obtained by precipitation of the cellulose.
- the moulding is washed and optionally dried after further treatment steps.
- a process for production of lyocell fibers is described, for instance, in US 4,246,221 , WO 93/19230 , WO95/02082 or WO97/38153 .
- lyocell fibers with enhanced fibrillation tendencies which were produced without any chemical pre-treatment.
- the chemical pre-treatment step weakens the fiber properties (working capacity) on the one hand and adds cost to the fiber production on the other hand.
- the fiber in accordance with the present invention shows well-balanced fibrillation dynamics between standard lyocell fibers and fast fibrillated fibers obtained with additional chemical pre-treatments. Accordingly, the lyocell fiber in accordance with the present invention avoids the need for chemical pre-treatment whilst achieving fast fibrillation.
- Standard lyocell fibers are currently commercially produced from high quality wood pulps with high ⁇ -cellulose content and low non-cellulose contents such as hemicelluloses.
- lyocell fibers such as TENCEL TM fibers produced from Lenzing AG, show excellent fiber properties for non-wovens and textile applications. As mentioned in the patents referred to above, if a high fibrillation tendency is required these lyocell fibers are chemically pre-treated using f.e. mineral acids or bleaching reagents. By this chemical treatment the fiber properties are weakened drastically and the working capacity decreases.
- the present invention overcomes the shortcomings of the state of the art by providing lyocell fibers as described herein.
- the fibers in accordance with the present invention are fibers produced using large scale production equipment, while the fibers described in the paper by Zhang et al are produced with lab equipment not allowing the production of lyocell fibers in commercial quality (as for example drawing ratios, production velocities and after treatment do not reflect scale-up qualities).
- the fibers, not being produced with sufficient drawing and a sufficient after-treatment therefore show different structure and properties compared to the fibers produced at production scale at titers reflecting market applications.
- the fibers in accordance with the present invention were produced on a semi-commercial pilot plant ( ⁇ 1 kt/a) and a complete, commercial-like after-treatment of the fiber. A straightforward scale-up from this production unit to a commercial unit (>30 kt/a) is feasible and reliable.
- the hemicellulose content may be adjusted according to procedures known in the art.
- the hemicellulose may be the hemicelluloses originating from the wood from which the pulp is obtained, it is however also possible to add individual hemicelluloses depending on the desired fiber properties from other sources to high purity cellulose with a low original hemicellulose content.
- the addition of individual hemicelluloses may also be employed to adjust the composition of the hemicelluloses content, for example to adjust the ratio of hexoses to pentoses.
- the pulp enabling the preparation of the fibers in accordance with the present invention preferably shows a ratio of C5/xylan to C6/mannan of from 125:1 to 1:3, preferably in the range of 25:1 to 1:2.
- the hemicellulose content is 7 wt.-% or more, preferable 10 wt.-% or more, more preferably 14 wt.-% or more and in embodiments up to 25 wt.-% or even 30 wt.-%.
- the xylan content is 5 wt.-% or more, such as 8 wt.-% or more, and in embodiments 10 wt.-% or more.
- the mannan content is 3 wt.-% or more, such as 5 wt.-% or more. In other embodiments the mannan content, preferably in combination with a high xylan content as defined above, may be 1 wt.-% or less, such as 0.2 wt.-% or 0.1 wt.-% or less.
- the hemicelluloses content in the fibers of the present invention generally is higher, as compared to standard lyocell fibers. Suitable contents are 5 wt.-% or more and up to 30 wt.-%.
- the fiber in accordance with the present invention shows a ratio of C5/xylan to C6/mannan of from 125:1 to 1:3, preferably in the range of 25:1 to 1:2.
- the xylan and/or mannan content the above provided embodiments described in relation with the pulp are applicable also for the fiber as such.
- the fibers in accordance with the present invention typically have a titer of 9 dtex or less, such as 3.3 dtex or less, such as 2.2 dtex, depending on the desired application. If the fiber is intended to be used in non-woven applications a titer of 1.3 or higher such as 1.7 dtex typically is suitable. However, the present invention also covers fibers with much lower titers, with suitable lower limits for titers being 0.5 dtex or higher, such as 0.8 dtex or higher, and in embodiments 1.3 dtex or higher. These upper and lower values as disclosed here define ranges of from0.5 to 9 dtex, and including all further ranges formed by combining any one of the upper values with any one of the lower values.
- the fiber in accordance with the present invention may be prepared using lyocell technology employing a solution of cellulose and a spinning process employing a precipitation bath according to standard lyocell processes, known to the skilled person. Furthermore the fiber employed does not require any chemical pre-treatment known to enhance fibrillation tendencies, as the present invention achieves fibrillation to the required extend without such treatment, which typically decreases DP by several hundred units.
- the fibers in accordance with the present invention may be employed for a variety of applications, such as the production of non-woven fabrics.
- examples of products include tissues, wipes and speciality papers (f.e. filter applications) produced by wet-laid and/or air-laid techniques.
- the fibers in accordance with the present invention may by employed as the only fiber of a desired product or they maybe mixed with other types of fibers. The mixing ratio can depend from the desired end use. If for example a wipe with increased mechanical properties is desired the fibers in accordance with the present invention may be present in a higher amount, relative to other high fibrillation fibers according to the prior art, in order to secure the desired mechanical properties, while in other applications a lower relative amount of fibers of the present invention may be sufficient.
- parameter values and ranges as defined herein in relation to fibers refer to properties determined with fibers derived from pulp and containing only additives, such as processing aids typically added to the dope as well as other additives, such as matting agents (TiO 2 , which often is added in amounts of 0.75 wt.-%), in a total amount of up to 1 wt.-% (based on fiber weight).
- additives such as processing aids typically added to the dope as well as other additives, such as matting agents (TiO 2 , which often is added in amounts of 0.75 wt.-%), in a total amount of up to 1 wt.-% (based on fiber weight).
- the unique and particular properties as reported herein are properties of the fibers as such, and not properties obtained by addition of particular additives and/or post spinning treatments (such as fibrillation improving treatments etc.).
- the fibers as disclosed and claimed herein may comprise additives, such as inorganic fillers etc. in usual amounts as long as the presence of these additives has no detrimental effect on dope preparation and spinning operation.
- the type of such additives as well as the respective addition amounts are known to the skilled person.
- the standard 1.7 dtex 14 mm lyocell fibers are commercially available as TENCEL TM fibers from Lenzing AG ("lyocell standard").
- Lyocell fibers subjected to a chemical pre-treatment were produced as described in WO 2016065377 .
- a fiber tow with single titers of 1.7 dtex was impregnated with diluted sulfuric acid at room temperature with a liquor ratio 1:10 and afterwards pressed to -200% moisture.
- After-treatment of the fiber tow in a steamer for -10 min allows application of water vapor under pressure.
- the fiber bundle is washed acid-free, a soft-finish is applied and the fibers are dried.
- the dried fiber tow is cut into 4 mm shortcut fibers subsequently ending up with 1.7 dtex / 4 mm "lyocell chemical fibrillation" fibers.
- “Lyocell increased fibrillation” fibers were produced from a hemicellulose-rich pulp with a hemicelluloses content of >10% (xylan, mannan, arabinan,%), yielding after post-spinning treatment 1.7 dtex / 4 mm "lyocell increased fibrillation" fibers.
- Table 1 Comparison of different hemicellulose contents of pulps Sugar [%ATS] Standard lyocell pulp Hemicellulose-rich pulp Glucan 95.5 82.2 Xylan 2.3 8.3 Mannan 0.2 5.7 Arabinan ⁇ 0.1 0.3 Rhaman ⁇ 0.1 ⁇ 0.1 Galactan ⁇ 0.1 0.2
- the 3 different fiber types were refined in an Andritz Laboratory plant 12-1C plate refiner (NFB, S01-218238) at a starting concentration of 6 g/l, 1400 rpm and 172 I/min flow rate.
- the gap was fixed at 1 mm.
- Example 2 Comparison fibrillation time and tenacity
- both types of fibers show a high fibrillation tendency.
- both types of fibers require a time of less than 60 minutes.
- the chemical treatment also has a detrimental effect on the fiber properties as the working capacity is lowered significantly to about 60% of its initial value.
- the fiber in accordance with the present invention only shows, if at all, a minor decrease in working capacity thereby proving the superiority of the lyocell increased fibrillation fiber of the present invention.
- the fibers are produced according to example 1 with a cutting length of 38 mm.
- the nonwoven fibers (NW) are incorporated with 0,75% TiOz as a dulling agent.
- the composition of the hemicellulose-rich pulp used to produce the lyocell increased fibrillation II is shown in table 3. The results again confirm that in accordance with the present invention lyocell fibers are obtained with an increased tendency to fibrillate, without need for a chemical treatment and without the detrimental effects associated in the prior art with such treatments.
- Table 3 Sugar content of hemicellulose-rich pulp employed to produce lyocell increased fibrillation II.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Multicomponent Fibers (AREA)
Claims (20)
- Lyocellfaser mit erhöhter Neigung zur Fibrillierung ohne chemische Behandlung, die zur Erreichung eines 50° SR-Wertes gemäß ISO 5267-111999 eine Zeit von weniger als 80 Minuten erfordert, wobei die Verringerung der Arbeitskapazität [cN/tex*%] bei dem 50° SR-Wert weniger als 50% beträgt,
wobei der Hemicellulosegehalt in der Faser 7 Gew.-% oder mehr und 30 Gew.-% oder weniger beträgt. - Lyocellfaser nach Anspruch 1, wobei die zur Erreichung des 50° SR-Wertes erforderliche Zeit weniger als 60 Minuten aber mehr als 40 Minuten beträgt.
- Lyocellfaser nach Anspruch 1 und/oder 2, wobei die Verringerung der Arbeitskapazität weniger als 40%, vorzugsweise weniger als 30% beträgt.
- Lyocellfaser nach einem der Ansprüche 1 bis 3, mit einem Titer von 9 dtex oder weniger, insbesondere 6 dtex oder weniger, vorzugsweise 3 dtex oder weniger.
- Lyocellfaser nach einem der Ansprüche 1 bis 4, hergestellt aus einem Zellstoff mit einem Hemicellulosegehalt von 7 Gew.-% oder mehr und 25 Gew.-% oder weniger.
- Lyocellfaser nach Anspruch 5, wobei die Hemicellulose ein Verhältnis von C5/Xylan zu C6/Mannan von 125:1 bis 1:3, vorzugsweise von 25:1 bis 1:2 aufweist.
- Lyocellfaser nach einem der Ansprüche 5 oder 6, wobei der Zellstoff 5 Gew.- % oder mehr Xylan, vorzugsweise 8 Gew.-% oder mehr, noch bevorzugter 10 Gew.-% oder mehr und/oder 3 Gew.-% oder mehr Mannan, vorzugsweise 5 Gew.-% oder mehr Mannan, und/oder 1 Gew.-% oder weniger Mannan aufweist.
- Verwendung eines Zellstoffs zur Herstellung eines Faserstoffs nach einem der Ansprüche 1 bis 7, wobei der Zellstoff einen Hemicellulosegehalt von 7 Gew.-% oder mehr und 25 Gew.-% oder weniger aufweist.
- Verwendung nach Anspruch 8, wobei die Hemicellulose ein Verhältnis von C5/Xylan zu C6/Mannan von 125:1 bis 1:3, vorzugsweise von 25:1 bis 1:2 hat.
- Verwendung nach Anspruch 8 oder 9, wobei der Zellstoff 5 Gew.-% oder mehr Xylan, vorzugsweise 8 Gew.-% oder mehr, besonders bevorzugt 10 Gew.-% oder mehr, und/oder 3 Gew.-% oder mehr Mannan, vorzugsweise 5 Gew.-% oder mehr Mannan, und/oder 1 Gew.-% oder weniger Mannan aufweist.
- Verfahren zur Herstellung der Lyocellfaser nach einem der Ansprüche 1 bis 7 unter Anwendung eines direkten Auflösungsprozesses.
- Verfahren zur Herstellung der Lyocellfaser nach Anspruch 11 unter Anwendung eines Aminoxid-Verfahrens, wobei eine wässrige Lösung des Aminoxids und der Zellstoff eine Zellulosesuspension und eine formbare Lösung bilden, die in einem Spinnbad geformt und koaguliert wird, wobei nach Wasch- und Vorbehandlungsschritten der Lyocellfaserstoff erhalten wird.
- Verfahren zur Herstellung der Lyocellfaser nach Anspruch 12 unter Verwendung eines wässrigen tertiären Aminoxids, vorzugsweise wässriges NMMO.
- Verfahren nach einem der Ansprüche 11 bis 13, wobei die Spinnlösung einen Zellstoff mit einem Gehalt an Hemicellulosen von mehr als 10 Gew.-% bezogen auf das Gesamtgewicht der enthaltenen Cellulose und Hemicellulosen auweist.
- Lyocellfaser, Verwendung oder Verfahren nach einem der Ansprüche 1 bis 14, wobei der Zellstoff eine Scan-Viskosität von 300 bis 440 ml/g aufweist.
- Produkt mit einer Lyocellfaser nach einem der Ansprüche 1 bis 7 oder 15, oder mit einer nach einem der Ansprüche 11 bis 15 hergestellten Faser.
- Produkt nach Anspruch 16, wobei das Produkt ein Vliesstoff ist.
- Produkt nach Anspruch 16 und/oder 17, ausgewählt aus Taschentüchern und Wischtüchern.
- Produkt nach Anspruch 16, wobei das Produkt ein Spezialpapier ist.
- Produkt nach Anspruch 19, wobei das Spezialpapierprodukt ein Filter ist.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18160137.8A EP3536851A1 (de) | 2018-03-06 | 2018-03-06 | Lyocellfaser mit erhöhter neigung zur fibrillierung |
PCT/EP2019/055549 WO2019170732A1 (en) | 2018-03-06 | 2019-03-06 | Lyocell fiber with increased tendency to fibrillate |
Publications (2)
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EP3762536A1 EP3762536A1 (de) | 2021-01-13 |
EP3762536B1 true EP3762536B1 (de) | 2024-05-01 |
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EP18160137.8A Withdrawn EP3536851A1 (de) | 2018-03-06 | 2018-03-06 | Lyocellfaser mit erhöhter neigung zur fibrillierung |
EP19707837.1A Active EP3762536B1 (de) | 2018-03-06 | 2019-03-06 | Lyocellfaser mit erhöhter neigung zur fibrillierung |
Family Applications Before (1)
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EP18160137.8A Withdrawn EP3536851A1 (de) | 2018-03-06 | 2018-03-06 | Lyocellfaser mit erhöhter neigung zur fibrillierung |
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US (1) | US20210010163A1 (de) |
EP (2) | EP3536851A1 (de) |
TW (1) | TWI767110B (de) |
WO (1) | WO2019170732A1 (de) |
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TWI814782B (zh) * | 2018-03-06 | 2023-09-11 | 奧地利商蘭仁股份有限公司 | 溶劑紡絲之纖維素纖維 |
JP7259088B2 (ja) * | 2020-01-14 | 2023-04-17 | 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 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
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US4246221A (en) | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
ATA53792A (de) | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | Verfahren zur herstellung cellulosischer formkörper, vorrichtung zur durchführung des verfahrens sowie verwendung einer spinnvorrichtung |
US5456748A (en) | 1993-05-24 | 1995-10-10 | Courtaulds Fibres (Holdings) Ltd. | Premix storage hopper |
US5413631A (en) | 1993-05-24 | 1995-05-09 | Courtaulds (Holding) Limited | Formation of a cellulose-based premix |
AT401271B (de) | 1993-07-08 | 1996-07-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung von cellulosefasern |
GB9412500D0 (en) | 1994-06-22 | 1994-08-10 | Courtaulds Fibres Holdings Ltd | Fibre manufacture |
AT402410B (de) | 1995-04-19 | 1997-05-26 | Chemiefaser Lenzing Ag | Verfahren zur herstellung einer cellulosesuspension |
AT409130B (de) | 1995-04-25 | 2002-05-27 | Chemiefaser Lenzing Ag | Verwendung einer vorrichtung zum halten und abgeben einer homogenen cellulosesuspension |
GB9607456D0 (en) | 1996-04-10 | 1996-06-12 | Courtaulds Fibres Holdings Ltd | Spinning of filaments |
AT404594B (de) | 1996-08-01 | 1998-12-28 | Chemiefaser Lenzing Ag | Verfahren zur herstellung einer cellulosesuspension |
US6471727B2 (en) | 1996-08-23 | 2002-10-29 | Weyerhaeuser Company | Lyocell fibers, and compositions for making the same |
US6210801B1 (en) * | 1996-08-23 | 2001-04-03 | Weyerhaeuser Company | Lyocell fibers, and compositions for making same |
CN1191395C (zh) * | 2000-04-21 | 2005-03-02 | 韦尔豪泽公司 | 具有机械拉细的熔喷工艺 |
US8187422B2 (en) | 2006-03-21 | 2012-05-29 | Georgia-Pacific Consumer Products Lp | Disposable cellulosic wiper |
US20090165969A1 (en) * | 2007-12-31 | 2009-07-02 | Weyerhaeuser Co. | Enzymatic treatment of pulp for lyocell manufacture |
AT509289B1 (de) * | 2009-12-28 | 2014-06-15 | Chemiefaser Lenzing Ag | Funktionalisierter cellulosischer formkörper und verfahren zu seiner herstellung |
TWI392779B (zh) | 2009-12-31 | 2013-04-11 | A method for preparing natural cellulose nonwoven fabric by wet meltblowing | |
US9222222B2 (en) | 2010-08-20 | 2015-12-29 | Weyerhaeuser Nr Company | Dried highly fibrillated cellulose fiber |
AT514136A1 (de) * | 2013-04-05 | 2014-10-15 | Lenzing Akiengesellschaft | Polysaccharidfaser mit erhöhtem Fibrillationsvermögen und Verfahren zu ihrer Herstellung |
US20150184338A1 (en) * | 2013-12-31 | 2015-07-02 | Weyerhaeuser Nr Company | Treated kraft pulp compositions and methods of making the same |
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 |
-
2018
- 2018-03-06 EP EP18160137.8A patent/EP3536851A1/de not_active Withdrawn
-
2019
- 2019-03-06 WO PCT/EP2019/055549 patent/WO2019170732A1/en unknown
- 2019-03-06 EP EP19707837.1A patent/EP3762536B1/de active Active
- 2019-03-06 TW TW108107358A patent/TWI767110B/zh active
- 2019-03-06 US US16/978,220 patent/US20210010163A1/en active Pending
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US20210010163A1 (en) | 2021-01-14 |
EP3536851A1 (de) | 2019-09-11 |
TW201938858A (zh) | 2019-10-01 |
TWI767110B (zh) | 2022-06-11 |
WO2019170732A1 (en) | 2019-09-12 |
EP3762536A1 (de) | 2021-01-13 |
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