• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a process for the production of a cellulosic shaped body by the viscose process by shaping a spinning mass containing cellulose xanthate, which is characterized in that the cellulose xanthate xylan in a proportion of at least 1 wt.%, Based on cellulose, preferably 1 wt.% To 20 Wt.%, Particularly preferably 3 wt.% To 15 wt.% Is added. The invention further relates to cellulosic molded articles obtained by the viscose process with a proportion of high molecular weight xylan having an average degree of polymerization (DP) of 75 to 350, preferably 110 to 220 of at least 0.5% by weight, preferably 2% by weight to 8% by weight. ,
    公开号:AT514001A1
    申请号:T505642012
    申请日:2012-12-06
    公开日:2014-09-15
    发明作者:
    申请人:Chemiefaser Lenzing Ag；
    IPC主号:
    专利说明:

    1 L 522-15792
    Process for the preparation of a cellulosic molding
    The invention relates to a process for producing cellulosic shaped bodies by the viscose process.
    In particular, the invention relates to the production of fibers and filaments.
    The production of viscose fibers by the viscose process comprises the following steps: alkalizing a cellulosic starting material, in particular pulp (mash,
    Pre-maturity) • reaction of the alkalized cellulose starting material ("alkali cellulose") to cellulose xanthogenate • dissolving the cellulose xanthate with alkali, the so-called viscose is obtained as a dope • optionally adding modifiers to the viscose for the production of dope for modal fibers • spinning the viscose to Endlosformformkörpem • Regenerate of the cellulose in a precipitation bath from the endless molded articles • Aftertreatment, and drying. If necessary, cutting the continuous tablets into staple fibers.
    The fibers produced by this process are known by the generic term viscose fibers and modal fibers. The modal process differs from the standard viscose process by changed composition of the dope, additional modifiers in the dope and modified Spinnbadzusammensetzung.
    The pulp used in the viscose process must meet certain criteria to allow appropriate fiber qualities.
    The pulp used in the viscose process has an alpha-cellulose content of greater than 90% and has only low proportions of secondary compounds, such as xylan and other hemicelluloses (such as, for example, mannan). These compounds are for the most part degraded and leached out during the alkalization of the pulp at the beginning of the viscose process (FIG. 1). Hemicelluloses remaining in the pulp are depolymerized in pre-maturity together with the cellulose and therefore have a much lower average molecular weight than in the starting pulp. This applies both to the use of chemical pulps and to the use of paper pulps.
    In Figure 2, the significantly lower molecular weight of the hemicelluloses becomes clear, which are introduced with the pulp in the viscose process and then subject to degradation in mash and pre-maturity. In contrast, the molecular weights are represented by distributions of hemicelluloses extracted from a softwood and a hardwood pulp without degradation.
    WO 95/00698 describes a process in which, during the production of kraft pulp, initially a substantial amount of hemicellulose is removed from the production stream and is re-deposited on the pulp in a later stage.
    US Pat. No. 7,390,566 B2 and WO 2007/128026 disclose the use of pulp with a relatively high proportion of xylan for producing viscose fibers. The use of hemicellulose-rich pulp for producing lyocell fibers is known from WO 99/47733 A1 and WO 01/88236 A2.
    WO 2005/118950 describes the separation of beta-cellulose from lye obtained by pressing after a cold or hot alkaline extraction (CCE, HCE) of a pulp.
    There is still a need to increase the yield of the viscose process while maintaining the quality of the end products. There is also a need to provide novel viscose fibers with modified properties, in particular increased absorbency.
    The object of the present invention is achieved in one aspect by a process for the production of a cellulosic molded body by the viscose method by shaping a spinning mass comprising cellulose xanthate, which is characterized in that the cellulose xanthate xylan in a proportion of at least 1 wt.%, Based on cellulose , preferably 1 wt.% To 20 wt.%, Particularly preferably 3 wt.% To 15 wt.% Is added.
    In a further aspect, the invention relates to a cellulosic molded body obtained by the viscose process with a high molecular weight xylan content of 3/23 L 522-15792 having an average degree of polymerization (DP) of 75 to 350, preferably 110 to 220, of at least 0.5 % By weight, based on cellulose, preferably 2% by weight to 8% by weight.
    Brief description of the figures
    FIG. 1 shows the degradation of low-molecular constituents in the viscose process.
    Figure 2 shows the molecular weight distributions of high molecular weight hemicelluloses from pulps and degraded hemicellulose from the mash in the viscose process Figure 3 shows fiber strengths of viscose fibers with an increased content of high molecular weight xylan compared to a standard fiber without additional Xylanzugabe Figure 4 shows the development of water retention capacity (WRV) of Viscose fibers by the addition of high molecular weight xylan in the Löselauge
    FIG. 5 shows the molecular weight distribution of xylan precipitated after a CCE treatment of a eucalyptus kraft pulp and the molecular weight distribution of a viscose fiber after addition of this high molecular weight xylan.
    FIG. 6 shows the molecular weight distribution of a viscose fiber with a proportion of 4.8% high molecular weight xylan and its molecular weight distribution after mathematical removal of the high molecular weight xylan content.
    Detailed description of the invention
    Unless stated otherwise, percentages in each case below mean percentages by weight.
    It has surprisingly been found that, with the addition of xylan to the cellulose xanthogenate in the viscose process, an increase in the production yield can be achieved with constant or even improved properties of the resulting cellulose shaped bodies.
    In contrast to the prior art, in which the xylans contained in the pulp are largely dissolved out during the alkalization of the pulp and obtained as a waste product, according to the invention the xylan is added to the cellulose xanthate. In the subsequent steps of the viscose process (spinning, regeneration, etc.), no significant degradation or dissolution of the xylan takes place more, so that it remains largely in the resulting molded body. 4/23 4 L 522-15792
    According to the invention, the xylan is preferably added in the form of an alkaline solution. The alkaline solution may have a xylan content of 1 to 60 g / l.
    In particular, the xylan can be added to the cellulose xanthate as a constituent of an alkaline solution.
    In the dissolution of the cellulose xanthogenate for the preparation of the spinning solution, an alkaline solution is known to be used. In this may be contained according to the preferred embodiment of the present invention, the xylan to be added.
    Particularly preferably, the xylan originates from a pressing liquor produced during the pressing off of alkalized pulp at the beginning of the viscose process. In particular, it is possible to add to the cellulose xanthogenate the press liquor obtained during the pressing off of alkalized pulp.
    As mentioned above, the pulp is alkalized at the beginning of the viscose process. When the alkalized pulp is pressed off, an alkaline press liquor is obtained which contains a high proportion of xylan dissolved out by alkalization from the pulp.
    If this press liquor is used as the dissolving liquor to dissolve the cellulose xanthogenate, the xylan previously dissolved out of the pulp is returned to the process, thus increasing its yield.
    This xylan is relatively low molecular weight. One skilled in the art would expect that addition of low molecular weight xylan would adversely affect the strength properties of the resulting fiber. However, it has been shown that the addition of low molecular weight xylan does not adversely affect the strength of the fibers and thus an increase in yield with constant strength properties is possible.
    According to a particularly preferred embodiment of the process according to the invention, at least part of the added xylan is a high molecular weight xylan having an average degree of polymerization (DP) of 75 to 350, preferably 110 to 220.
    As already mentioned, in the embodiment described above, the xylan derived from the caustic liquor of the alkalization of the pulp by the viscose process is comparatively low in molecular weight during the degradation in the alkalization (see FIG. 2).
    It has been found that viscose fibers obtained by adding such low molecular weight xylan 5/23 5 L 522-15792, in their properties such. Strength and elongation do not fall behind conventional viscose fibers. Surprisingly, it has been found that the addition of high molecular weight xylan to cellulose xanthate results in comparable strength values and, in addition, an increased water retention capacity and also a better resistance of the xylan present to further process steps.
    The high molecular weight xylan is added in a proportion of 1% to 20%, preferably 3% to 15%, based on cellulose.
    The high molecular weight xylan may preferably originate from a hemicellulose-rich material stream obtained in the course of an extraction step in the production of a pulp.
    Process for the extraction of pulps in the course of their production, such as e.g. Alkaline pre-extraction directly from the wood chips before wood pulping or cold alkali extraction (CCE) are known. Also, non-alkaline method for extraction with Komplexbildnem such. As nitrenes or organic solvents such. B. DMSO are presented in the literature. In contrast to the alkalization of the (finished) pulp at the beginning of the viscose process, the xylan is indeed dissolved out of the pulp in these extraction process, but not degraded substantially.
    If the press liquor obtained by pressing off the pulp after extraction is removed by appropriate methods, e.g. Membrane filtration as in WO 2005/118050, concentrated, it produces a stream with a high proportion of high molecular weight xylan. This liquor may e.g. be added again directly as Löselauge or as part of the cellulose xanthate.
    This means in particular in an integrated viscose, in which the starting pulp is made to the viscose process itself, an increase in yield, because the otherwise incurred as a waste stream xylan is returned to the process.
    The present invention also relates to a cellulosic molded body obtained by the viscose process with a high molecular weight xylan content having an average degree of polymerization (DP) of 75 to 350, preferably 110 to 220, of at least 0.5% based on cellulose, preferably 2% to 8 %. 6/23 6 L 522-15792
    The molding according to the invention is novel since, without the addition of high molecular weight xylan to the cellulose xanthate according to the invention, no high molecular weight xylan is contained in the resulting molding in the conventional viscose process due to the degradation and dissolution of xylan.
    The cellulosic shaped body according to the invention is preferably in the form of a fiber, e.g. Staple fiber or filament fiber.
    The invention also relates to the use of the cellulosic molding according to the invention in absorbent products.
    Examples
    The invention will be explained in more detail with reference to the following examples:
    Until the preparation of the cellulose xanthate, the manufacturing process follows the conventional viscose process. According to the invention, the solution solution used is a pure alkali which has been enriched with xylan or an alkali which already contains xylan.
    The lye may contain low molecular weight and / or high molecular weight xylans.
    If a lye with only low molecular weight xylans is used, the lye can be added together with a possibly also used dissolving water.
    In the case of a lye containing high molecular weight xylans, it should first be added to the cellulose xanthate in order to prevent precipitation of the xylans and any addition of dissolving water should be carried out separately.
    In the following Examples 2 to 6, a high molecular weight xylans-containing liquor was used.
    To obtain the high molecular weight xylan rich liquor used in these examples, a pulp of eucalyptus wood made by the Kraft process was treated with 90 g / l NaOH at a stock consistency of 10% for 30 minutes. The resulting liquor was unchanged and after an enrichment process z. B. by membrane filtration, used as Löselauge. 7/23 7 L 522-15792
    The Lösleauge contained between 1 and 66 g / 1 dissolved xylan. The xylan was added to the xanthogenate with the alkaline Löselauge after xanthogenation and homogeneously mixed. The xylan had the following molecular weight distribution:
    Mw Mn PDI DP kg / mol kg / mol xylan 22 13 1.7 167
    Table: Molecular weight of the xylan used from a CCE liquor
    Figure 2 shows the molecular weight distribution of high molecular weight xylan as prepared from a CCE liquor from coniferous or hardwood pulps. It can be clearly seen that the xylan obtained after application of a CCE stage has a much higher average molecular weight than the xylan already degraded in the mash of the viscose process.
    The xylan was added to the xanthate from a conventional beech sulfite pulp and therefore was not present during the sulfidation, but only in the subsequent process step, the dissolution of the xanthate. The xylan is thus not xanthogenated, but dissolved in NaOH. The fibers were spun out in the laboratory. Fibers were thus produced with a significantly higher content of xylan (see Table 2 below).
    Example 1 (comparative example)
    A pulp (beech sulfite pulp) was mixed with about 18% NaOH, pressed and subjected to a pre-ripeness at about 34 ° C for 19 hours. A dope having the base composition 32% CS2, 8.6 to 8.9% cellulose and 5.2 to 5.6% alkali was prepared. The experiment was repeated with the same arrangement (Examples 1-1 and 1-2, respectively).
    The Löselauge contained 0% xylan. The resulting dope was conventionally spun into fibers having the properties shown in Table 2, Example 1. The present in the fibers (low molecular weight) xylan of 0.6 and 0.7% comes from the pulp used.
    Example 2 8/23 8 L 522-15792
    To a xanthate according to Example 1, a Löselauge with 8.5 g / 1 high molecular weight xylan was added. The resulting dope was spun into fibers having the properties shown in Table 2, Example 2. The xylan uptake was 63% of the high molecular weight xylan present in the Löselauge, which corresponds to a proportion of high molecular weight xylan of 0.7% based on the fiber.
    Example 3
    To a xanthate according to Example 1, a Löselauge with 22.0 g / 1 high molecular weight xylan was added. The resulting dope was spun into fibers having the properties shown in Table 2, Example 3. The xylan uptake was 79.2% of the high molecular weight xylan present in the Löselauge, which corresponds to a high molecular weight xylan content of 2.7% based on the fiber.
    Example 4
    To a xanthate according to Example 1, a Löselauge with 39.0 g / 1 high molecular weight xylan was added. The resulting dope was spun into fibers having the properties shown in Table 2, Example 4. The xylan uptake was 77.2% of the high molecular weight xylan present in the Löselauge, which corresponds to a high molecular weight xylan content of 4.8% based on the fiber.
    To detect the high molecular weight xylan on the fiber, the molecular weight distributions of the xylan-enriched fiber and that of the CCE-xylan used were determined by size exclusion chromatography (Figure 5). In the area of the xylan peak, there is clearly a shoulder on the fiber that suggests an accumulation of added xylan in the fiber. If this xylan content is deducted by calculation, the result is a curve of a standard viscose fiber, as shown in FIG. The xylene content of 5.5% reported in Figures 5 and 6 refers to the total content of xylan in the fiber (i.e., xylan from pulp used plus added high molecular weight xylan).
    Example 5
    To a xanthate according to Example 1, a Löselauge with 31.7 g / 1 xylan was added. The resulting dope was spun into fibers having the properties shown in Table 2, Example 5 9/23 9 L522-15792. The xylan uptake was 60.2% of the high molecular weight xylan present in the Löselauge, which corresponds to a high molecular weight xylan content of 6.9% based on the fiber.
    Example 6
    To a xanthate according to Example 1, a Löselauge with 66.3 g / 1 xylan was added. The resulting dope was spun into fibers. The xylan uptake was 54.4% of the high molecular weight xylan present in the Löselauge, which corresponds to a high molecular weight xylan content of 10.0% based on the fiber.
    In this example, the xylan-containing solubilizer was added to the cellulose xanthate along with solvent water. Obviously due to this, there was a partial precipitation of the xylan in the spinning mass, so that the quality of the spinning solution (filter value etc.) and also those of the spun fibers lagged behind those of Examples 2 to 5.
    Example 7 (comparative example)
    In a pilot plant, the same beech sulphite pulp was used for the production of viscose fibers. After the mash of the pulp, a low-molecular-weight xylan enriched press liquor was obtained by pressing. This liquor was subjected to nanofiltration. The permeate from the nanofilter, which has only a low content of low molecular weight xylan, was then used as Löselauge in the pilot plant.
    Because of the low supply of 0.38% xylan based on cellulose in the dope and its low molecular weight, no additional xylan was precipitated on the viscose fiber. The xylan content of the spun fiber was 0.5%. This xylan is derived from the pulp used.
    Example 8
    In a pilot plant, the same beech sulphite pulp was used for the production of viscose fibers. As Löselauge the rich low molecular weight xylan retentate from the nanofiltration described in Example 7 was used. 10/23 10 L 522-15792
    The xylan supply in the dope was 5.67% based on cellulose. Of these, 30.0% were spun into the fiber. A fiber with 2.2% xylan was obtained.
    Test Methods
    Determination of sugars in the fiber:
    Following a two-step total hydrolysis with sulfuric acid H2SO4, the sugar monomers were determined by anion exchange chromatography (AEC) using a pulsed amperometric detector (PAD). The method has been described in the following publication: Sixta H, Schelosky N, Milacher W, Baidinger T, Röder T (2001) Characterization of alkali-soluble pulp fractions by chromatography. Proceedings of the 11 * ISWPC, Nice, France: 655-658.
    Determination of the molecular weight distribution in the fiber:
    The molecular weight distribution in fibers was determined by size exclusion chromatography (SEC). The samples were dissolved in DMAc-LiCl (dimethylacetamide / lithium chloride). A MALLS detector (multi-angle laser light scattering) was used. Further details were published by Schelosky N, Röder T, Baidinger T (1999), Molar Mass Distribution of Cellulosic Products by Size Exclusion Chromatography in DMAc / LiCl, Paper 53, 12: 728-738.
    Determination of the molecular weight distribution of the added high molecular weight xylan: The xylan was precipitated from the CCE liquor under acidic conditions, analogous to the standard method Tappi T 203 om-93: 1993 to determine the beta and gamma fraction. It was then continued as in the determination of the molecular weight distribution of fibers by the SEC method.
    List of abbreviations: CCE cold caustic extraction, cold-alkali upgrading CS2 carbon disulfide DP Degree of Polymerization, degree of polymerization MW molecular weight Mw weight average molecular weight Mn number average molecular weight SEC Size exclusion chromatography, size exclusion chromatography WRV water retention PDI polydispersity index Mw / Mn 11/23 11 L522 -15,792
    The properties of the respectively obtained viscose spinning compositions and the resulting fibers according to Examples 2 to 5 are summarized in the following Table 2:
    Example 1-1 1-2 2 3 4 5 Filter Value 358 374 353 330 372 364 Particulate ppm 14.7 17.7 22.0 13.6 15.3 15.6 Xylan in the solvent eye Φ 0.0 0.0 8 , 5 22.0 39.0 31.7 xylan uptake% 0.0 0.0 63.0 79.2 77.2 60.2 Low molecular weight xylan in the fiber% or 0.6 0.7 0.7 0, 7 0.7 0.7 High molecular weight xylan in the fiber% or 0 0 0.7 2.7 4.7 6.9 Total xylan in fiber% or 0.6 0.7 1.4 3.4 5.5 7.5 molecular weight distribution of the viscose fiber: number average Mn kg / mol 26.5 28.5 29.3 27.6 27.5 26.6 weight average Mw kg / mol 63 65 66 66 63 61.5 polydispersity index PDI (Mw / Mn) 2.4 3.3 2.3 2.4 2.4 2.3 2.3 parts by weight of the polymers with DP <50% 5.6 5.0 4.8 5.2 5.1 5.6 part by weight of the polymers DPclOO% 11 , 7 11.7 11.5 12.8 13.0 13.8 titer dtex 1.30 1.29 1.34 1.37 1.34 1.34 Stability conditioned, 60% stretch cN / tex 26.0 25 , 0 26.5 24.8 24.8 23.8 Elongation conditioned, 60% stretch% 17.8 17.7 16.0 18.0 16.6 15.5 Working capacity% cN / tex 465 443 424 447 412 370 Wasserrückhaltevermö WRV% 90.0 92.4 94.5 95.6 98.5 97.1
    Table 2: Properties of viscose fibers of beech sulfite pulp with spun xylan from a CCE stage as co-polymer
    The high molecular weight xylan was taken up to an unexpectedly high level by the fiber. The uptake into the viscose fiber was 63% to 79% of the xylan offered in the Löselauge. From the filter value and the number of particles it becomes clear that the quality of the dope and the processability by no means suffered from the addition of this co-polymer. 12/23 12 L 522-15792
    In contrast, xylan, which is introduced into the process with only a chemical or paper pulp, is degraded and as a result is removed by 63 to 80% during the mash and spin bath (see Table 3 below). The filter value and particle content of the Viskosespinnmasse are - especially at a high input of xylan from a pulp - significantly reduced.
    Pulp Process xylan in pulp [%] Filter value [-] Particle content [pm] Xylan in pulp / fiber [%] Xylan loss [%] Chemistry Pulp Beech sulfite 3,1 364 15,6 0,6 80,6 Pulp Eucalyptus force 22.1 8 671 8.1 63.3 paper pulp Poplar force 19.8 69 118 7.3 63.1
    Surprisingly, it has been found that the textile mechanical properties of the fibers produced remain virtually constant (see FIG. 3). The xylan contents indicated in Figure 3 again refer to the total content of xylan in the fiber (i.e., xylan from pulp used plus added xylan).
    The water retention capacity WRV could also be significantly increased by the incorporation of xylan into the viscose fiber (see Table 2 and FIG. 4). That The uptake of water and the ability to adsorb water could not only be increased, but also selectively adjusted via the xylan content of the fiber. This is z. B. for use in absorbent products a whole new way to make product features. The abscissa (xylan content) in Figure 4 again refers to the total content of xylan in the fiber.
    FIG. 4 also shows the water retention capacity of the fiber produced according to Example 6 (high molecular weight xylan content: 10.0%). This was 106.0%.
    The properties of the respectively obtained viscose spinning compositions and the resulting fibers according to Examples 7 and 8 are summarized in the following Table 4:
    Example 7 8 Filter value 389 401 13/23 13 L 522-15792
    Example 7 8 Particles 4.5 5.0 Total xylan uptake% 0 30.0 Total xylan in the fiber% od 0.5 2.2 Molecular weight distribution of the viscose fiber: Number average Mn kg / mol 22.1 22.0 Weight average Mw kg / mol 60.1 66.7 Polydispersity index PDI (Mw / Mn) 2.7 3.0 parts by weight of the polymers with DP <50% 7.1 8.0 parts by weight of the polymers DPclOO% 15.3 15.1 titer dtex 1.40 1.45 Stability conditioned, 60% stretch cN / tex 26.8 25.8 Elongation conditioned, 60% stretch% 17.0 15.9 Workability% cN / tex 455.6 410.2
    Table 4. Properties of viscose fibers prepared with the addition of xylan from Visko seproduktion 14/23
    权利要求:
    Claims (11)
    [1]
    Claims 1. A process for the preparation of a cellulosic shaped body by the viscose method by shaping a spinning mass comprising cellulose xanthate, characterized in that the cellulose xanthate xylan in a proportion of at least 1 wt.%, Based on cellulose, preferably 1 wt.% to 20 wt.%, Particularly preferably 3 wt.% To 15 wt.% Is added.
    [2]
    2. The method according to claim 1, characterized in that the xylan is added in the form of an alkaline solution.
    [3]
    3. The method according to claim 1 or 2, characterized in that the xylan is added to the cellulose xanthate as part of an alkaline Löselauge.
    [4]
    4. The method according to any one of claims 2 or 3, characterized in that the xylan comes from a obtained during the pressing of alkalized pulp at the beginning of the viscose process caustic.
    [5]
    5. The method according to claim 4, characterized in that the cellulose xanthate is added to a pressing off of alkalized pulp at the beginning of the viscose process resulting caustic.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that at least a portion of the added xylan is a high molecular weight xylan having an average degree of polymerization (DP) of 75 to 350, preferably 110 to 220, is.
    [7]
    7. The method according to claim 6, characterized in that the high molecular weight xylan in a proportion of 1 wt.% To 20 wt.%, Preferably 3 wt.% To 15 wt.%, Based on cellulose added.
    [8]
    8. The method according to claim 6 or 7, characterized in that the high molecular weight xylan comes from a resulting in the course of an extraction step in the production of a pulp hemicellulose-rich stream.
    [9]
    9. A cellulosic shaped body obtained by the viscose process and having a high molecular weight xylan content with an average degree of polymerization (DP) of 15/23 15 522-15792 75 to 350, preferably 110 to 220, of at least 0.5% by weight, based on cellulose , preferably 2 wt.% To 8 wt.%.
    [10]
    10. Cellulosic molding according to claim 9 in the form of a fiber.
    [11]
    11. Use of a cellulosic molding according to one of claims 9 or 10 in absorbent products. 16/23
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    同族专利:
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    引用文献:
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    AT503611B1|2006-05-10|2009-05-15|Chemiefaser Lenzing Ag|METHOD FOR PRODUCING A PULP|EP3536833A1|2018-03-06|2019-09-11|Lenzing Aktiengesellschaft|Lyocell fibres without mannan|
    EP3536850A1|2018-03-06|2019-09-11|Lenzing Aktiengesellschaft|Pulp and lyocell articles with reduced cellulose content|
    EP3536832A1|2018-03-06|2019-09-11|Lenzing Aktiengesellschaft|Lyocell fiber with improved disintegration properties|
    EP3536831A1|2018-03-06|2019-09-11|Lenzing Aktiengesellschaft|Lyocell fiber with novel cross section|
    EP3536852A1|2018-03-06|2019-09-11|Lenzing Aktiengesellschaft|Pulp and lyocell fibre with adjustable degree of whiteness|
    CN109913967A|2019-03-19|2019-06-21|阿拉尔市富丽达纤维有限公司|A kind of technique preparing viscose rayon using low polymerizing degree pulp|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50564/2012A|AT514001B1|2012-12-06|2012-12-06|Process for the preparation of a cellulosic molding|ATA50564/2012A| AT514001B1|2012-12-06|2012-12-06|Process for the preparation of a cellulosic molding|
    ES13801568.0T| ES2622567T3|2012-12-06|2013-12-04|Procedure for the production of a cellulosic molded body|
    CN201380063944.7A| CN104919097B|2012-12-06|2013-12-04|The method for manufacturing cellulosic molded body|
    SI201330615A| SI2929071T1|2012-12-06|2013-12-04|Method for producing a cellulosic molded body|
    PCT/EP2013/075575| WO2014086883A1|2012-12-06|2013-12-04|Method for producing a cellulosic molded body|
    PL13801568T| PL2929071T3|2012-12-06|2013-12-04|Method for producing a cellulosic molded body|
    EP13801568.0A| EP2929071B1|2012-12-06|2013-12-04|Method for producing a cellulosic molded body|
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