• 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 producing films from polysaccharides containing ~ (1- ~ 3) -glucan as a film-forming substance, and the films prepared therefrom and their use.
    公开号:AT514123A2
    申请号:T279/2013
    申请日:2013-04-10
    公开日:2014-10-15
    发明作者:
    申请人:Lenzing Akiengesellschaft；
    IPC主号:
    专利说明:

    ΗΠ: 1
    IkJ-t-r'K-cMU Ib: ^ From: LHb KHItNINtbtN / 'Wlbl fbfC! fbl bbHb
    Lenzing AG, PL0549:! :: ..: * T
    Polysaccharide film and process for its preparation
    The present invention relates to a process for producing films of polysaccharides containing a (1- * 3) -glucan as a film-forming substance and the films prepared therefrom and their use. The terms "film" and "film" are to be used as synonymous for purposes of the present invention.
    State of the art
    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 obtained from other cellulosic raw materials such. B. Cellulosic synthetic fibers is becoming increasingly important. In addition to the fibers, there are also other cellulosic shaped bodies; an example of this is the cellophane film. At present, cellulosic films are produced almost exclusively by the cellophane process and are stretched one-dimensionally.
    The generic name "lyocell-fasem" has been assigned by the BISFA (The International 20 Bureau for the Standardization of Man-made Fibors) to cellulose fibers made from solutions in an organic solvent without formation of a derivative.
    To date, however, has only one method for large-scale production of fibers of the genus Lyocell prevailed and that the amine oxide-25 method. In this process, the solvent used is a tertiary amine oxide, preferably N-methylmorpholine-N-oxide (NMMO).
    Tertiary amine oxides have long been known as alternative solvents for cellulose. From US Pat. No. 2,179,181 it is known, for example, that tertiary amine oxides are able to dissolve pulp without derivatization and that from these solutions cellulosic shaped bodies such as e.g. Fibers manufactured 1 10/04/2013 19:49 P.005 / 014 i /. L0R910 iü-HKK-dtfllJ delete: c " t From: LHta Ι-HltNIWtbtN''WlBJ. + Ό rbrd fül dbHÖ
    Lenzing AG, PL0549. US Pat. No. 3,447,939 describes cyclic amine oxides as solvents for cellulose.
    How this method is carried out, the expert is known in principle for many years from many patents and other publications. For example, EP 356 419 B1 describes the preparation of solutions and EP 5Θ4 318 B1 describes the spinning of such solutions of cellulose in hydrous tertiary amine oxides into fibers. DE 10261496 A1 describes the production of cellulosic flat films from such solutions, while WO 00/23250 A1 describes the preparation of cellulosic blown films from comparable solutions.
    Cellulose films produced by the Amlnoxld process have clear product advantages over cellophane: they have high strength in the longitudinal and transverse directions and are isotropic or anisotropic depending on their preparation. 16 DE 10035798 A1 describes the production of cellulosic
    Tubular films according to the amine oxide method. It mentions in the description (Sp. S, Z. 13) as a possible NMMO concentration 50-95% by weight, in particular 70-80% by weight. In all examples of DE 10035798 A1 - as in all other publications on this subject - in 20 concrete examples always a cellulose solution with NMMO monohydrate (87 wt .-% NMMO) used as a solvent. With cellulose as the polysaccharide other solution compositions, ie those with higher water contents are simply not processable. Usually, an aqueous NMMO solution with a higher water content is used for mashing the cellulose before dissolution, and during the dissolution process in the dissolving unit, the excess water is evaporated by applying reduced pressure. This evaporation requires a lot of energy and investment for the vacuum generation plant.
    DE 10029044 A1 also describes the production of cellulosic moldings, inter alia fibers and films, by the amine oxide process. The spinning solution may be, for example, in a film extruder or <3/10 P.006 / 014 _10 / 04/2013 19:50 Nr .: R910 lü-HI-'K-dkJIJ ItCciD From: LHb h'HltmHfcbfcN'Wlöi + 4J Cb (d. (m bb ^ b Hn: + 4b i bJ4c! 4 Dbb b. (ΊΗ
    Lenzing AG, PL0549: ············· ········· Kneaders are made with simultaneous evaporation of water. Again, the water content of the finished dope before extrusion should be 11 wt .-%, based on the total amount of the spinning solution. Again, a lot of evaporation energy is required. 5 Even recent scientific publications come to no other knowledge. Singha, International Journal of Materials Engineering 2012,2 (3): 10-16 describes in detail for the dissolution of cellulose in aqueous NMMO by means of a solubility diagram that at a water content of more than about 22% by weight in the total system cellulose not io dissolves.
    The cellulosic raw material mainly used in the amine oxide process is pulp which is obtained from wood. The cellulose molecules present in the wood, as well as in other vegetable cellulose sources such as cotton linters, straw, etc., are very long-chained, i. H. they have a high degree of polymerization. In order to obtain a cellulosic spinning solution which can be readily processed on an industrial scale, the degree of polymerization of the cellulose molecules must be adjusted in a targeted manner, whereby inevitably a portion of the polymer molecules are shortened. This is done in the usual pulp production process as well as in separate pretreatment stages 20 such as bleaching, acid treatment or irradiation by splitting the originally long cellulose molecules. In addition to the shorter chains with the desired degree of polymerization arise but also much shorter fragments such as oligomers or even monomers that remain in solution at the latest when precipitating the spinning solution in the precipitation bath, 25 do not contribute to Faserblldung and thus lost. The losses of raw materials occurring in this way can be significant and affect the economy of the entire Amnnoxld process.
    US 7,000,000 describes fibers made by spinning a solution of polysaccharides consisting essentially of hexose repeat units 3o linked via a (1-> 3) glycosidic linkages. These polysaccharides can be prepared by: u-fa rm tm wfcbfciN'WiBi rbrd rüi bb ** b b .ö'I4 * Hn: + HJ 1 D, ». _ _, __ YES · · · · · ··· · · ····
    Lenzing AG, PL0549: an aqueous solution of sucrose with GtfJ glucosyltraneferase. isolated from Streptococcus sallvarius (Simpson et al.
    Mlcrobiology, vol 41, pp 1451-1460 (1995)). "Substantially" in this context means that within the polysaccharide chains occasionally 5 defects may occur, where other binding configurations occur. These polysaccharides are to be considered as "a {1-> 3) glucan" for the purposes of the present invention. be designated.
    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 produced without loss
    Monomerbausteinen be prepared, since the polymer chains are composed of the monomer units. In contrast to the preparation of short-chain cellulose molecules, the shorter the polymer chains, the cheaper the production of a (1- »3) -glucan, since then only a small is residence tenth in the reactors is necessary.
    According to US Pat. No. 7,000,000, the a (1-> 3) -glucan is to be derivatized, preferably acetylated. The solvent is preferably an organic acid, an organic halogenated compound, a fluorinated alcohol or a mixture of such components. These solvents are expensive and difficult to regenerate.
    It has therefore been attempted to use a (1- * 3) -glucans instead of cellulose in an aminoxl process under commercial industrial process conditions for producing polysaccharide fibers. Unfortunately, under these conditions a (1-> 3) -25 glucans were not satisfactorily processed into fibers. In particular, gluing of the individual fibers occurred very frequently, making them unsalable.
    task
    The object of this prior art was to provide 30 polysaccharide films and a process for their preparation. 4 10/04/2013 19:50 l * i / l0R910 P.008 / 014 lÜ-HrK-ö31J iö: db VonlLHb KHItmWtbtN'Wlbl +4.1 fbfd fbl db4b Hn: +4,1 I D.34c; 4 bJb b.b ': i4
    Lenzing AG, PL0549, which do not have the disadvantages mentioned above. In particular, the manufacturing process should be more economically feasible compared to the preparation of cellulose films by the aminoxlide process.
    DESCRIPTION OF THE INVENTION The solution to the above-described object is a process for producing a polysaccharide film in which the finished spinning solution for extrusion comprises an amine oxide, at least 23% by weight, preferably at least 26% by weight, based on water the total amount of the spinning solution, and as polysaccharide cc (1-> 3) -glucan. This may indicate the use of a combined evaporation and dissolving unit, e.g. of a film extruder or thick layer kneader (LIST Discotherm or similar) can be dispensed with.
    The terms "movie" and "slide" should be used as synonymous for the purposes of the present invention.
    The process for producing the fiber according to the invention consists of 16 steps: 1. Preparation of a spinning solution containing aqueous amine oxide and a (1-> 3) -glucan. For this purpose, the above-mentioned methods which are generally known for the preparation of cellulose-aminoxide solutions come into consideration .: 20. 2, extruding the spinning solution through a die through an air gap under stretching into a spin amine bath containing aqueous amine oxide, washing the regenerated film to remove amine oxide and drying.
    The concentration of the a (1-> 3) -glucan substance in the spinning solution may be between 5 and 20% by weight, preferably 8 to 15% by weight.
    Preferably, the amine oxide is N-methylmorpholine-N-oxide. 6/10 10/04/2013 19:51
    No .: R910 P.009 / 014 lü-H-'K-cmJ IfcCcto From: LHta rm tNI WtbtN'Wibi + HJ Tb Cd mi db ^ b Hn: + HJ i bJMd <H bJb b. ΙΰΊΗ
    Lenzing AG, PL0549 jj jVxi'V ·: · ·· ·· ·· * · · · φ · ·
    The a (1-> 3) -glucan used in the present invention can be prepared by contacting an aqueous solution of sucrose with GtfJ glucosyltransferase isolated from Streptococcus sallvarfus (Simpson et al. Microbiology, vol 41, pp 1451-1460 (1995) )). In a preferred embodiment of the process according to 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 degree of polymerization of the io a (1-3) glucan used in the process according to the invention, expressed as weight average DPw, can be between 200 and 2000; Values between 500 and 1000 are preferred. Surprisingly, it has also been found that the process according to the invention not only allows the use of dry a (1- * 3) -glucan. The use of hydrous, in particular initial humidified a (1-> 3) -15-glucan, which has never been dried after its production, is also possible. In this process variant, only the water content of the amine oxide to be added must be adjusted accordingly. This further reduces the total energy required for the evaporation of water. This variant is of particular economic interest if the system for producing 20 of the α (1-> 3) -glucan is directly adjacent to the product solution system of the film according to the invention.
    The extrusion or shaping of the spinning composition according to the invention can be carried out by means of basically known methods; Either in a flat film method by means of a straight slit nozzle or by means of a 25 Ringschlltzdüse In a tubular film process, as z. From WO 98/42492 A2 or in a blown film process, known e.g. from WO 95/35340 A1 or WO 00/23250 A1.
    Typically, the spinning solution is drawn after extrusion. This can either be in one direction only, i. H. axially, or both in the machine direction and transversely thereto, d. H. biaxially. The 6 10/04/2013 19:51 V / 10 R910 P.010 / 014
    lh-Hh'K-dülb ifcCcib From: LHb mhItNI Wtbtr'KWlBi + ** b rbrd rkJl db ^ b b. 11 / IH ΗΓι: + HJ 1 DJD ····························· - A
    Lenzing AG, PL0549: appropriate stretching is preferably carried out in Luflspait before entering the spinning bath.
    The subject of the present invention is also a polysaccharide film, characterized in that the film-forming substance consists essentially of a (1-> 3) -glucan.
    In a preferred embodiment, 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 linkages.
    The degree of polymerization of the ίο a (1-> 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 weighted.
    In a preferred embodiment, the polysaccharide film according to the invention is oriented at least in one dimension. In a further preferred embodiment, the polysaccharide film 15 according to the invention is oriented perpendicular to one another in two dimensions. The orientation is carried out by a corresponding stretching, preferably in the air gap, before entry into the spinning bath.
    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 percentages are given below in each case as wt .-%, unless otherwise stated. 25 Example 1
    The a (1- »3) -glucan is first suspended in 50% aqueous NMMO and then with 78% NMMO to give a spinning solution containing 10% α-glucan, 7 P.011 / 014 10/04/2013 19:52 . /. 10 R910
    lU-HI-'K-cildib IfcCbf From ^ Hta KHI fcN I WfcbtN · 'W1B1 Cb fei fbl dbHB b. Hn: + ^ J 1 DJHdH DJD ································································································· ····
    Lenzing AG, PL0649 ·. ··% ··.: ..: 29.9% water, 60% NMMO and 0.1% stabilizer.
    The ropyl gallate was stirred into 2155 g of 5% aqueous NMMO, then 567 ga (1-> 3) -glucan was slowly collected and stirred for 15 min with an Ultraturrax® T50, to this suspension 2559 g of 78% saturated aqueous NMMO were added Drained 106 g of water.
    The spinning solution was extruded at 100 "C through a 60 mm film die with a 350 μm gap at a rate of 26.9 g / min dope, a 1: 2 draft applied, coagulated in a coagulation bath, washed free of water with NMMO, dried and wound up. The film produced had the following properties: film thickness: 11 μm, longitudinal strength: 87 MPa, transverse strength: 41 MPa, longitudinal elongation at break: 5.2%.
    Example 2 (Comparative Example)
    Pulp is reacted with 78% aqueous NMMO to give a spinning solution containing 10% 15% cellulose, 11.9% water, 78% NMMO and 0.1% propyl gallate stabilizer.
    The GPE was stirred into 5000 g of 78% aqueous NMMO, then 532 g of cellulose were mixed and this suspension was then removed under vacuum 532 g of water. The spinning solution was extruded at 100 eC through a 60 mm long film die with a gap of 350 μm, a distortion of 1: 2 applied, the shaped body coagulated in a precipitation bath, washed with water, NMMO-free, dried and wound up.
    The film produced had the following properties: film thickness: 11 μm, 25 longitudinal strength: 173 MPa, transverse strength 84 MPa, longitudinal elongation at break: 7.1%. 8 10/04/2013 19:52 9/10 .012 / 014
    No .: R910 p
    权利要求:
    Claims (8)
    [1]
    b. ui 'in W-HW-tBij Itüclf by: LHb HHIfcN'lWtbtN'WitU + ^ J fbfji (Ul db'HÖ · ** · *** *** * * &quot; · · ** «· **» * • · » 1. A process for the preparation of a polysaccharide film, characterized in that the finished spinning solution for the extrusion s amine oxide, at least 23 wt .-% water, based on the total amount of the spinning solution, and as polysaccharide a (1 - * 3) -Glucan contains.
    [2]
    2. The method of claim 1, wherein the amine oxide is N-methylmorpholine N-oxide. in
    [3]
    3. The method of claim 1, wherein the a (l-> 3) -glucan consists of at least 90% hexose units and at least 50% of the hexose units are linked by tt (1-> 3) glycosidic bonds ,
    [4]
    4. The method according to claim 1, wherein the extrusion takes place by means of a straight slot nozzle or a Ringschlitzdüse 15
    [5]
    5. Process according to claim 1, wherein the spinning solution is drawn after extrusion,
    [6]
    6. Polysaccharld film, characterized in that the fllmbildende substance consists essentially of a (1 ~ * 3) glucan
    [7]
    A polysaccharide film according to claim 6, wherein the a (1 * 3) -glucan is at least 90% hexose-containing and at least 50% of the hexose units are a {1-> 3) -fllycoside bonds are linked.
    [8]
    The polysaccharide film of claim 6 wherein the film is oriented at least in one dimension. 10/10 P.013 / 014 10/04/2013 19:52 No .: R910
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2179181A|1936-04-21|1939-11-07|Soc Of Chemical Ind|Cellulose solutions and process of making same|
    US3447939A|1966-09-02|1969-06-03|Eastman Kodak Co|Compounds dissolved in cyclic amine oxides|
    JPS6054322B2|1977-09-30|1985-11-29|Hayashibara Seibutsu Kagaku Kenkyusho Kk|
    US4246221A|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|
    US4562020A|1982-12-11|1985-12-31|Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo|Process for producing self-supporting glucan film|
    JPS59111817A|1982-12-11|1984-06-28|Hayashibara Biochem Lab Inc|Manufacture of pullulan self-supporting film|
    JPH0475214B2|1984-03-30|1992-11-30|
    CN1036967A|1988-02-04|1989-11-08|武田药品工业株式会社|Edible film|
    JPH01289457A|1988-02-04|1989-11-21|Takeda Chem Ind Ltd|Edible film|
    AT392972B|1988-08-16|1991-07-25|Chemiefaser Lenzing Ag|METHOD FOR PRODUCING SOLUTIONS OF CELLULOSE AND DEVICE FOR IMPLEMENTING THE METHOD|
    GB9103297D0|1991-02-15|1991-04-03|Courtaulds Plc|Fibre production method|
    ATA53792A|1992-03-17|1995-02-15|Chemiefaser Lenzing Ag|METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE|
    JPH06298999A|1993-02-16|1994-10-25|Mitsubishi Rayon Co Ltd|Solution for casting cellulose and method for casting using the same|
    DE4421482C2|1994-06-20|1997-04-03|Fraunhofer Ges Forschung|Process for producing oriented cellulose films and the films produced by this process and their use|
    GB9412500D0|1994-06-22|1994-08-10|Courtaulds Fibres Holdings Ltd|Fibre manufacture|
    GB9412501D0|1994-06-22|1994-08-10|Courtaulds Fibres Holdings Ltd|Manufacture of fibre|
    AT403296B|1995-08-11|1997-12-29|Chemiefaser Lenzing Ag|METHOD FOR PRODUCING A CELLULOSE MOLDED BODY|
    AT404595B|1997-03-21|1998-12-28|Chemiefaser Lenzing Ag|DEVICE AND METHOD FOR PRODUCING CELLULOSIC TUBE FILMS|
    GB9823086D0|1998-10-21|1998-12-16|Devro Plc|Film manufacturing method|
    DE60009886T2|1999-01-25|2005-03-31|E.I. Du Pont De Nemours And Co., Wilmington|polysaccharide|
    DE10029044A1|2000-06-13|2002-01-03|Lueder Gerking|Process and device for the production of threads, fibers, foils or molded articles made of cellulose|
    DE10035798A1|2000-07-22|2002-01-31|Kalle Nalo Gmbh & Co Kg|Method and device for producing a seamless film tube and seamless film tube|
    DE10261496A1|2002-12-23|2004-07-01|Kalle Gmbh & Co. Kg|Edible flat foil|
    CN101120776B|2007-06-23|2011-04-06|西藏天麦力健康品有限公司|Method for extracting beta-glucan from cereal bran using membrane separation technology|
    US20090165969A1|2007-12-31|2009-07-02|Weyerhaeuser Co.|Enzymatic treatment of pulp for lyocell manufacture|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA279/2013A|AT514123B1|2013-04-10|2013-04-10|Polysaccharide film and process for its preparation|ATA279/2013A| AT514123B1|2013-04-10|2013-04-10|Polysaccharide film and process for its preparation|
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    US14/782,168| US9701800B2|2013-04-10|2014-04-10|Polysaccharide film and method for the production thereof|
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    JP2016506722A| JP6488482B2|2013-04-10|2014-04-10|Polysaccharide film and method for producing the polysaccharide film|
    CN201480020399.8A| CN105121523B|2013-04-10|2014-04-10|Polysaccharide films and methods of making the same|
    US15/604,177| US20170283568A1|2013-04-10|2017-05-24|Polysaccharide film and method for the production thereof|
    US16/121,149| US20180371193A1|2013-04-10|2018-09-04|Polysaccharide film and method for the production thereof|
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