EP3536850A1 - Pulpe et articles en lyocell avec un taux en cellulose réduit - Google Patents

Pulpe et articles en lyocell avec un taux en cellulose réduit Download PDF

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Publication number
EP3536850A1
EP3536850A1 EP18160123.8A EP18160123A EP3536850A1 EP 3536850 A1 EP3536850 A1 EP 3536850A1 EP 18160123 A EP18160123 A EP 18160123A EP 3536850 A1 EP3536850 A1 EP 3536850A1
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EP
European Patent Office
Prior art keywords
pulp
content
lyocell
hemicellulose
weight
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.)
Withdrawn
Application number
EP18160123.8A
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German (de)
English (en)
Inventor
Verena Silbermann
Martina OPIETNIK
Gabriele Schild
Susanne MÖDERL
Magdalena Körbler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Priority to EP18160123.8A priority Critical patent/EP3536850A1/fr
Priority to TW108107361A priority patent/TWI746936B/zh
Priority to ES19708327T priority patent/ES2968528T3/es
Priority to CA3092615A priority patent/CA3092615C/fr
Priority to PCT/EP2019/055593 priority patent/WO2019170763A1/fr
Priority to CN201980017308.8A priority patent/CN111788348B/zh
Priority to EP19708327.2A priority patent/EP3762537B1/fr
Priority to BR112020017780-6A priority patent/BR112020017780A2/pt
Priority to US16/978,340 priority patent/US20210002825A1/en
Priority to FIEP19708327.2T priority patent/FI3762537T3/fi
Priority to RU2020132856A priority patent/RU2781410C2/ru
Publication of EP3536850A1 publication Critical patent/EP3536850A1/fr
Priority to CL2020002286A priority patent/CL2020002286A1/es
Priority to ZA2020/06048A priority patent/ZA202006048B/en
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • D01F2/30—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate by the dry spinning process
    • 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
    • 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
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • 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
    • 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
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • 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

Definitions

  • the present invention describes special pulp compositions which make it possible to produce a lyocell fiber with a reduced cellulose content in a technically stable manner and the lyocell fiber produced therefrom.
  • Lyocell fibers are used in a variety of applications. Purified cellulose is often used as a raw material, with a very low content of cellulose endings.
  • the present invention provides a pulp according to claim 1, a lyocell product according to claim 9, and the methods according to claims 16 and 18.
  • Preferred embodiments of the invention are given in the subclaims and the following detailed description of the invention.
  • the main constituents of non-cellulosic material in the raw material wood are the hemicelluloses (mainly polyoses from the sugar monomers xylose, arabinose, mannose, galactose, glucose and rhamnose), lignin and accessory components.
  • Cellulose It is the skeletal substance of the cell walls in the wood and serves mainly the tensile strength.
  • the long molecular chains of glucose units are assembled in so-called fibrils several times in a helical structure. This helical arrangement in the cell wall ensures a good bending strength of the tree, e.g. at a wind load or wood z. B. in a roof construction.
  • Cellulose is hydrophilic but not water-soluble due to its high crystallinity.
  • Lignin Binder for the firm bonding of cellulose in the form of an amorphous matrix.
  • lignin is mainly responsible for the compressive strength, on the other hand, is less flexible and hydrophobic in contrast to cellulose. It is responsible for the stamina of the tree. Plants that do not store lignin only reach low stature heights. Lignin is biologically relatively stable and biologically degradable only slowly.
  • Hemicellulose for the purposes of the present invention are components present in wood in the form of short-chain polymers of C5 and / or C6 sugars. In contrast to cellulose, they have side groups and can therefore form crystals only to a much lesser extent. Their basic building blocks are mannose, xylose, glucose, rhamnose, galactose. The side groups preferably consist of arabinose groups, acetyl groups and galactose residues as well as O-acetyl groups and 4-O-methylglucuronic acid side groups. It is known that mannans are preferably associated with cellulose, while xylans are more likely to associate with lignin. The composition of hemicelluloses varies greatly depending on the type of wood used.
  • hemicelluloses includes those in their native structure as well as those modified by their processing and also those which have been adjusted by specific chemical modification for the particular application. Also included are short chain celluloses and other polyoses with a DP of up to 500.
  • Accessory ingredients are wood-derived organic and inorganic non-lignin, cellulose, and hemicellulose, and commonly include salts and low molecular weight organic compounds of up to about 100 atoms, such as tannins, resins, fats and waxes, tanning agents. and humic substances, terpenes, terpenoids and phenolic compounds, pectins, suberines, polyphenols and polyoses.
  • a fraction of hemicelluloses of at least 7% by weight is present, whereby the ratio of sugars with five C atoms, such as, for example, B. xylan to sugars with six carbon atoms such. Mannan (hereinafter called C5 / C6 ratio) is in the range of 125: 1 to 1: 3.
  • the pulps used here which are preferably used in the context of the present invention, show, as already stated, a relatively high content of hemicelluloses the composition defined here.
  • the pulps preferably used in the context of the present invention also show other differences which are listed below.
  • the pulps preferably used in the context of the present invention show a rather fluffy view. This results after milling (during the preparation of starting materials for the production of spinning solutions for the lyocell process) in a particle size distribution with a high proportion of larger particles. As a result, the bulk density is much lower, compared to standard pulps with a low hemicellulose content. Such a low bulk density requires adaptations with regard to metering parameters (eg metering using at least two storage tanks) in the preparation of the spinning solutions.
  • the pulps preferably used in the context of the present invention show an impregnation behavior with respect to NMMO, which shows that the impregnation is more difficult in comparison with standard pulps.
  • the pulp used for the production of lyocell products exhibits a SCAN viscosity in the range of 300 to 440 ml / g, in particular 320 to 420 ml / g, more preferably 320 to 400 ml / g.
  • the SCAN viscosity is determined in accordance with SCAN-CM 15:99 using a Cupriethylendiaminannon, a method which is known in the art and which can be performed with commercially available devices, such as with the device Auto PulpIVA PSLRheotek, available from the company PSL Reotek.
  • the viscosity of SCAN is an important parameter which influences in particular the processing of pulps in the production of spinning solutions. Even if two pulps show great agreement with respect to their composition, etc., different SCAN viscosities result in completely different behavior during processing.
  • a direct solution spinning process like the lyocell method, the pulp is dissolved in NMMO as such. There is no maturation step, comparable for example with the viscose method, where the degree of polymerisation of the cellulose can be adapted to the needs of the process. Therefore, the specifications for the viscosity of a raw pulp are typically for the lyocell process in a small target window. Otherwise problems can occur during production.
  • the pulp viscosity is preferably as previously described.
  • Lower viscosities lead to a deterioration of the mechanical properties of the lyocell products.
  • Higher viscosities can in particular lead to an increased viscosity of the spinning solution, so that spinning is slower overall.
  • With lower spinning speeds lower draw ratios are obtained, which again can have a significant influence on the fiber structure and the fiber properties ( Cabohydrate Polymers 2018, 181, 893-901 ). This would require process adaptations that would lead to capacity reduction.
  • the use of pulps with the viscosities defined herein, on the other hand, allows for easy processing and the production of high quality products.
  • the fiber properties are strongly influenced by the type and by the assembly of the polymers. It is also known that cellulosic fibers produced by the lyocell process have a very high crystallinity of about 44 to 47%, while fibers from the viscose process have a crystallinity of about 29 to 34%.
  • the crystallinity describes the alignment of the cellulosic polymers to each other and thus, for example, their ability to absorb, swell and store water.
  • the polymer chains are more ordered in the non-crystalline regions of the lyocell fibers than in the viscose fibers. As a result, ordinary lyocell fibers swell less and are less suitable for highly absorbent products than viscose fibers.
  • celluloses with reduced cellulose content By using the celluloses with reduced cellulose content according to the invention, a completely different type of aggregation of the polymers and thus a different structure of the lyocell fibers is unexpectedly made possible.
  • Their crystallinity is significantly lower, typically 40% or less, such as 39% or less and, for example, in the range of 38% to 30%, such as in the range of 37 to 33%.
  • the values for WRV for fibers in accordance with the present invention, isolated or in combination with the other preferred embodiments described herein, preferably in combination with the fiber crystallinity values described herein, are preferably 70% or greater, more preferably 75% or greater , like 80% or more, eg from 70 to 85%.
  • the hemicelluloses still have side groups, since the glucuronic acid side groups of xylan under the conditions of acid digestion are relatively stable ( Sixta H (Ed.) (2006): Handbook of Pulp Vol. 1; Wiley VCH p. 418 ).
  • the hemicelluloses thus fulfill all conditions to disrupt the crystallization of the cellulose and thus form a more disordered structure compared to standard lyocell fibers.
  • higher hemicellulose content and reduced cellulose content would give useless products, especially fibers.
  • it has unexpectedly been shown that the content of hemicelluloses in combination with the C5 / C6 ratio allows targeted control of product properties.
  • the grades of the new reduced cellulosic lyocell fibers are similar to those of conventional TENCEL® fibers. It can be seen that the fiber strengths are slightly lower than those of the TENCEL® fibers, measured in the examples as strength and workability. At the same time, the cellulose content could be significantly reduced, recorded in the examples as glucan value. The uptake of other wood constituents reduces the crystallinity by up to 21% and the absorbency increases significantly by up to 27%, measured in the examples as crystallinity index and water retention capacity.
  • the crystallinities of the new lyocell fibers according to the invention lie between those of conventional TENCEL® fibers and nonwovens Lenzing Viscose® fibers; at the same time, WRV is in the Lenzing Viscose® range.
  • the WRV increases more than would be explained by the decreasing crystallinity of the fibers.
  • the other ingredients such as in particular hemicelluloses, but also lignin and accessory Components from the wood therefore not only ensure a significant increase in yield, ie improved sustainability, but also a significant improvement in product properties, such as water retention capacity.
  • the pulp of the invention is characterized by a reduced content of cellulose, a minimum amount of hemicelluloses and a certain C5 / C6 ratio with respect to the composition of the hemicellulose.
  • the pulp which may also be a mixture of different pulps (as long as the essential conditions are met), is a pulp having a hemicellulose content of from 7 to 50% by weight, preferably from 7 to 25% by weight preferably 10 to 20 wt .-%.
  • the pulp to be used according to the invention is furthermore preferably a pulp which has a xylan content of at least 9% by weight, preferably a fraction of at least 10% by weight.
  • the proportion of mannan can, in combination or independently, be chosen within a wide range, as long as the ratio defined according to the invention is fulfilled. Suitable mannan contents are in the range of 0.1 to 10% by weight, such as from 0.1 to 9% by weight and in embodiments from 0.1 to 6% by weight, from 0.1 to 4% by weight. %, from 5 to 10% by weight, from 6 to 10% by weight, etc.
  • the Mannangehalt in the range of 0.1 to 1 wt .-%, preferably in combination with a xylan content of at least 9 wt. -%, preferably at least 10 wt .-%. In other embodiments, the Mannangehalt is higher, preferably in the range of 6 wt .-% or more.
  • the cellulose content in the pulp is in a range of equal to or less than 90% by weight to 50% by weight, preferably in the range of 90% by weight. % to 60 wt%, such as from 85 wt% to 70 wt%.
  • the weight ratio of cellulose to hemicellulose may range from 1: 1 to 20: 1.
  • the level of accessory constituents may be more than 0.05% by weight, preferably more than 0.2% by weight, more preferably more than 0.5% by weight. It has unexpectedly been found that with such proportions of accessory constituents in the pulp according to the invention, the effect can be promoted that the C5 / C6 ratio is also stable in the prepared lyocell products, in particular fibers, and the hemicellulose content does not change significantly (ie the content does not decrease in the lyocell product or only slightly in comparison to the pulp).
  • the inventive C5 / C6 ratio achieves such a high retention capacity that at the same time a proportion of metal compounds, generally present as their oxides and hydroxides of up to 25% by weight, based on the weight of the lyocell product (eg, Mg (OH) 2 or Al (OH) 3 for flame retardancy purposes), which further substantially reduces the cellulose content.
  • metal compounds are in particular TiO 2 , Al 2 O 3 , MgO, SiO 2 , CeO 2 , Mg (OH) 2 , Al (OH) 3 , BN, ZnO and originate in part from the mineral constituents of the wood or can be used as the cellulose solution functional additives (flame retardant, matting agent, biocide ...) are added.
  • lyocell fibers having a cellulose content reduced to less than 70% can be prepared which not only meet the practical requirements in comparison with the known lyocell fibers (mechanical strengths, etc.), but also due to the novel properties resulting for some applications even better.
  • the investigations have shown that fibers in the proposed composition have, in particular, an increased water retention capacity and a rapid biodegradability during composting.
  • the ratio of C5 / C6 sugars of the non-cellulosic polymers has been shown to be an important factor in adjusting the fiber composition and its resulting properties. Through targeted adjustment of this ratio, also in combination with the content of hemicelluloses, desired product properties can be adjusted in a targeted manner.
  • the person skilled in the art is aware of how he / she can control or adjust the C5 / C6 ratio. This can be achieved by a mixture of different pulps such. As softwood pulps with a higher Mannananteil be achieved with hardwood pulps with a higher xylan content. Attempts have confirmed another very effective way to adjust accordingly. By a targeted adjustment of cooking parameters such. As the H-factor, the ratio of C5 to C6 sugars can be controlled. This is shown in Figures 2 and 3. The H factor is considered to be an essential parameter for the control of sulfite boiling (Sixta (Vol. 1 2006) p. 432). He summarizes cooking temperature and cooking time as one size.
  • Figure 2 shows the influence of the H-factor in sulfite boiling on the hemicellulose ratio in hardwood using the example of beech.
  • xylan content is inherently higher.
  • H-factor increases, xylan degrades more than mannan.
  • the ratio C5 / C6 decreases.
  • Another way to adjust the pulp composition according to the invention is the admixing of C5 and / or C6 sugars, which were previously obtained in other processes or process steps, such as. B. in an alkaline extraction, be it a cold-alkali extraction or an E-stage or the like.
  • an alkaline extraction be it a cold-alkali extraction or an E-stage or the like.
  • viscose the addition of hemicelluloses in dissolved form to the spinning mass and the subsequent co-spinning are known ( WO2014086883 ).
  • viscose fibers can be produced with a reduced cellulose content.
  • the viscose process takes place in the aqueous medium and the hemicelluloses are correspondingly alkali-soluble, so the cellulose xanthogenate and the dissolved hemicelluloses can be mixed together and spun together.
  • the solution of the pulp in the lyocell process takes place in NMMO or similar solvents, so here no alkaline or aqueous solutions can be added. You would dilute the solvent and reduce the solubility or even lead to unwanted precipitation.
  • the hemicelluloses can not be added in the form of solutions in spinning solution production, but must be introduced differently in the process.
  • One possibility is the addition in the pulp manufacturing process, so that the mixture can then be dried with the pulp.
  • the ratio of xylan to mannan is between 18: 1 to 1: 3, preferably 9: 1 to 1: 2.
  • such a mixing ratio allows the incorporation of 0.5-5% by weight of lignin (and / or other accessory Constituents) into the fiber structure without adversely affecting the desired properties.
  • the fibers provided according to the invention have typical fiber titers, such as 7 dtex or less, for example 2.2 dtex or less, such as 1.3 dtex or less, possibly even lower, such as 0.9 dtex or less, depending on the desired application. For applications in the nonwoven sector, titres of 1.5 to 1.8 dtex are typical, while for textile applications lower titers, such as 1.2 to 1.5 dtex are suitable.
  • the present invention also includes fibers having even lower titers, as well as fibers having significantly higher titers, such as 10 dtex or less, such as 9 dtex or less, or even 7 dtex or less.
  • Suitable lower limits for fiber titers are values of 0.5 dtex or greater, such as 0.8 dtex or greater and, in embodiments, 1.3 dtex or greater.
  • the upper and lower limits disclosed herein may be combined and the regions formed thereby, such as from 0.5 to 9 dtex, are also included.
  • the present invention enables the production of fibers with titers, which allows use in the entire spectrum of fiber applications, including textile applications as well as nonwoven applications.
  • the determination of the crystallinity index is carried out by means of Raman spectroscopy. This method is calibrated with data from the X-ray wide-angle method (WAX) and was used by Röder et al. (2009) ( Röder T, Moosbauer J, Kliba G, Schlader S, Zucker Toor G, and Sixta H (2009): Comparative Characterization of Man-Made Regenerated Cellulose Fibers. Lenzinger Berichte Vol. 87, p. 98 ff .).
  • Table 1 shows the results of setting the C5 / C6 ratio for two species of wood, using the example of H-factor variation in magnesium bisulfite digestion.
  • Table 1 shows the results of setting the C5 / C6 ratio for two species of wood, using the example of H-factor variation in magnesium bisulfite digestion.
  • Table 1 shows the results of setting the C5 / C6 ratio for two species of wood, using the example of H-factor variation in magnesium bisulfite digestion.
  • Table 1 shows the results of setting the C5 / C6 ratio for two species of wood, using the example of H-factor variation in magnesium bisulfite digestion.
  • Table 4 shows mechanical characteristics for standard fibers (lyocell and viscose) compared with characteristics obtained with lyocell fibers made with pulps of the invention. The results clearly demonstrate the advantages of the present invention.
  • the new lyocell fibers according to the invention thus combine the respective advantageous properties of hitherto commercially available lyocell or viscose fibers.
  • Table 4 ⁇ / b> Properties of conventional and cellulosic reduced lyocell fibers compared to a standard viscose fiber.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Knitting Of Fabric (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP18160123.8A 2018-03-06 2018-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit Withdrawn EP3536850A1 (fr)

Priority Applications (13)

Application Number Priority Date Filing Date Title
EP18160123.8A EP3536850A1 (fr) 2018-03-06 2018-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit
BR112020017780-6A BR112020017780A2 (pt) 2018-03-06 2019-03-06 Polpa de celulose e corpo de lyocell tendo teor de celulose reduzido
US16/978,340 US20210002825A1 (en) 2018-03-06 2019-03-06 Cellulose pulp and shaped lyocell article having a reduced cellulose content
CA3092615A CA3092615C (fr) 2018-03-06 2019-03-06 Pulpe et articles en lyocell avec un taux en cellulose reduit
PCT/EP2019/055593 WO2019170763A1 (fr) 2018-03-06 2019-03-06 Cellulose et corps moulé en lyocell à teneur réduite en cellulose
CN201980017308.8A CN111788348B (zh) 2018-03-06 2019-03-06 具有减少的纤维素含量的浆粕和莱赛尔成型体
EP19708327.2A EP3762537B1 (fr) 2018-03-06 2019-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit
TW108107361A TWI746936B (zh) 2018-03-06 2019-03-06 具有降低的纖維素含量的木漿、其製造方法、使用其製造萊纖成形體之方法及萊纖成形體
ES19708327T ES2968528T3 (es) 2018-03-06 2019-03-06 Pasta de celulosa y cuerpos moldeados de Lyocell con contenido reducido de celulosa
FIEP19708327.2T FI3762537T3 (fi) 2018-03-06 2019-03-06 Selluloosa ja lyosellikappaleet, joissa on pienennetty selluloosapitoisuus
RU2020132856A RU2781410C2 (ru) 2018-03-06 2019-03-06 Древесная масса и лиоцелловое изделие с уменьшенным содержанием целлюлозы
CL2020002286A CL2020002286A1 (es) 2018-03-06 2020-09-03 Artículos de pulpa y fibra de lyocell con menor contenido de celulosa
ZA2020/06048A ZA202006048B (en) 2018-03-06 2020-09-30 Cellulose pulp and shaped lyocell article having a reduced cellulose content

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EP18160123.8A EP3536850A1 (fr) 2018-03-06 2018-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit

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EP18160123.8A Withdrawn EP3536850A1 (fr) 2018-03-06 2018-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit
EP19708327.2A Active EP3762537B1 (fr) 2018-03-06 2019-03-06 Pulpe et articles en lyocell avec un taux en cellulose réduit

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US (1) US20210002825A1 (fr)
EP (2) EP3536850A1 (fr)
CN (1) CN111788348B (fr)
BR (1) BR112020017780A2 (fr)
CA (1) CA3092615C (fr)
CL (1) CL2020002286A1 (fr)
ES (1) ES2968528T3 (fr)
FI (1) FI3762537T3 (fr)
TW (1) TWI746936B (fr)
WO (1) WO2019170763A1 (fr)
ZA (1) ZA202006048B (fr)

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* Cited by examiner, † Cited by third party
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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
CN113109205A (zh) * 2021-03-29 2021-07-13 杭州融凯盛科技有限公司 一种快速检测莱赛尔纤维成型状态方法

Citations (16)

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ZA202006048B (en) 2022-03-30
CN111788348A (zh) 2020-10-16
WO2019170763A1 (fr) 2019-09-12
BR112020017780A2 (pt) 2020-12-22
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