US 2016.0053406A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0053406 A1 Dirnberger et al. (43) Pub. Date: Feb. 25, 2016

(54) POLYSACCHARIDE FIBERS AND METHOD (30) Foreign Application Priority Data FOR THE PRODUCTION THEREOF Apr. 5, 2013 (AT) ...... A257-2013 (71) Applicant: LENZING AG, Lenzing (AT) Publication Classification (72) Inventors: Franz Dirnberger, A-4860 Lenzing (AT); Sigrid Redlinger, A-4860 Lenzing (51) Int. C. (AT); Christoph Schrempf, A-4701 Bad DOIF 2/00 (2006.01) Schallerbach (AT); Hartmut Rif, D04H 3/03 (2006.01) A-4861 Schörfling (AT); Heinrich D04H L/4258 (2006.01) Firgo, A-4840 Vöcklabruck (AT); Gert D2 IIH 3/08 (2006.01) Kroner, A-4863 Seewalchen (AT) (52) U.S. C. CPC ...... D0IF 2/00 (2013.01); D2IH 13/08 (73) Assignee: LENZING AG, A-4860 Lenzing (AT) (2013.01): D04EI 3/013 (2013.01): D04EI (21) Appl. No.: 14/782,148 I/4258 (2013.01) (22) PCT Fled: Apr. 4, 2014 (57) ABSTRACT The present invention relates to a method for the production (86) PCT NO.: PCT/AT2O14/OOOOT2 of polysaccharide fibers which, as a fiber-forming Substance, S371 (c)(1), comprise a mixture of cellulose and C.(1->3)-glucan, as well (2) Date: Oct. 2, 2015 as to the fibers made thereof and to their use. US 2016/0053406 A1 Feb. 25, 2016

POLYSACCHARIDE FIBERS AND METHOD consist of repeating hexose units linked via C.(1->3)-glyco FOR THE PRODUCTION THEREOF sidic bonds. These polysaccharides can be produced by bring ing an aqueous Solution of Saccharose into contact with Gitf BACKGROUND OF THE INVENTION glucosyltransferase, isolated from Streptococcus salivarius 0001 1. Field of the Invention (Simpson et al. Microbiology, Vol. 41, pp 1451-1460 (1995)). 0002 The present invention relates to a method for the As used in this context, “substantially’ means that within the production of polysaccharide fibers which, as a fiber-forming polysaccharide chains there may exist occasional defective Substance, comprise a mixture of cellulose and C.(1->3)-glu locations where other bond configurations may occur. For the can, as well as to the fibers made thereof and to their use. purposes of the present invention, these polysaccharides are 0003 2. Description of Related Art referred to as “C.(1->3)-glucan'. 0004 Polysaccharides are becoming increasingly impor (0011 U.S. Pat. No. 7,000,000 first discloses possibilities tant, as they are materials that can be obtained from renewable for the enzymatic production of C.(1->3)-glucan from raw materials. One of the most frequently occurring polysac monosaccharides. In this way, relatively short-chained charides is cellulose. Cotton fibers, which consist almost polysaccharides can be produced without the loss of mono exclusively of cellulose, are an example of the significance of mer units, as the polymer chains are built from the monomer polysaccharides. However, also materials obtained from units. Contrary to the production of short-chained cellulose other cellulosic raw materials, e.g., cellulosic synthetic fibers, molecules, the production of C.(1->3)-glucan keeps getting are continuing to gain in importance. less expensive the shorter the polymer chains are, as in that 0005. The generic name “lyocell fibers” was assigned by case the required residence time in the reactors will be short. BISFA (the International Bureau for the Standardization of (0012. According to U.S. Pat. No. 7,000,000, the O.(1->3)- Man-made Fibers) to cellulose fibers produced from solu glucan is to be derivatized, preferably acetylated. Preferably, tions in an organic solvent without the formation of a deriva the solvent is an organic acid, an organic halogen compound, tive. a fluorinated alcohol, or a mixture of such components. These 0006. However, to date, only one method for the large Solvents are costly and complex to regenerate. scale production offibers of the lyocell type has gained accep 0013 Therefore, attempts were made to use O(1->3)-glu tance, namely, the amine-oxide process. In this method, a cans instead of cellulose in an amine oxide process under tertiary amine oxide, preferably N-methylmorpholine-N-ox commercially applied large-scale process conditions. Unfor ide (NMMO), is used as the solvent. tunately, it was found that under these conditions C(1->3)- 0007 Tertiary amine oxides have long been known as glucans could not be processed satisfactorily into fibers. alternative solvents for cellulose. From U.S. Pat. No. 2,179, 181, it is known, for example, that tertiary amine oxides are Object capable of dissolving pulp without derivatization and that 0014. In view of such prior art, the object was to provide a cellulosic shaped bodies, e.g., fibers, can be made from these polysaccharide fiber and a method for its production, which solutions. U.S. Pat. No. 3,447,939 describes cyclic amine did not include the above mentioned disadvantages. The oxides as solvents for cellulose. polysaccharide raw material was to be inexpensive to manu 0008. From numerous patent specifications and other pub facture, and the processing method was to be known and lications, it has been known to those skilled in the art for quite cost-effective as well as executable on existing facilities. some time how this method is carried out. EP356 419 B1, for example, describes how the solution is prepared, and EP 584 DESCRIPTION OF THE INVENTION 318 B1 describes how such solutions of cellulose in water containing tertiary amine oxides are spun. 0015 The above described object is solved by a method 0009. The main cellulosic raw material used in the amine for the production of a lyocell fiber, wherein the spinning oxide process is pulp obtained from wood. The cellulose Solution comprises aqueous amine oxide and, as a fiber-form molecules existing in wood and also in other plant-based ing Substance, a mixture of cellulose and C.(1->3)-glucan. For Sources of cellulose Such as cotton linters, straw, etc. form the purposes of the present invention, such a fibershall also be very long chains, i.e., they exhibit a high degree of polymer referred to as a lyocell fiber even though it contains yet ization. In order to obtain a cellulose spinning Solution that is another fiber-forming polysaccharide in addition to cellulose, well Suited for large-scale processing, it is necessary to spe namely, the C.(1->3)-glucan. cifically adjust the degree of polymerization of the cellulose 0016 For the purposes of the present invention, the term molecules, which inevitably causes part of the polymer mol “fiber' shall comprise both staple fibers having a defined ecules to be shortened. This takes place in the usual pulp Staple length and continuous filaments. All principles of the preparation methods and also in separate pretreatment steps invention that are described hereinafter apply, in principle, to Such as bleaching, acid treatment, or irradiation by splitting both staple fibers and continuous filaments. the originally long cellulose molecules. In addition to the (0017. The single fibertiter of the inventive fibers can be shorter chains having the desired degree of polymerization, between 0.1 and 10 dtex. Preferably, it is between 0.5 and 6.5 this also creates significantly shorter fragments such as oli dtex, and more preferably between 0.9 and 3.0 dtex. In the gomers or even monomers which remain in Solution after the case of staple fibers, the staple length is usually between 0.5 precipitation of the spinning Solution in the precipitation bath, and 120 mm, preferably between 20 and 70 mm, and more do not contribute to the formation of the fibers, and thus are preferably between 35 and 60 mm. In the case of continuous lost. The quantities of raw material lost in this process can be filaments, the number of individual filaments in the filament substantial and can affect the cost-effectiveness of the entire yarn is between 50 and 10,000, preferably between 50 and amine oxide process. 3,000. 0010 U.S. Pat. No. 7,000,000 describes fibers obtained by 0018. The C.(1->3)-glucan can be prepared by bringing an spinning a solution of polysaccharides which Substantially aqueous solution of saccharose into contact with Gitf gluco US 2016/0053406 A1 Feb. 25, 2016

Syltransferase isolated from Streptococcus salivarius (Simp by weight of C.(1->3)-glucan. More preferably, the content of son et al. Microbiology, Vol. 41, pp 1451-1460 (1995)). C.(1->3)-glucan is between 5 and 30% by weight and in 0019. In a preferred embodiment of the method according particular preferred a content of the C.(1->3)-glucan between to the invention, at least 90% of the C.(1->3)-glucan are hex 10 and 20% by weight. Below 5%, the economic benefit of the ose units and at least 50% of the hexose units are linked via added C.(1->3)-glucan is too low for typical types of use: C.(1->3)-glycosidic bonds. above 30%, fibers may to an increasing extent be caused to 0020. The method for the preparation of the inventive fiber Stick together. However, in certain cases and/or for certain consists of the following steps: types of use of the inventive fibers, both limits may be 0021 1. Preparation of a spinning Solution comprising exceeded; the scope of the present invention expressly also aqueous amine oxide and, as a fiber-forming Substance, a includes fibers having an O(1->3)-glucan content between 1 mixture of cellulose and C.(1->3)-glucan, according to one of and 5% by weight and between 30 and 99% by weight, the two following methods: respectively. 0022 a. The O.(1->3)-glucan can be added in the form 0031. In a preferred embodiment, at least 90% of the of a solution in aqueous amine oxide to the cellulose C.(1->3)-glucan of the inventive lyocell fiber are hexose units Solution prepared according to known methods. and at least 50% of the hexose units are linked via C.(1->3)- 0023 b. The C.(1->3)-glucan can be admixed to the pulp glycosidic bonds. already before the bringing into contact with aqueous 0032. The use of the inventive fibers for the production of amine oxide. textile products such as yarns, woven fabrics, or knitted fab 0024 2. Extruding the spinning Solution through a die, via rics is also subject-matter of the present invention. an air gap, and into a spinning bath containing aqueous amine 0033 Surprisingly, it was discovered that the inventive oxide, washing the regenerated fiber for removal of amine fibers are very well suited—even better than commercially oxide, and drying. available lyocell fibers without C.(1->3)-glucan to to pro 0025. The concentration of the fiber-forming substance in duce textiles with peach-skin-effect by treatment methods the spinning solution can be between 5 and 20% by weight, generally known to those skilled in the art from the processing preferably between 8 and 15% by weight, and more prefer of lyocell fibers, for example, from Schmidt M., Lenzinger ably between 10 and 14% by weight. Berichte 9 (1994), pp. 95-97. This suitability is due to the high 0026. The fiber-forming substance in the method accord fibrillation capability of the fibres according to the invention. ing to the invention may comprise between 1 and 99% by 0034. In order to remove fibrils, which appear in various weight of O.(1->3)-glucan. Preferred is a content of the treatment steps of the textile chain, from the fiber surface, C.(1->3)-glucan between 5 and 30% by weight and in particu often a so-called mechanical polishing step or also an enzy lar preferred a content of the O.(1->3)-glucan between 10 and matic polishing step ('bio-polishing’; see for example 20% by weight. Below 5%, the economic benefit of the added Schmidt M., Lenzinger Berichte 9 (1994), pp. 95-97) is C.(1->3)-glucan is too low for typical types of use of the employed. The inventive fibers are generally very well suited inventive fibers; above 30%, fibers may to an increasing for use in a production method for textiles wherein such a step extent be caused to Stick together in the spinning process. of mechanical or enzymatic polishing is employed. Hence, However, under certain conditions and/or for certain types of such use of the inventive fibers is also subject-matter of the use of the inventive fibers, both limits may be exceeded; the present invention. Dyed fabrics (textiles) made out of the Scope of the present invention expressly also includes fibers fibers according to the invention further show an improved having an O.(1->3)-glucan content between 1 and 5% by white-abrasion behavior and after washing show less greying weight and between 30 and 99% by weight, respectively. For and less pilling. example, in the event of a low perforation density of the 0035. The inventive fibers are particularly well suited for spinneret, i.e., a large spacing between the individual fila all products that can be produced in the dry or wet laying ments in the air gap, the risk of Sticking together is signifi processes. This includes for example all paper applications cantly lower. and nonwoven fabrics, the so-called nonwoven products. 0027. The degree of polymerization of the C.(1->3) glucan Fibrillation can also be induced by strong mechanical impact employed in the method according to the invention, expressed on the fibers according to the invention when they are dis as weight average DP, can be between 200 and 2000; values persed in a liquid like e.g. water. Suitable machines are e.g. between 500 and 1000 are preferred. Preferably, the amine refiners, which are well-known in paper industry. Compared oxide is N-methylmorpholine-N-oxide. to Lyocell fibers consisting of 100% cellulose the fibers 0028. In the process according to the invention are also the according to the invention are forming fibrils of larger diam following process parameters preferred: Extrusion tempera eter which results in a particular good Suitability of Such ture of the spinning solution at the dies between 90 and 135° fibrillated fibers for the nonwovens applications described C., preferably between 120 and 130° C.; output from the above. spinneret between 0.01 and 0.2 g/perforation*min, depend 0036 Furthermore, the inventive fibers are very well ing on the target single fibertiter, preferably between 0.02 and Suited for all types of use where they are used in a greatly 0.1 g/perforation*min; length of the air gap between 7 and 70 shortened form for the surface treatment of other shaped mm, preferably between 20 and 35 mm; concentration of bodies or sheet-like structures. This includes surface coatings NMMO in the aqueous spinning bath between 0 and 35% by and flockings, among others. For this purpose, the inventive weight, preferably between 0 and 25% by weight. fibers are produced in lengths from 10 to approx. 500 um, for 0029. A lyocell fiber that comprises cellulose and example, by cutting or grinding in a cutting mill. C.(1->3)-glucan is also subject-matter of the present inven 0037. The invention will be described below with refer tion. ence to examples. However, the invention is not expressly 0030. According to the invention, the fiber-forming sub limited to these examples but also includes all other embodi stance of the inventive fiber can comprise between 1 and 99% ments that are based on the same inventive concept. US 2016/0053406 A1 Feb. 25, 2016

EXAMPLES 2. The method according to claim 1, wherein the fiber forming substance comprises between 1 and 99% by weight 0038. The degree of polymerization of the C.(1->3)-glu of C.(1->3)-glucan. cans was determined by means of GPC in DMAc/LiCl. Sub 3. The method according to claim 1, wherein the amine sequently, it is always the weight average of the degree of oxide is N-methylmorpholine-N-oxide. polymerization (DP) that is specified. 4. The method according to claim 1, wherein at least 90% 0039 Spinning solutions each containing 13% by weight of the C.(1->3)-glucan are hexose units and at least 50% of the of solids (cellulose+C.(1->3)-glucan) / 77% by weight of hexose units are linked via O.(1->3)-glycosidic bonds. N-methylmorpholine-N-oxide/10% by weight of water were 5. The method according to claim 1, wherein the fiber is selected from the group consisting of a staple fiber and a spun at 130°C. from a spinneretvia an air gap (length 30 mm) continuous filament. in water. In the air gap, dry air (i.e., humidity=0% rh.) was 6. A lyocell fiber comprising cellulose and C.(1->3)-glu used for blowing at room temperature. The output from the Ca. spinneret was 0.05 g/perforation*min. The cellulosic raw 7. The lyocell fiber according to claim 6, wherein the material used was Saiccor pulp having a SCAN viscosity of fiber-forming substance comprises between 1 and 99% by 450 ml/g. C.(1->3)-glucans having two different degrees of weight of C.(1->3)-glucan. polymerization were used. The glucan quantities are related 8. The lyocell fiber according to claim 6, wherein at least to the proportion of C.(1->3)-glucan in the fiber-forming sub 90% of the C.(1->3)-glucan are hexose units and at least 50% Stance. of the hexose units are linked via C.(1->3)-glycosidic bonds. 0040. The properties of the fibers obtained are listed in 9. The fiber according to claim 6, wherein the fiber is Table 1: selected from the group consisting of a staple fiber and a continuous filament. TABLE 1. 10. A textile product comprising the fiber according to claim 6. quantity FFk FF 11. The textile product according to claim 10, wherein the of glucan tilter cN. FDk cN. FDn product has peach-skin effect. example additive % dtex tex % tex % 12. A process for making textiles which comprise the fiber 1 Ole 1.58 34.2 10.1 27.0 11.9 according to claim 6, the process comprising a step of reference mechanical or enzymatic polishing is employed. example 13. A nonwoven product comprising the fiber according to 2 glucan 5 1.58 34.5 11.2 26.4 14.7 claim 6. DP1000 3 glucan 10 1.59 31.8 10.7 20.9 14.7 14. A paper product comprising the fiber according to DP1000 claim 6. 4 glucan 2O 1.61. 27.4 9.2 16.3 9.2 15. The textile product according to claim 10, wherein the DP1000 5 glucan 2O 1.6S 25.4 9.6 186 10.7 fiber is selected from the group consisting of a staple fiberand DP,800 a continuous filament. 16. The method according to claim 2, wherein the fiber Therein means: forming substance comprises between 5 and 30% by weight FFk fiber strength, conditioned FDk fiber elongation, conditioned of C.(1->3)-glucan. FFn fiber strength, wet 17. The lyocell fiber according to claim 7, wherein the FDn fiber elongation, wet fiber-forming substance comprises between 5 and 30% by weight of C.(1->3)-glucan. 1. A method for the production of a lyocell fiber, wherein 18. The textile product according to claim 10, wherein the the spinning solution contains aqueous amine oxide and, as a product is selected from the group consisting of yarns, woven fiber-forming substance, a mixture of cellulose and C.(1->3)- fabrics, and knitted fabrics. glucan. k k k k k