Endless Core-Sheath Fibers on the Basis of Hyaluronan or C11-C18 Acylated Derivatives Thereof, Method of Preparation and Use Thereof, Staple Fibers, Yarn and Textiles Made of These Fibers and Use Thereof

Abstract

The invention relates to two-component biodegradable core-sheath fibers comprising a combination of native and C 11 -C 18 acylated hyaluronan or C 11 -C 18 acylated hyaluronans. It further relates to method of preparation and use thereof, especially for controlled release of the active agent. Fibers may be further processed into the form of staple fibers, yarn, braided, woven, knitted and non-woven textiles.

1 . Endless fiber of the type core-sheath on the basis of hyaluronan or C 11 -C 18  acylated derivative thereof, characterized in that it comprises a combination of hyaluronan and acylated derivative thereof or a combination of acylated derivatives thereof, the fiber core and the sheath being in any of the following arrangements:
 A) the core contains hyaluronic acid or a salt thereof, the sheath contains C 11 -C 18  acylated hyaluronan;   B) the core contains C 11 -C 18  acylated hyaluronan, the sheath contains hyaluronic acid or a salt thereof;   C) the core contains C 11 -C 18  acylated hyaluronan, the sheath contains different C 11 -C 18  acylated hyaluronan differing in C 11 -C 18  acyl from C 11 -C 18  acylated hyaluronan of the core, the degree of substitution of C 11 -C 18  acylated hyaluronan in the sheath being identical or different from the degree of substitution of C 11 -C 18  acylated hyaluronan in the core; or   D) the core contains C 11 -C 18  acylated hyaluronan, the sheath contains different C 11 -C 18  acylated hyaluronan differing in degree of substitution of C 11 -C 18  acylated hyaluronan of the sheath.   
     
     
         2 . Fiber according to  claim 1 , characterized in that C 11 -C 18  acylated hyaluronan is acylated in primary alcohol of N-acetyl-glucosamine. 
     
     
         3 . Fiber according to  claim 1 , characterized in that molar mass of C 11 -C 18  acylated hyaluronan is in the range 1×10 5  to 7×10 5  g/mol. 
     
     
         4 . Fiber according to  claim 1 , characterized in that the degree of substitution of C 11 -C 18  acylated hyaluronan of arrangement A or B is in the range 5 to 80%. 
     
     
         5 . Fiber according to  claim 1 , characterized in that the degree of substitution of C 11 -C 18  acylated hyaluronan contained in the core of arrangement C is in the range 5 to 80%, and the degree of substitution of C 11 -C 18  acylated hyaluronan contained in the sheath of arrangement C is in the range 5 to 80%; or the degree of substitution of C 11 -C 18  acylated hyaluronan contained in the core of arrangement D is in the range 5 to 29% and the degree of substitution of C 11 -C 18  acylated hyaluronan contained in the sheath of arrangement D is in the range 30 to 80. 
     
     
         6 . Fiber according to any one of  claims 1  to  5 , characterized in that C 11 -C 18  acylated hyaluronan is selected from a group containing palmitoyl hyaluronan, stearoyl hyaluronan or oleoyl hyaluronan. 
     
     
         7 . Fiber according to any one of  claims 1  to  4 , characterized in that hyaluronic acid and/or a salt thereof has molar mass in the range 1×10 5  to 2×10 6  g/mol, the salt of hyaluronic acid being selected from a group containing alkali metal ions, alkaline earth metals ions. 
     
     
         8 . Fiber according to any one of  claims 1  to  5 , characterized in that fiber fineness is in the range 10 to 40 tex. 
     
     
         9 . Fiber according to any one of  claims 1  to  5 , characterized in that the volume ratio core:sheath is in the range 3:1 to 1:6. 
     
     
         10 . Fiber according to any one of  claims 1  to  5 , characterized in that it contains at least one active agent. 
     
     
         11 . Fiber according to  claim 10 , characterized in that both core and sheath contain at least one identical or different active agent. 
     
     
         12 . Fiber according to  claim 10 , characterized in that the active agent is selected from a group containing antibacterial, antiseptic, antibiotic, anti-inflammatory, hemostatic agents, anesthetics, cytostatics, hormones, immunomodulators, immunosuppressives or agents for contrast imagining. 
     
     
         13 . Fiber defined in any one of  claims 1  to  5  for use in manufacturing of yarns, braided, woven, knitted or non-woven textiles. 
     
     
         14 . Method of preparation of fibers defined in any one of  claims 1  to  5 , characterized in that the first spinning solution containing hyaluronic acid or a salt thereof of concentration in the range 1 to 8 wt % is separately prepared in water and the second spinning solution containing C 11 -C 18  acylated hyaluronan of concentration 2 to 8 wt % is prepared in the mixture of water and lower alcohol, wherein water content is in the range 30 v/v % to 90 v/v %, lower alcohol content is in the range 10 v/v % to 70 v/v %, after which both the first and second spinning solution are extruded together into the coagulation bath containing 2 to 40 wt % of organic acid, at least 50 wt % of lower alcohol, and 2 to 48 wt % of water resulting in fiber of arrangement A or B, that is consequently scoured with lower alcohol and dried. 
     
     
         15 . Method of preparation of fibers defined in any one of  claims 1  to  5 , characterized in that the first spinning solution containing C 11 -C 18  acylated hyaluronan of concentration in the range 2 to 8 wt % is separately prepared in a mixture of water and lower alcohol and the second spinning solution containing different C 11 -C 18  acylated hyaluronan of concentration 2 to 8 wt % is prepared in a mixture of water and lower alcohol, wherein water content in both solutions is in the range 30 v/v % to 90 v/v %, lower alcohol content is in the range 10 v/v % to 70 v/v %, after which both the first and second spinning solution are extruded together into the coagulation bath containing 2 to 40 wt % of organic acid, at least 50 wt % of lower alcohol, and 2 to 48 wt % of water resulting in fiber of arrangement C or D, that is consequently scoured with lower alcohol and dried. 
     
     
         16 . Method according to  claim 14 , characterized in that the first spinning solution and/or the second spinning solution contain an active agent. 
     
     
         17 . Method according to  claim 14 , characterized in that the first spinning solution and/or the second spinning solution contain nanomicellar composition based on acylated hyaluronan containing the active agent. 
     
     
         18 . Staple fibers made from fibers defined in any one of  claims 1  to  5 . 
     
     
         19 . Non-woven textile made of staple fibers defined in  claim 18 . 
     
     
         20 . Yarn made of at least one fiber defined in any one of  claims 1  to  5 . 
     
     
         21 . Yarn according to  claim 20 , characterized in that it is formed of a bundle of fibers containing 2 to 10 fibers. 
     
     
         22 . Yarn according to  claim 21 , characterized in that it is in the form of twisted bundle of fibers. 
     
     
         23 . Yarn formed of at least two fibers, characterized in that at least one fiber is fiber defined in any one of  claims 1  to  5 , and at least one fiber is fiber selected from a group of fibers of other biodegradable materials, the biodegradable material being selected from a group comprising polylactic acid, polyglycolic acid, copolymer of polylactic and polyglycolic acid, polycaprolactone, polydioxanone or polyhydroxyalkanoates. 
     
     
         24 . Yarn according to  claim 20 , characterized in that it has fineness in the range 10 to 400 tex. 
     
     
         25 . Braided textile, woven textile or knitted textile, characterized in that it contains at least one yarn defined in  claim 20 . 
     
     
         26 . Braided, woven or knitted characterized in that it is made of yarn defined in  claim 20 . 
     
     
         27 . Braided, woven or knitted textile according to  claim 25 , characterized in that fiber core and sheath in the yarn are in arrangement A, C or D, whereas in the case of arrangement A there is the degree of substitution C 11 -C 18  acylated hyaluronan in the range 30 to 80% in the sheath, preferably 40 to 60% and in the case of arrangement C or D there is the degree of substitution of C 11 -C 18  acylated hyaluronan in the core in the range 5 to 29%, and the degree of substitution of C 11 -C 18  acylated hyaluronan is in the range 30 to 80% in the sheath. 
     
     
         28 . Braided, woven or knitted textile according to  claim 25 , characterized in that it is in the form of linear, flat or tubular textile. 
     
     
         29 . Braided textile according to  claim 25 , characterized in that it contains at least 8 yarns, containing at least one filling fiber inside the textile. 
     
     
         30 . Braided textile according to  claim 29 , characterized in that the diameter of filling fiber is in the range 0.0001 to 1 mm, preferably 0.01 to 0.1 mm. 
     
     
         31 . Braided textile according to  claim 29 , characterized in that the filling fiber is formed of a polymer selected from a group containing hyaluronic acid or derivatives thereof, polylactic acid, polyglycolic acid, copolymer of polylactic and polyglycolic acid, polycaprolactone, polydioxanone, polyhydroxyalkanoates, polyethylene, polypropylene, polyetherester, polyamide or polyester, preferably polylactic acid or copolymer of polylactic acid and polyglycolic acid. 
     
     
         32 . (canceled) 
     
     
         33 . (canceled) 
     
     
         34 . (canceled) 
     
     
         35 . Non-woven textile according to  claim 19  for use in the area of medicine, tissue engineering and systems for controlled release.