• 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 present invention relates to a process for the preparation of Polysaccharldfasem containing as a fiber-forming substance (1 3) Giucan, and the fibers produced therefrom and their use.
    公开号:AT514475A1
    申请号:T485/2013
    申请日:2013-06-17
    公开日:2015-01-15
    发明作者:
    申请人:Lenzing Akiengesellschaft；
    IPC主号:
    专利说明:

    Polysaccharide fiber and process for its preparation
    The present invention relates to a process for producing polysaccharide fibers containing a (1-> 3) -glucan as the fiber-forming material, and the fibers produced therefrom and their use.
    Stand dar technique
    Polysaccharides play an increasingly important role as materials that can be obtained from renewable raw materials. One of the most abundant polysaccharides is cellulose. Cotton fibers, which consist almost exclusively of cellulose, are an example of the importance of polysaccharides. But also from other celluloslschen raw materials obtained materials such. B. Cellulosic synthetic fibers are becoming increasingly important.
    The generic names "Viscose-Fasem" and "Modal-fibers" have been assigned by the BISFA (Bureau for the International Standardization of Man-Made Fibers) to cellulose fibers produced by chemical derivatization of cellulose using caustic soda and carbon disulfide (CS2).
    The term "modal fiber" is a generic term used in the definition of BISFA for a cellulose fiber with a defined high wet strength and high wet modulus (ie the force required to stretch the fiber by 5% when wet) ) stands.
    However, to date, only a process for large-scale production of fibers of the genera Viscose and Modal has prevailed and that the viscose method and modifications thereof.
    How this method is carried out, the expert is known in principle for many years from many patents and other publications. A method for the production of modal fibers is known for example from AT 287.905 B. CS2 has in the known viscose 2 essential tasks:
    Lenzing AG, PL0551 1. Reaction with Alkali Cellulose to Form a Xanthate that Is Soluble in Alkaline Solution 2. "Effect in Spin Bath "
    In the viscose spinning bath, colloid chemical (coagulation of sodium cellulose xanthate) and chemical (decomposition of xanthate to hydrate cellulose) processes take place in parallel. Both are influenced by the CS2 used.
    The viscose process has a serious drawback compared to the new resource and environmentally friendly lyocell process: the use of large amounts of CS2 and caustic soda. This problem affects the production of modal fibers even more. In the text below, the term viscose fiber is used for all viscose methods and modifications, including the modal method and fibers made therewith.
    The cellulosic raw material previously used in the viscose process is pulp, which is mainly obtained from wood. Despite many investigations, no method based on the viscose technology has been developed so far, with which the use of CS2 or NaOH can be significantly reduced.
    US 7,000,000 describes fibers obtained by spinning a solution of polysaccharides consisting essentially of hexose repeat alcohols linked via a (1-> 3) glycosidic linkages. These polysaccharides can be prepared by contacting an aqueous solution of sucrose with glucosyltransferase (GtfJ) isolated from Streptococcus sallvarius (Simpson et al., Microbiology, vol 41, pp 1451-1460 (1995)). "Substantially" in this context means that occasionally defects can occur within the polysaccharide chains at which other binding configurations occur. These polysaccharides are to be referred to as "a (1-" 3) -glucan "for purposes of the present invention.
    The US 7,000,000 first discloses possibilities for the enzymatic production of a (1-> 3) -glucan from monosaccharides. In this way, relatively short-chain polysaccharides can be prepared without loss of monomer units, since the polymer chains are built up from the monomer units. In contrast to the production of short-chain cellulose molecules, the shorter the polymer chains, the cheaper the production of a (1- »3) -glucan, since then only a small residence tenth is necessary in the reactors.
    According to US Pat. No. 7,000,000, the a (1 →> 3) fluorene is to be derivatized, preferably acetylated. The solvent is preferably an organic acid, an organic halogen compound, a fluorinated alcohol or a mixture of such components. These solvents are expensive and expensive to regenerate.
    However, studies have also shown that a (1-> 3) -glucans are soluble in dilute sodium hydroxide solution (about 4 to 5.5%).
    WO 2013/052730 A1 discloses fibers with a (1- »3) -glucan as a fiber-forming substance, which were prepared by the so-called amine oxide process with NMMO as solvent by spinning. The amine oxide process is fundamentally different from the viscose or modal process and requires a completely different product purification system. A viscose production plant can not be converted to the amine oxide process by simple conversion measures.
    task
    The object over this prior art therefore was to provide an alternative process for the production of polysaccharide fiber, with which the amount of CS2 and sodium hydroxide per unit of fiber produced can be significantly reduced.
    Lenzing AG, PL0551 Description of the invention
    The solution of the above-described object is a novel process for producing a polysaccharide fiber whose fiber-forming substance is a (1- »3) -glucan, the process being a modified viscose process. Thus, a viscosity-like fiber can be produced, wherein a (1-> 3) -glucan-containing sodium hydroxide solution with small amounts of CS2 is added. At most 30% of CS2 based on the fiber-forming substance is used, preferably less than 25% of CS2 and more preferably less than 15% of C $ 2. Preferably, an amount used between 5 and 30 percent by weight of CS2, calculated on fiber-forming material, preferably between 5 and 25%, particularly preferably between 5 and 15%. Such fiber, for the purposes of the present invention, should also be referred to as viscose fiber, although it contains, instead of cellulose, another fiber-forming polysaccharide, namely a (1- + 3) -glucan.
    Surprisingly, it was found that CS2 is not required in this modified process, as in the case of cellulose for the solution of polysaccharide in caustic soda, but only for the slowing down of the thread formation in the spinning bath.
    According to the invention, the NaOH concentration in the spinning solution should be between 4.0 and 5.5% by weight, calculated on the total amount of the spinning solution. Outside this range, the solubility of glucan is insufficient. For purposes of the present invention, the term "cheese" is intended to encompass both staple fibers of defined cut length and continuous filaments. All principles of the invention described below apply in principle both to staple fibers and to continuous filaments.
    The single fiber titer of the fibers according to the invention can be between 0.1 and 10 dtex. It is preferably between 0.5 and 6.5 dtex and more preferably between 0.9 and 6.0 dtex. In the case of staple fibers, the cut length is usually between 0.5 and 120 mm, preferably between 20 and 70 mm and particularly preferably between 35 and 60 mm. In the case of endless filaments, the number of single filaments in the filament yarn is between 50 and 10,000, preferably between 50 and 3,000.
    The a (l ~ * 3) glucan can be prepared by contacting an aqueous solution of sucrose with glucosyltransferase (GtfJ) isolated from Streptococcus salivarius (Simpson et al., Microbiology, vol 41, pp 1451-1460 ( 1995)).
    In a preferred embodiment of the process of the invention, at least 90% of the a (1-> 3) -glucan consists of hexose units and at least 50% of the hexose units are linked by a (1- »3) -glycosidic bonds.
    The process for the preparation of the fiber according to the invention consists of the following steps: 1. Preparation of a (1-> 3) -glucan solution in dilute sodium hydroxide 2. Addition and mixing of CS2, a short post-maturation, filtration and deaeration of the spinning solution 3. Spinning the oc (1 -> 3) glucan-containing spinning solution through a nozzle Into a sulfuric spinning bath, stretching of the fibers and post-treatment.
    The concentration of the fiber-forming substance in the spinning solution can be between 4 and 18% by weight, with 4.5 to 15% by weight being preferred.
    The degree of polymer activity of the α (ΐ-> 3) glucan used in the method according to the invention, expressed as weight average DPW, can be between 200 and 2000: values between 500 and 1000 are preferred.
    The present invention is also a viscose or modal fiber containing cellulose and a (1- »3) -glucan,
    Lenzing AG, PL05S1
    In a preferred embodiment, the a (1-> 3) glucan of the viscose fiber of the present invention is at least 90% hexose and at least 50% of the hexose moieties are linked by a (1- »3) glycosidic bonds ,
    Likewise provided by the present invention is the use of the fibers according to the invention for the production of various dry and wet laid papers, nonwovens, hygiene articles such as tampons, panty liners and diapers and other nonwovens, in particular absorbent nonwovens products, but also of textile products such as yarns, fabrics , Crocheted or knitted.
    In the following the invention will be described by way of examples. However, the invention is expressly not limited to these examples, but includes all other embodiments based on the same inventive concept.
    Examples
    The degree of polymerization of the a (1 ^ 3) -glucan wound was determined by means of GPC in DMAc / LiCl. In the following, the weight average of the degree of polymerization (DPW) is always stated.
    Example 1:
    An aqueous glucan solution containing 9.1% a (1- »3) -glucan with a DP" of 800 and 4.5 wt% NaOH was reacted with 7.5% CS2 (weight percent calculated on fiber-forming material). The viscose thus prepared contains 9% by weight of fiber-forming material, 4.5% by weight of NaOH and 0.57% by weight of sulfur. The solution was spun by means of a spinneret into a regenerating bath containing 100 g / l of sulfuric acid, 330 g / l of sodium sulfate and 35 g / l of zinc sulfate. The spinneret had 1053 holes of 50pm diameter. To the viscose spinning solution was added 2.5% by weight of a nitrogen containing auxiliary (Leomin AC80). In order to achieve a corresponding fiber strength, a drawing is carried out in the secondary bath (92 C, 15 g / l H2SO4) of about 75%. The take-off speed is 30 m / min.
    The properties of the resulting fibers are given in Table 1: Example 2
    An aqueous glucan solution containing 11% cx (1-> 3) glucan having a DPW of 1000 and 4.8 wt% NaOH was reacted with 15% CS2 (weight percent calculated on fiber-forming material). The viscose thus prepared contains 10.8% by weight of fiber-forming material, 4.7% by weight of NaOH and 1.37% by weight of sulfur. The solution was spun by means of a spinneret into a regenerating bath containing 100 g / l of sulfuric acid, 330 g / l of sodium sulfate and 45 g / l of zinc sulfate. The spinneret had 1053 holes of 50pm diameter. To the viscose spinning solution was added 3% by weight of a nitrogen containing auxiliary. To achieve a corresponding fiber strength, a draw in the secondary bath (92 C, 15 g / l H2SO4) of about 75%. The take-off speed is 25 m / mln. The properties of the obtained fibers are given in Table 1:
    Example 3:
    An aqueous glucan solution containing 12.5% a (1- »3) -glucan having a DPW of 800 and 4.4% by weight NaOH was reacted with 12% CS2 (weight percent calculated on fiber-forming material). The viscose thus prepared contains 12.3% by weight of fiber-forming material, 4.3% by weight of NaOH and 1.24% by weight of sulfur. The solution was spun by means of a spinneret into a regenerating bath containing 90 g / l of sulfuric acid, 330 g / l of sodium sulfate and 45 g / l of zinc sulfate. The spinneret had 1053 holes of SOpm diameter. The viscose spinning solution was added to 1% of a nitrogen-containing adjuvant. To achieve a corresponding Faeerfestigkeit a stretching in the second bath (92 ° C, 15 g / l H2S04) of about 75%. The take-off speed is 27 m / min. The properties of the obtained fibers are given in Table 1:
    Lenzing AG, PL0551
    The properties of the fibers obtained are given in Table 1: TABLE 1
    FFk fiber strength conditioned FDk fiber elongation conditioned
    权利要求:
    Claims (10)
    [1]
    A process for producing a polysaccharide fiber whose fiber-forming substance is a (1-> 3) -glucan, characterized in that the process is a modified viscose process.
    [2]
    2. The method of claim 1, wherein the a (1-> 3) -glucan consists of at least 90% hexose units and at least 50% of the hexose units are linked by a (1- * 3) -glycosidic linkages.
    [3]
    A method according to the preceding claims, wherein the fiber is a staple fiber or an endless filament.
    [4]
    4. The method according to the preceding claims, wherein a maximum of 30 wt .-% CS2 are used based on fiber-forming substance, preferably less than 26 wt .-% CS2, more preferably less than 15 wt .-% CS2.
    [5]
    Polysaccharide fiber produced by a modified viscose method, characterized in that the fiber-forming substance is a (1- »3) -glucan.
    [6]
    A fiber according to claim 5, wherein the a (1- »3) -glucan consists of at least 90% hexose units and at least 50% of the hexose units are linked by a (1- * 3) -glycosidic bonds.
    [7]
    A fiber according to the preceding claims, wherein the fiber is a staple fiber or a continuous filament.
    [8]
    8. Use of the fiber according to claim 5 for the production of textile products such as yarns, fabrics, knitted or knitted fabrics.
    [9]
    9. Use of the fiber according to claim 5 for the production of nonwovens, hygiene articles, in particular tampons, panty liners and diapers and other absorbent nonwovens products and papers.
    [10]
    Use according to the preceding claims, wherein the fiber is a staple fiber or an endless filament.
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    引用文献:
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    法律状态:
    2022-02-15| MM01| Lapse because of not paying annual fees|Effective date: 20210617 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA485/2013A|AT514475B1|2013-06-17|2013-06-17|Polysaccharide fiber and process for its preparation|ATA485/2013A| AT514475B1|2013-06-17|2013-06-17|Polysaccharide fiber and process for its preparation|
    CN201480034438.XA| CN105745368B|2013-06-17|2014-06-13|Polysaccharide fiber and preparation method thereof|
    ES14747289T| ES2711901T3|2013-06-17|2014-06-13|Polysaccharide fibers and procedure for their production|
    PT14747289T| PT3011085T|2013-06-17|2014-06-13|Polysaccharide fibres and method for producing same|
    TR2019/00258T| TR201900258T4|2013-06-17|2014-06-13|Polysaccharide fiber and method for its production.|
    KR1020167000959A| KR102145519B1|2013-06-17|2014-06-13|Polysaccharide fibers and method for producing same|
    US14/899,197| US20160138195A1|2013-06-17|2014-06-13|Polysaccharide fibers and method for producing same|
    EP14747289.8A| EP3011085B1|2013-06-17|2014-06-13|Polysaccharide fibres and method for producing same|
    JP2016520185A| JP6496920B2|2013-06-17|2014-06-13|Polysaccharide fiber and method for producing the same|
    PCT/AT2014/000123| WO2014201482A1|2013-06-17|2014-06-13|Polysaccharide fibres and method for producing same|
    CN201810156936.1A| CN108251904B|2013-06-17|2014-06-13|Polysaccharide fiber and preparation method thereof|
    US15/980,140| US10876225B2|2013-06-17|2018-05-15|Polysaccharide fibers and method for producing same|
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