Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
  • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
  • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
  • A61L15/28—Polysaccharides or their derivatives
• • 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
  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
  • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
  • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
• • 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
  • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/04—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres having existing or potential cohesive properties, e.g. natural fibres, prestretched or fibrillated artificial fibres
  • D04H1/28—Regenerated cellulose series
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/425—Cellulose series
  • D04H1/4258—Regenerated cellulose series
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
  • D04H3/013—Regenerated cellulose series

Definitions

• the present invention relates to a novel, highly absorbent
• Polysaccharide fiber its preparation and properties and their
• Nonwovens are non-woven fabrics made of textile fibers, and the lengths of the fibers used are determined to be between nonwoven spunbonded nonwovens which can be obtained by directly depositing the fibers after the spinning process, and
• Spunfibre webs of fibers with defined cutting length differentiated. These are either dry way, for example by pressing card slivers, as is the case with tampon manufacture, or by wet methods, for. B. similar to the papermaking with subsequent solidification produced.
• natural fibers such as wool or
• Cotton also finds chemical fibers, including polypropylene or polyester use. In the field of absorbent nonwovens products, predominantly cellulosic fibers are used because of their extremely hydrophilic character. Their high absorption capacity is based on the ability of cellulose to form strong hydrogen bonds with water molecules. In addition, these fibers are characterized by complete biodegradability. In addition to cotton and pulp, it is above all manmade cellulose fibers, so-called regenerated cellulose fibers, such as viscose or lyocell fibers, which are used as natural cellulose fibers
• Xanthogenate are called, since in them always polysaccharides are reacted with CS2 to the corresponding xanthogenates.
• Xanthate method for the production of cellulose fibers are the
• absorbent nonwovens products include wipes and wipes, sanitary products such as tampons or sanitary napkins, sterile drapes or medical wound care products, and cosmetic products such as cleansing pads or napkins.
• sanitary products such as tampons or sanitary napkins
• sterile drapes or medical wound care products and cosmetic products such as cleansing pads or napkins.
• cosmetic products such as cleansing pads or napkins. The requirements for these products vary depending on the product
• Nonwovens are concerned with the uptake, transport, distribution, release and / or retention of liquids under their respective conditions of use.
• numerous test methods have been established, including the water retention capacity according to DIN 53814, the sinking time, the water holding capacity, the suction capacity and suction speed according to Demand Wettability test, the
• Thickness swelling and water vapor absorption are important requirements for the fibers used in the field of absorbent nonwovens.
• the water retention capacity and the water retention capacity are used.
• the water retention capacity also known as the swelling value, represents the amount of water retained after wetting and defined centrifuging in percent, based on the dry starting weight of the fibers. It is mainly due to the supermolecular fiber structure and the
• the water holding capacity corresponds to the amount of water that is held by a fiber swab after immersion in water and defined dripping. These are mainly water trapped in the capillary spaces between the fibers. Key influencing factors concern the titer, the curling, the cross-sectional shape and the equipment of the fibers.
• Cellulose regenerated fibers with high absorbency can be divided into three groups:
• Hollow fibers, collapsed hollow fiber structures or fibers with multi-limbed, so-called multilobal cross-sections are characterized by particular absorption power.
• Hollow fibers can be prepared for example by the addition of sodium carbonate to viscose. Upon contact with the acidic spinning bath, carbon dioxide is released, which swells the fibers and results in the formation of the hollow structure.
• US4129679 (A) describes fibers made by such a process. A special feature of this method is that the inflated fibers collapse and thus form multi-limbed cross-sections.
• Other ways to produce fibers with multilobal cross-sectional shape the spinning of the cellulose solution by spinnerets whose openings three or more legs, preferably with a
• Length / width ratio of the legs of 2: 1 or more have. Such a method is described in WO8901062 (A1).
• High crimp fibers also have pronounced hydrophilic properties. Influencing the rippling of
• Viscose fibers for example, by using alternative,
• curling modifier and / or low modifier concentrations which, as described in ⁇ 0 ⁇ 49710 (A1), may possibly be reduced to zero, in combination with modified viscose compositions and spinning conditions possible.
• a disadvantage of these cross-section-modified fibers is the significantly reduced processability in the further processing steps (eg carding).
• hydrophilic polymers such as carboxymethylcellulose (US4289824 (A)), alginic acid or its salts (AT402828 (B)), guar gum (W09855673 (A1)) or copolymers of acrylic and methacrylic acid to the cellulose solution, the water absorption capacity of
• Reactions that are carried out directly on the cellulose regenerated fibers or the fiber-forming cellulose increase. Examples are the graft copolymerization of the cellulose with acrylic acid or the
• water retention capacity is the most important parameter in the field of absorbent nonwovens because, in contrast to the water holding capacity, it more closely corresponds to practical conditions. So it is not enough that a tampon or a
• Wound dressing only absorbs body fluid. For the usability is It is essential that the absorbed liquid is maintained even when exposed to external forces within the fiber material.
• Substantial surface properties such as the cross-sectional shape and the crimp of the fibers, and therefore only cause an increase in water absorption capacity.
• the water retention capacity is not or hardly influenced.
• Absorbing substances can change the water retention capacity of the fibers, but the introduction of non-cellulosic groups is not without problems. Thus, under certain circumstances, the biodegradability may no longer be given in full. This is the case, for example, in the incorporation of copolymers of acrylic and methacrylic acid. Another disadvantage is the risk of exceeding maximum allowable extract or ash contents. Thus, in the ashing of cellulose fibers containing sodium carboxylate groups, a certain amount of sodium carbonate is always formed. The introduction of charged groups makes compliance with prescribed pH tolerance ranges difficult.
• nonwovens containing sodium carboxylate groups often have a pH which is clearly in the alkaline range.
• sporadia may occur occasionally within the polysaccharide chains where other binding configurations occur.
• These polysaccharides should be termed "a (1- »3) -glucan".
• the a (1 ⁇ 3) -glucan is to be derivatized, preferably acetylated.
• the solvent is preferably an organic acid, an organic halogen compound, a fluorinated alcohol or a
• Process steps is too high, used high-absorbing substances are too expensive or rejected from a physiological and / or toxicological point of view, the desired absorption properties are not achieved or certain minimum mechanical standards, for example, at high required levels of filling can not be achieved.
• the object was compared to this prior art to provide a fiber and a process for their preparation that does not require cross-sectional and chemical modification, and is completely harmless from a physiological and / or toxicological point of view, but still has a significantly increased Water retention has.
• the solution of the above-described object is a method for producing a superabsorbent polysaccharide fiber according to one
• the fiber-forming substance contains a mixture of cellulose and a (1 - »3) -glucan.
• this is achieved by the cellulose xanthate solution containing a (1-> 3) -glucan-containing
• Such a polysaccharide Fiber is also to be referred to as viscose or modal fiber for the purposes of the present invention, although it contains, in addition to cellulose, another fiber-forming polysaccharide, namely a (1-3) glucan.
• fiber is intended to include both staple fibers of defined cut length and continuous filaments All of the principles of the invention described below apply in principle to both staple fibers and continuous filaments.
• the individual 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.
• 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.
• the number of individual filaments in the filament yarn is between 50 and 10,000, preferably between 50 and 3,000.
• the a (1- »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). , US 7,000,000).
• GtfJ glucosyltransferase
• the (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.
• the process for producing the fiber according to the invention consists in principle of the following essential steps:
• the total concentration of the fiber-forming substance in the spinning solution may be between 4 and 15 wt .-%, preferably 5.5 to 12 wt .-%.
• the fiber-forming substance in the process according to the invention may contain between 1 and 99% by weight of a (1- »3) -glucan. Particularly preferred is a proportion of a (1 - »3) -glucan between 5 and 45 wt .-%. Below 5%, the effect of the a (1 - 3) glucan additive is too low for conventional applications of the fibers according to the invention; Above 45%, competitive reactions around the CS2 in the spinning solutions become too great and the spinnability of the solution drops significantly. However, both limits can be exceeded under special conditions or for special applications of the fibers according to the invention; also fibers with a cx (1 - 3) -glucan content. between 1 and 5% by weight and between 45 and 99% by weight are expressly included within the scope of the present invention.
• the remaining portion of the fiber-forming substance preferably consists essentially of cellulose.
• "Substantially” in this context means that small amounts of other substances can be contained, which are mainly derived from the cellulosic raw material, generally the pulp, such as hemicellulose and other saccharides, lignin residues or the like contained in commercially available viscose and modal fibers.
• the degree of polymerization of the (1-3) glucan used in the process according to the invention may be between 200 and 2000; preferred are values between 500 and 1000.
• the present invention is also a highly absorbent
• Polysaccharide fiber produced by a xanthate method containing cellulose and (1-3) -glucan contains between 1 and 99% by weight, preferably between 5 and 45% by weight of a (1 ⁇ 3) -glucan
• the a (1- »3) -glucan of the polysaccharide fiber according to the invention consists of at least 90% hexose units and at least 50% of the hexose units are linked by (1 ⁇ 3) -glycosidic bonds.
• the fiber according to the invention has an extraordinarily high water retention capacity of at least 90%. Depending on the composition and method of preparation, the water retention capacity is even greater than 100%.
• the fibers according to the invention for the production of a wide variety of 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 fabrics.
• the degree of polymerization of the cx (1 ⁇ 3) -glucans was determined by GPC in
• the viscose thus prepared contained 8.90% by weight of fiber-forming material, 5.20% by weight of NaOH, and 2.4% by weight of sulfur (for 100% cellulose as the fiber-forming material) having a ripeness index of 14 Hottenroth and a Falling ball viscosity of 80 seconds (determined according to the Zellcheming leaflet III / 5 / E). Viscose solutions were prepared with 10 and 25% a (1 ⁇ 3) glucan.
• the quantities of glucan refer to the proportion of a (1- »3) -glucan on the
• Viscose spinning solution was added to 0.5% by weight of a nitrogen-containing adjuvant.
• a draw in the secondary bath (92 C, 15 g / l H2SO4) of about 75%.
• Example 2 The properties of the resulting fibers are given in Table 1:
• Example 2 The properties of the resulting fibers are given in Table 1:
• Falling ball viscosity of 75 seconds was spun by means of a spinneret into a regeneration bath containing 100 g / l sulfuric acid, 310 g / l sodium sulfate and 15 g / l zinc sulfate.
• the spinneret had 1053 holes of 50pm diameter.
• To the viscose spinning solution was added 0.5% by weight of a nitrogen-containing auxiliary.
• a draw in the secondary bath (92 C, 15 g / l H2SO4) of about 75%.
• the viscose solution was pre-spun using a
• glucan-NaOH solution 5 wt .-% NaOH, 8 wt .-% a (1 -> 3) -glucan added
• glucan refer to the proportion of ⁇ (1 ⁇ 3) glucan in the total fiber-forming substance of the polysaccharide fibers.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Textile Engineering (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Biochemistry (AREA)
• Molecular Biology (AREA)
• Analytical Chemistry (AREA)
• Veterinary Medicine (AREA)
• Epidemiology (AREA)
• Animal Behavior & Ethology (AREA)
• Public Health (AREA)
• Hematology (AREA)
• Artificial Filaments (AREA)
• Absorbent Articles And Supports Therefor (AREA)
• Materials For Medical Uses (AREA)
• Knitting Of Fabric (AREA)
• Woven Fabrics (AREA)
• Nonwoven Fabrics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Cited By (12)

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• 2013
  • 2013-06-17 AT ATA483/2013A patent/AT514468A1/de not_active Application Discontinuation
• 2014
  • 2014-06-13 PL PL14747290T patent/PL3011090T3/pl unknown
  • 2014-06-13 JP JP2016520187A patent/JP6412118B2/ja not_active Expired - Fee Related
  • 2014-06-13 KR KR1020167001024A patent/KR102145575B1/ko not_active Expired - Fee Related
  • 2014-06-13 US US14/899,214 patent/US10220111B2/en active Active
  • 2014-06-13 WO PCT/AT2014/000125 patent/WO2014201484A1/de not_active Ceased
  • 2014-06-13 CN CN201480034437.5A patent/CN105705690B/zh active Active
  • 2014-06-13 ES ES14747290.6T patent/ES2623284T3/es active Active
  • 2014-06-13 EP EP14747290.6A patent/EP3011090B1/de active Active

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