WO2021140115A1 - Biologisch abbaubare polymerfaser aus nachwachsenden rohstoffen - Google Patents
Biologisch abbaubare polymerfaser aus nachwachsenden rohstoffen Download PDFInfo
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- WO2021140115A1 WO2021140115A1 PCT/EP2021/050119 EP2021050119W WO2021140115A1 WO 2021140115 A1 WO2021140115 A1 WO 2021140115A1 EP 2021050119 W EP2021050119 W EP 2021050119W WO 2021140115 A1 WO2021140115 A1 WO 2021140115A1
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Classifications
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- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
- D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- 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
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- 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
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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- 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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
- D04H1/43828—Composite fibres sheath-core
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- 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
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/732—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by fluid current, e.g. air-lay
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/12—Physical properties biodegradable
Definitions
- the invention relates to a biodegradable polymer fiber made from renewable raw materials with good physical properties, a process for its production, and its use.
- Polymer fibers i.e. fibers based on synthetic polymers
- the underlying synthetic polymer is processed using a melt spinning process.
- the thermoplastic, polymeric material is melted and fed into a spinning beam in the liquid state by means of an extruder.
- the molten material is fed from this spinning beam to so-called spinnerets.
- the spinneret usually has a spinneret plate provided with several bores, from which the individual capillaries (filaments) of the fiber are extruded.
- wet or solvent spinning processes are also used to produce staple fibers. Instead of the melt, a highly viscous solution of a synthetic polymer is extruded through nozzles with fine bores. Both processes are referred to by those skilled in the art as so-called multi-digit spinning processes.
- the polymer fibers produced in this way are used for textile and / or technical applications. It is advantageous here if the polymer fibers have good dispersibility in aqueous systems, e.g. in the production of wet-laid nonwovens. In addition, it is advantageous for textile applications if the polymer fibers have good mechanical strength, for example in order to function well in fiber post-processing, for example in drawing on conveyor belts. In addition, it is advantageous for textile applications if the polymer fibers, in particular in the form of nonwovens, have a low thermal shrinkage.
- the modification or finishing of polymer fibers for the respective end use or for the necessary intermediate treatment steps, e.g. drawing and / or crimping, is usually carried out by applying suitable aviages or sizes, which are applied to the surface of the finished or to be treated polymer fiber.
- additives such as antistatic agents or colored pigments can be incorporated into the molten thermoplastic polymer or incorporated into the polymer fiber during the multi-digit spinning process.
- the dispersing behavior of a polymer fiber is influenced, among other things, by the nature of the synthetic polymer.
- the dispersibility in aqueous systems is therefore influenced and adjusted by the aviages or sizes applied to the surface.
- the task of providing a polymer fiber made from renewable raw materials which on the one hand should have good physical properties, so that good fiber post-processing, for example in the stretching on conveyor belts, is possible and the polymer fibers also have a low thermal shrinkage and, on the other hand, biologically are degradable.
- the polymer fiber made from renewable raw materials has good dispersibility, in particular long-term dispersibility, which is still available even after prolonged storage.
- the aforementioned object is achieved by the bi-component polymer fiber according to the invention, the fiber comprising a component A (core) and a component B (shell), the melting point of the thermoplastic polymer in component A is at least 5 ° C higher than that Melting point of the thermoplastic polymer in component B and the fiber material forming component A has a biopolymer A and the fiber material forming component B has a biopolymer B.
- the bi-component polymer fiber according to the invention is usually deposited as a tow and then stretched and post-treated on a conveyor belt using a special process.
- the tow can also be further processed directly and the filing of the tow in so-called cans can be completely or partially dispensed with.
- the combination of certain biopolymers, ie of component A (core) and a component B (shell) in connection with the special stretching leads to the bi-component polymer fibers according to the invention, which also have a low thermal shrinkage.
- the polymers used according to the invention are thermoplastic polycondensates based on so-called biopolymers.
- thermoplastic polymer denotes a plastic which can be (thermoplastically) deformed in a certain temperature range, preferably in the range from 25 ° C. to 350 ° C. This process is reversible, i.e. it can be repeated as often as required by cooling and reheating until it reaches the molten state, as long as the so-called thermal decomposition of the material does not set in due to overheating. This is where thermoplastic polymers differ from thermosets and elastomers.
- thermoplastic polycondensates based on so-called biopolymers
- synthetic biopolymers in particular melt-spinnable synthetic biopolymers, are particularly preferred.
- synthetic biopolymer denotes a material that consists of biogenic raw materials (renewable raw materials). This is used to distinguish it from conventional, petroleum-based materials or plastics, such as B. polyethylene (PE), polypropylene (PP) and polyvinyl chloride (PVC).
- PE polyethylene
- PP polypropylene
- PVC polyvinyl chloride
- the bi-component fibers according to the invention are made from biodegradable synthetic biopolymers, the term biodegradable for example according to ASTM D5338-15 (Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials Under Controlled Composting Conditions, Incorporating Thermophilic Temperatures, ASTM International, West Conshohocken, PA, 2015, www.astm.org).
- the synthetic biopolymer A forming component A is an aliphatic polyester, in particular a biopolymer comprising repeat units Lactic acid, hydroxybutyric acid and / or glycolic acid, preferably lactic acid and / or glycolic acid, in particular lactic acid.
- Polylactic acids are particularly preferred.
- Aliphatic polyesters are understood to be polyesters which typically have at least about 50 mol%, in some embodiments preferably at least about 60 mol% and in particularly preferred embodiments at least about 70 mol% aliphatic monomers.
- Polylactic acid is understood here to mean polymers that are built up from lactic acid units. Such polylactic acids are usually produced by condensation of lactic acids, but are also obtained in the ring-opening polymerization of lactides under suitable conditions.
- Polylactic acids particularly suitable according to the invention include poly (glycolide-co-L-lactide), poly (L-lactide), poly (L-lactide-co-s-caprolactone), poly (L-lactide-co-glycolide), poly (L -lactide -co-D, L-lactide), poly (D, L-lactide-co-glycolide) and poly (dioxanone).
- Such polymers are, for example, by the company Boehringer Ingelheim Pharma KG (Germany) under the trade name Resomer ® GL 903, Resomer ® L 206 S, Resomer ® L 207 S, Resomer ® L 209 S, Resomer ® L 210, Resomer ® L 210 S , Resomer ® LC 703 S, Resomer ® LG 824 S, Resomer ® LG 855 S, Resomer ® LG 857 S, Resomer ® LR 704 S, Resomer ® LR 706 S, Resomer ® LR 708, Resomer ® LR 927 S, Resomer ® RG 509 S and Resomer ® X 206 S are commercially available.
- Polylactic acids which are particularly advantageous for the purposes of the present invention are in particular poly-D-, poly-L- or poly-D, L-lactic acids.
- polylactic acid generally refers to homopolymers of lactic acid such as e.g. y (L-lactic acid), poly (D-lactic acid), poly (DL-lactic acid), mixtures thereof and copolymers containing lactic acid as the predominant component and a small proportion, preferably less than 10 mol%, of a copolymerizable comonomer .
- biopolymer A is copolymers or terpolymers based on polylactic acid, polyglycolic acid, polyalkylene carbonates (such as polyethylene carbonate), polyhydroxyalkanoates (PHA), polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV) and polyhydroxybutyrate-hydroxyvalerate copolymers (PHBV).
- the biopolymer A is exclusively a thermoplastic polycondensate based on lactic acids.
- the polylactic acids used according to the invention have a number average molecular weight (Mn), preferably determined by
- the numerical average is preferably a maximum of 1,000,000 g / mol, expediently a maximum of 500,000 g / mol, advantageously a maximum of 100,000 g / mol, in particular a maximum of 50,000 g / mol.
- a number average molecular weight in the range from at least 10,000 g / mol to 500,000 g / mol has proven particularly useful in the context of the present invention.
- the weight average molecular weight (Mw) of preferred lactic acid polymers is preferably in the range from 750 g / mol to 5,000,000 g / mol, preferably in the range from 5,000 g / mol to 1,000,000 g / mol, particularly preferably in the range from 10,000 g / mol to 500,000 g / mol, in particular in the range from 30,000 g / mol to 500,000 g / mol, and the polydispersity of these polymers is conveniently in the range from 1.5 to 5.
- the inherent viscosity of particularly suitable lactic acid polymers is in the range of 0.5 dl / g to 8.0 dl / g, preferably in the range from 0.8 dl / g to 7.0 dl / g, in particular in the range from 1.5 dl / g to 3.2 dl / g.
- biopolymers in particular thermoplastic synthetic biopolymers, with a glass transition temperature greater than 20 ° C., advantageously greater than 25 ° C., preferably greater than 30 ° C., particularly preferably greater than 35 ° C., in particular greater than 40 ° C., are extremely advantageous .
- the glass transition temperature of the polymer is in the range from 35.degree. C. to 55.degree. C., in particular in the range from 40.degree. C. to 50.degree.
- polymers are particularly suitable which have a melting temperature greater than 120 ° C., advantageously of at least 130 ° C., preferably greater than 150 ° C., and a maximum of 250 ° C., particularly preferably a maximum of 210 ° C., and particularly preferably in the range from 120 ° C. to 250 ° C., in particular in the range from 150 ° C. to 210 ° C.
- the glass transition temperature and the melting temperature of the polymer are preferably determined by means of differential scanning calorimetry (DSC for short). The following procedure has proven particularly useful in this context:
- the synthetic biopolymer B forming component B is preferably a biopolymer which has a melting point at least 5 ° C lower than the synthetic biopolymer A forming component A.
- the melting point of biopolymer A is preferably at least 10 ° C, preferably at least 20 ° C , particularly preferably at least 30 ° C, in particular at least 40 ° C, higher than the melting point of the synthetic biopolymer B.
- the biopolymer B is an aliphatic polyester, in particular an aliphatic polyester, which has repeat units which differ from the repeat units of the biopolymer A with regard to their chemical structure.
- Aliphatic polyesters are understood to be polyesters which typically have at least about 50 mol%, in some embodiments preferably at least about 60 mol% and in particularly preferred embodiments at least about 70 mol% aliphatic monomers.
- the biopolymer B usually has a number average molecular weight (Mn) of at least 10,000 Daltons, in particular of at least 12,000 Daltons, particularly preferably of at least 12500 Daltons and a maximum of up to 120,000 Daltons, in particular up to 100,000 Daltons, particularly preferably up to 80,000 Daltons
- Mn number average molecular weight
- the number average molecular weight (Mn) is usually determined by gel permeation chromatography against narrowly distributed polystyrene standards.
- the biopolymer B usually has a weight average molecular weight (Mw) of at least 50,000 Daltons and a maximum of up to 240,000 Daltons, in particular up to 190,000 Daltons, particularly preferably up to 100,000 Daltons.
- Mw weight average molecular weight
- Mn number average molecular weight
- the biopolymer B usually has a melt flow index of 5 to 200 grams per 10 minutes, in particular 15 to 160 grams per 10 minutes, particularly preferably 20 to 120 grams per 10 minutes, measured according to ASTM test method D1238-13 (ASTM D1238-13, Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer, ASTM International, West Conshohocken, PA, 2013, www.astm.org).
- Melt flow index is the weight (in grams) of a polymer that can be forced through an extrusion rheometer orifice (0.0825 inch diameter) when subjected to a force of 2160 grams in 10 minutes at 190 ° C.
- biopolymers B based on aliphatic polyesters with an apparent viscosity that is too high are generally difficult to process and - on the other hand - apparent viscosities that are too low generally lead to an extruded fiber that has no tensile strength and insufficient binding capacity ( Thermo-Bonding).
- biopolymers B are those which have a melting temperature of greater than 50 ° C., advantageously of at least 100 ° C., preferably greater than 120 ° C., and a maximum of 180 ° C., particularly preferably a maximum of 160 ° C., and particularly preferably in the range of 50 ° C. to 160.degree. C., in particular in the range from 120.degree. C. to 160.degree.
- the glass transition temperature of the biopolymer B is preferably at least 5 ° C., in particular at least 10 ° C., very particularly preferably at least 15 ° C., below the glass transition temperature of the biopolymer A.
- the glass transition temperature is determined by means of DSC.
- biopolymers B which can have a low melting point and a low glass transition temperature, are aliphatic polyesters with repeating units of at least 5 carbon atoms (e.g. polyhydroxyvalerate, polyhydroxybutyrate-hydroxyvalerate copolymer and polycaprolactone) and succinate-based aliphatic polymers (e.g. B. polybutylene succinate, polybutylene succinate adipate and polyethylene succinate).
- More specific examples can be polyethylene oxalate, polyethylene malonate, Polyethylene succinate, polypropylene oxalate, polypropylene malonate,
- polypropylene succinate polybutylene oxalate, polybutylene malonate, polybutylene succinate, and mixtures and copolymers of these compounds.
- Such aliphatic polyesters are known in principle (WO 2007/070064) and are typically synthesized by the condensation polymerization of a polyol and an aliphatic dicarboxylic acid or an anhydride thereof.
- polybutylene succinate and butylene succinate copolymers are particularly preferred.
- Biopolymers B which have a high degree of melting and crystallization enthalpy, are particularly suitable for thermal bonding.
- the biopolymers B are usually selected so that they have a degree of crystallinity or a latent heat of fusion (Delta Hf) of more than about 25 joules per gram (“J / g”), particularly preferably more than 35 J / g, in particular more than 50 J / g.
- the latent heat of fusion (AHf), the latent heat of crystallization (AHC) and the crystallization temperature are determined by means of differential scanning calorimetry ("DSC") according to ASTM D-3418 (ASTM D3418-15, Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry, ASTM International, West Conshohocken, PA, 2015, www.astm.org).
- the special biopolymer B used in this embodiment of the present invention has a number average molecular weight (Mn) of at least 10,000 Daltons, in particular of at least 12,000 Daltons, particularly preferably of at least 12,500 Daltons and a maximum of up to 30,000 Daltons, in particular up to 28,000 Daltons, particularly preferably up to 25,000 Daltons.
- the number average molecular weight (Mn) is usually determined by gel permeation chromatography against narrowly distributed polystyrene standards.
- the special biopolymer B has a melting temperature greater than 50 ° C., advantageously of at least 100 ° C., preferably greater than 120 ° C., and at most 180.degree. C., particularly preferably a maximum of 160.degree. C., and particularly preferably in the range from 50.degree. C. to 160.degree. C., in particular in the range from 120.degree. C. to 160.degree.
- the glass transition temperature of the special biopolymer B is preferably at least 5 ° C., in particular at least 10 ° C., very particularly preferably at least 15 ° C., below the glass transition temperature of the biopolymer A.
- the glass transition temperature is determined by means of DSC.
- biopolymers B which can have a low melting point and a low glass transition temperature, are aliphatic polyesters with repeating units of at least 5 carbon atoms (e.g. polyhydroxyvalerate, polyhydroxybutyrate-hydroxyvalerate copolymer and polycaprolactone) and succinate-based aliphatic polymers (e.g. polybutylene succinate, polybutylene succinate adipate and polyethylene succinate).
- aliphatic polyesters with repeating units of at least 5 carbon atoms e.g. polyhydroxyvalerate, polyhydroxybutyrate-hydroxyvalerate copolymer and polycaprolactone
- succinate-based aliphatic polymers e.g. polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- More specific examples can be polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate,
- polypropylene succinate include polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate, and mixtures and copolymers of these compounds.
- polybutylene succinate and butylene succinate copolymers are particularly preferred as special biopolymers B.
- Special biopolymers B which have a high degree of melting and crystallization enthalpy, are particularly suitable for thermal bonding.
- the biopolymers B are usually selected so that they have a degree of crystallinity or a latent heat of fusion (Delta Hf) of more than about 25 joules per gram (“J / g”), particularly preferably more than 35 J / g, in particular more than 50 J / g.
- the latent heat of fusion (AHf), the latent heat of crystallization (AHC) and the crystallization temperature are determined by means of differential scanning calorimetry ("DSC") according to ASTM D-3418 (ASTM D3418-15, Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry, ASTM International, West Conshohocken, PA, 2015, www.astm.org).
- the special biopolymer B has a melt viscosity determined at a temperature of 190 ° C (Göttfert Rheo-Tester 1000) in the range of 250 to 400 Pa * s at 200s 1 (shear) and 125 to 190 Pa * s at 1200s -1 (shear ), preferably in the range from 260 to 380 Pa * s at 200s -1 (shear) and 130 to 180 Pa * s at 1200s- 1 (shear), in particular in the range from 275 to 375 Pa * s at 200s -1 (shear ) and 135 to 175 Pa * s at 1200s 1 (shear)
- the biopolymers A and B described above have customary additives, such as anti-oxidant, among others. It has been shown here that additives from the group of anti-oxidants are unavoidable for the production and finishing of the fibers, since the biopolymers A and B mentioned above are sensitive to oxidative degradation.
- additives are pigments, stabilizers, surfactants, waxes, flow promoters, solid solvents, plasticizers and other materials, e.g., nucleating agents, which are added to improve the processability of the thermoplastic composition.
- nucleating agents which are usually added, facilitate crystallization during quenching of the fiber, thereby facilitating its processing.
- One type of such nucleating agent is a multicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures of such acids as described in U.S. Patent No. 6177193.
- the nucleating agents are typically present in the biopolymer in an amount less than about 0.5% by weight, in some embodiments less than about 0.25% by weight, and in some embodiments less than about 0.1% by weight B present.
- the bi-component fibers according to the invention consist of at least 90% by weight of the aforementioned aliphatic polyester biopolymers A and B and typically have less than about 10% by weight, preferably less than about 8% by weight, particularly preferably less than about 5 % By weight of additives in the biopolymer B forming the shell.
- biopolymers require an addition of anti-oxidant, in particular biopolymer B (shell), due to their sensitivity to oxidative degradation. Due to the selected combination of raw materials and post-processing, the amount of anti-oxidant can be significantly reduced, ie the anti-oxidant content in biopolymer B (shell) is between 0.025% and 0.2% by weight.
- the bi-component fibers according to the invention are combined to form tow and post-treated in a strip line using methods known in principle, in particular drawn and, if necessary, crimped or textured.
- the special biopolymers B described above, in particular, can be used by selecting special conveyor belt parameters for the stretching.
- the bi-component fiber according to the invention can be present as a finite fiber, e.g. as a so-called staple fiber, or as an infinite fiber (filament).
- the fiber is preferably in the form of staple fiber.
- the length of the aforementioned staple fibers is not subject to any fundamental restriction, but is generally 2 to 200 mm, preferably 3 to 120 mm, particularly preferably 4 to 60 mm.
- the single titer of the bi-component fiber according to the invention is between 0.5 and 30 dtex, preferably 0.7 to 13 dtex.
- the bi-component fiber according to the invention shows a low hot air thermal shrinkage in the range from 0% and 10%, preferably from> 0% to 8%, measured at 110 ° C. in each case.
- the polymer fiber according to the invention is basically produced by customary processes. First, the polymer is dried, if necessary, and fed to an extruder. Subsequently, the melted material is means conventional devices with appropriate nozzles spun. The exit speed at the nozzle exit surface is matched to the spinning speed so that a fiber with the desired titer is produced. Spinning speed is to be understood as the speed at which the solidified threads are drawn off.
- the fibers formed can have round, oval and other suitable cross-sections or also other shapes.
- the fiber filaments produced in this way are combined into yarns and these in turn into tow.
- the tows are first placed in cans for further processing.
- the tow that is temporarily stored in the cans is picked up and a large staple fiber tow is produced.
- Another object of the present invention is the aftertreatment of the staple fiber tows produced by known processes, these usually have 10-600 ktex, using a conventional strip line, by means of a special stretching process.
- the entry speed of the spun fiber tow into the drawing or drawing device is preferably 10 to 110 m / min (entry speed). In this case, preparations can also be applied which promote stretching but do not adversely affect the subsequent properties.
- the stretching can be carried out in one stage or, optionally, using a two-stage stretching process (see, for example, US Pat. No. 3,816,486). Before and during stretching, one or more finishes can be applied using conventional methods.
- the stretching according to the invention takes place with a stretching ratio, in particular when using the special biopolymer B, between 1.2 and 6.0, preferably between 2.0 and 4.0, the temperature during the stretching of the tow being between 30.degree. C. and 80.degree C is.
- the drawing thus takes place in the region of the glass transition temperature of the tow to be drawn.
- the drawing according to the invention takes place in the presence of steam, i.e. in the so-called steam box, so that the draw point of the fiber is set in the steam box.
- the steam box is usually operated at 3 bar pressure.
- the thermal shrinkage of the fiber can be reduced and targeted, can be adjusted in a controlled manner.
- the belt line settings are preferably the following:
- the drawing takes place in one stage between the drawing system S2 and the drawing system S1 and in the steam box, i.e. the drawing point of the fibers is in the steam box. All godets (usually 7 pieces) from S1 have a temperature of 30 - 80 ° C. The entire stretching takes place in the steam box.
- the steam box is preferably operated with 3 bar steam.
- All godets (usually 7 pieces) of the downstream drafting system S2 are cold, cold means room temperature (approx. 20 - 35 ° C).
- the cold S2 has the advantage that there is no risk of the individual fibers sticking to the hot godets of the S2.
- the fiber is still insensitive to high temperatures when it is fixed in the oven without tension and can withstand temperatures of up to 100 ° C without sticking.
- the “cold stretching” described above is particularly suitable for polybutylene succinates (FZ71) whose melt viscosity determined at a temperature of 190 ° C (Göttfert Rheo-Tester 1000) in the range of 250 to 325 Pa * s at 200s 1 (shear) and 125 to 150 Pa * s at 1200s -1 (shear), preferably in the range from 260 to 300 Pa * s at 200s -1 (shear) and 130 to 150 Pa * s at 1200s -1 (shear), in particular in the range from 270 to 290 Pa * s at 200s -1 (shear) and 135 to 145 Pa * s at 1200s -1 (shear).
- FZ71 polybutylene succinates
- the polybutylene succinate (FZ91) has a melt viscosity determined at a temperature of 190 ° C. (Göttfert Rheo-Tester 1000) in the range from 340 to 400 Pa * s at 200 s -1 (shear) and 150 to 190 Pa * s at 1200 s -1 (Shear), preferably in the range from 350 to 390 Pa * s at 200s -1 (shear) and 160 to 185 Pa * s at 1200s- 1 (shear), in particular in the range from 360 to 385 Pa * s at 200s -1 (Shear) and 165 to 180 Pa * s at 1200s -1 (shear), the drafting system S2 is operated at a temperature in the range from 60 ° C to 100 ° C, ie. all godets (usually 7 pieces) have the aforementioned temperature.
- the tow is preferably 240-360 ktex before drawing.
- the cable is first usually heated to a temperature in the range from 50 ° to 100 ° C., preferably 70 ° to 85 ° C., particularly preferably to about 78 ° C.
- a pressure of the cable infeed rollers of 1.0 to 6 , 0 bar, particularly preferably at about 2.0 bar, a pressure in the crimping chamber of 0.5 to 6.0 bar, particularly preferably 1.5-3.0 bar, with steam at between 1.0 and 2.0 kg / min., particularly preferably 1.5 kg / min., treated.
- the smooth or, if necessary, crimped fibers are picked up, followed by cutting and, if necessary, flattening and depositing in pressed bales as flakes.
- the staple fibers of the present invention are preferably cut on a mechanical cutting device downstream of the relaxation. There is no need to cut for cable types. These cable types are stored in the bale in uncut form and pressed.
- the degree of crimp is preferably at least 2 crimps (crimped arcs) per cm, preferably at least 3 crimps per cm, preferably 3 arcs per cm to 9.8 arcs per cm and particularly preferably 3.9 arcs per cm to 8.9 arcs per cm.
- values for the degree of crimp of about 5 to 5.5 sheets per cm are particularly preferred.
- the degree of crimp has to be set individually for the sheeting of textile surfaces using the wet laying process.
- the fibers according to the invention can be used to produce flat textile structures, which are also the subject of the invention. Because of the good dispersibility of the fibers according to the invention, such flat textile structures are preferably produced by wet-laid processes.
- textile fabric is therefore to be understood in its broadest sense in the context of this description. It can be all structures act containing the fibers according to the invention which have been produced by a surface-forming technique. Examples of such flat textile structures are nonwovens, in particular wet-laid nonwovens, preferably based on staple fibers, which are produced by means of thermobonding.
- the fibers according to the invention also have a good permanence of the dispersibility, i.e. the fibers have a very good dispersibility even after prolonged storage, e.g. several weeks or months, in the form of balls or comparable structures.
- the fibers according to the invention have good long-term dispersion, i.e. when the fibers are dispersed in liquid media, e.g. in water, the fibers remain dispersed for a longer time and only begin to settle after a long time.
- the fibers according to the invention are cut to a length of 2-12 mm.
- the amount of fibers is 0.25 g per liter of deionized water. For a better assessment, 1 g of fibers and 4 liters of deionized water are usually used.
- the fiber A / E-water mixture is stirred for at least three minutes using a standard laboratory magnetic stirrer (e.g. IKAMAG RCT) and a magnetic fish (80mm) (speed in the range 750-1500 rpm) and the stirrer is switched off. It is then judged whether all the fibers are dispersed.
- a standard laboratory magnetic stirrer e.g. IKAMAG RCT
- a magnetic fish 80mm
- the dispersion behavior of the fiber is assessed as follows: not dispersed (-) partially dispersed (o) completely dispersed (+) The above assessment takes place at defined time intervals.
- Nitrogen flow is 50 ml / min; Weight in the range of 2 - 3 mg for fibers.
- the final temperature is always around 50 ° C above the highest expected melting point.
- DSC measurement is carried out using a TA / Waters model Q100.
- the melt viscosity is determined using a Göttfert Rheo-Tester 1000 at a temperature of 190 ° C., at 200 s 1 (shear) and at 1200 s 1 (shear).
- Melt flow index is the weight (in grams) of a polymer that can be forced through an extrusion rheometer orifice (0.0825 inch diameter) when subjected to a force of 2160 grams in 10 minutes at 190 ° C.
- the latent heat of fusion (AHf), the latent heat of crystallization (AHC) and the crystallization temperature are determined by means of differential scanning calorimetry ("DSC") according to ASTM D-3418 (ASTM D3418-15, Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry, ASTM International, West Conshohocken, PA, 2015, www.astm.org).
- test samples are prepared from the cable tape sample. With the help of a pair of tweezers, one end is clamped in a multiple clamp, and a de-curling weight is attached to the other end.
- the measurement is carried out using a bicomponent fiber of the type PLA / PBS (core / shell) with a titer of 2.2 dtex;
- the multiple clamp equipped with the test samples is attached to a stand so that the test samples hang freely in the stand under pretensioning force. There, the selected starting length (normally 150 mm) is marked on each fiber. This is done with the help of marking lines in the stand and marking points that are applied to the test samples. After marking, the assembled multiple terminal is removed and placed back on a velvet plate. There the de-crimping weights are removed and the free fiber ends are clamped in a second multiple clamp. The test specimens clamped between two multiple clamps are suspended in a wire frame without tension. This wire frame is placed in the middle of the shrink oven, which has been preheated to the correct treatment temperature (usual temperatures are 200 ° C, 110 ° C, 80 ° C).
- the wire frame is removed from the oven. After the two multiple clamps have cooled down, they are removed with the test samples and placed on a velvet plate. After an acclimatization time of 30 minutes, the back measurement can be made. For this purpose, the measuring samples are loaded again with the de-curling weights and hung in the stand.
- the adjustable marking line of the tripod is used for back measurement positioned so that the upper edge of the marking point can be brought into line with the marking line. Now read the length between the markings on the counter of the stand for each fiber individually to an accuracy of 1/10 mm.
- the raw materials PLA 6202D from NatureWorks and BioPBS Fz71PM were spun into a corresponding fiber using a bicspinning technology.
- the proportion of PLA as core material was 70% by weight and the sheath proportion was 30% by weight.
- an antioxidant with an active substance content of 0.05% was added to the PBS in order to achieve a correspondingly good spinning behavior at the spinning temperature of 240 ° C.
- a finishing agent was applied to the spinning material in order to be able to guarantee further processing.
- the spun material was then processed on a conventional staple fiber line with an undrawn cable thickness of approx. 42 ktex.
- BioPBS Fz71PM is a polybutylene succinate whose melt viscosity (190 ° C) is 279 Pa * s at 200s 1 (shear) and 139 Pa * s at 1200s 1 (shear).
- PLA 6202D is a polylactic acid whose relative density is 1.24 g / cm 3 (according to ASTM D792) and which has a melt flow index (g / 10min @ 210 ° C) in the range 15-30.
- the glass transition temperature is 55-60 ° C (according to ASTM D3417) and the crystalline melt temperature is 160-170 ° C (according to ASTM D3418).
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Multicomponent Fibers (AREA)
Abstract
Description
Claims
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES21700368T ES2980901T3 (es) | 2020-01-10 | 2021-01-06 | Fibra de polímero biodegradable a partir de materias primas renovables |
BR112022013645A BR112022013645A2 (pt) | 2020-01-10 | 2021-01-06 | Fibra de polímero biodegradável de matérias-primas renováveis |
EP21700368.0A EP4087962B8 (de) | 2020-01-10 | 2021-01-06 | Biologisch abbaubare polymerfaser aus nachwachsenden rohstoffen |
DK21700368.0T DK4087962T3 (da) | 2020-01-10 | 2021-01-06 | Biologisk nedbrydelig polymerfiber af fornyelige råstoffer |
FIEP21700368.0T FI4087962T3 (en) | 2020-01-10 | 2021-01-06 | BIODEGRADABLE POLYMER FIBER FROM RENEWABLE RAW MATERIALS |
MX2022008527A MX2022008527A (es) | 2020-01-10 | 2021-01-06 | Fibra de polimero biodegradable a partir de materias primas renovables. |
US17/791,804 US20230031661A1 (en) | 2020-01-10 | 2021-01-06 | Biologically Degradable Polymer Fibre Made of Renewable Raw Materials |
CN202180008434.4A CN115315545A (zh) | 2020-01-10 | 2021-01-06 | 由可再生原料制成的可生物降解聚合物纤维 |
JP2022541777A JP2023510254A (ja) | 2020-01-10 | 2021-01-06 | 再生可能な原料からなる生分解性ポリマー繊維 |
CA3164162A CA3164162A1 (en) | 2020-01-10 | 2021-01-06 | Biologically degradable polymer fiber made of renewable raw materials |
PL21700368.0T PL4087962T3 (pl) | 2020-01-10 | 2021-01-06 | Biodegradowalne włókno polimerowe wykonane z surowców odnawialnych |
KR1020227025263A KR20220119674A (ko) | 2020-01-10 | 2021-01-06 | 재생 가능한 원료로 이루어진 생분해성 중합체 섬유 |
Applications Claiming Priority (2)
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EP20151275 | 2020-01-10 | ||
EP20151275.3 | 2020-01-10 |
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WO2021140115A1 true WO2021140115A1 (de) | 2021-07-15 |
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Family Applications (1)
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PCT/EP2021/050119 WO2021140115A1 (de) | 2020-01-10 | 2021-01-06 | Biologisch abbaubare polymerfaser aus nachwachsenden rohstoffen |
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US (1) | US20230031661A1 (de) |
EP (1) | EP4087962B8 (de) |
JP (1) | JP2023510254A (de) |
KR (1) | KR20220119674A (de) |
CN (1) | CN115315545A (de) |
BR (1) | BR112022013645A2 (de) |
CA (1) | CA3164162A1 (de) |
DK (1) | DK4087962T3 (de) |
ES (1) | ES2980901T3 (de) |
FI (1) | FI4087962T3 (de) |
HU (1) | HUE066858T2 (de) |
MX (1) | MX2022008527A (de) |
PL (1) | PL4087962T3 (de) |
PT (1) | PT4087962T (de) |
WO (1) | WO2021140115A1 (de) |
Citations (6)
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US3816486A (en) | 1969-11-26 | 1974-06-11 | Du Pont | Two stage drawn and relaxed staple fiber |
US6177193B1 (en) | 1999-11-30 | 2001-01-23 | Kimberly-Clark Worldwide, Inc. | Biodegradable hydrophilic binder fibers |
JP2003336124A (ja) * | 2002-05-16 | 2003-11-28 | Nippon Ester Co Ltd | ポリ乳酸ノークリンプショートカット繊維 |
DE69826457T2 (de) * | 1997-05-02 | 2005-10-13 | Cargill, Inc., Minneapolis | Abbaubare polymerfasern: herstellung, produkte und verwendungsverfahren |
WO2007070064A1 (en) | 2005-12-15 | 2007-06-21 | Kimberly - Clark Worldwide, Inc. | Biodegradable multicomponent fibers |
WO2015164447A2 (en) * | 2014-04-22 | 2015-10-29 | Fiber Innovation Technology, Inc. | Fibers comprising an aliphatic polyester blend, and yarns, tows, and fabrics formed therefrom |
Family Cites Families (8)
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WO2000078839A1 (fr) * | 1999-06-18 | 2000-12-28 | Kanebo, Limited | Resine d'acide polyactique, articles textiles obtenus a l'aide de cette resine, et procedes de production de ces articles textiles |
JP2006097148A (ja) * | 2004-09-28 | 2006-04-13 | Toray Ind Inc | 生分解性を有する芯鞘型複合繊維 |
US20060159918A1 (en) * | 2004-12-22 | 2006-07-20 | Fiber Innovation Technology, Inc. | Biodegradable fibers exhibiting storage-stable tenacity |
JP5098554B2 (ja) * | 2006-10-11 | 2012-12-12 | 東レ株式会社 | 皮革様シートの製造方法 |
US20160153122A1 (en) * | 2013-07-23 | 2016-06-02 | Ube Exsymo Co., Ltd. | Method for producing drawn conjugated fiber, and drawn conjugated fiber |
SI3129530T1 (sl) * | 2014-04-07 | 2018-12-31 | Trevira Gmbh | Polimerno vlakno z izboljšano disperzibilnostjo |
JP7364829B2 (ja) * | 2017-03-31 | 2023-10-19 | 大和紡績株式会社 | 分割型複合繊維及びこれを用いた繊維構造物 |
JP6611969B2 (ja) * | 2019-01-25 | 2019-11-27 | ダイワボウホールディングス株式会社 | 複合繊維、不織布および吸収性物品用シート |
-
2021
- 2021-01-06 BR BR112022013645A patent/BR112022013645A2/pt not_active Application Discontinuation
- 2021-01-06 CN CN202180008434.4A patent/CN115315545A/zh active Pending
- 2021-01-06 KR KR1020227025263A patent/KR20220119674A/ko unknown
- 2021-01-06 MX MX2022008527A patent/MX2022008527A/es unknown
- 2021-01-06 FI FIEP21700368.0T patent/FI4087962T3/en active
- 2021-01-06 EP EP21700368.0A patent/EP4087962B8/de active Active
- 2021-01-06 HU HUE21700368A patent/HUE066858T2/hu unknown
- 2021-01-06 US US17/791,804 patent/US20230031661A1/en active Pending
- 2021-01-06 DK DK21700368.0T patent/DK4087962T3/da active
- 2021-01-06 WO PCT/EP2021/050119 patent/WO2021140115A1/de active Search and Examination
- 2021-01-06 PL PL21700368.0T patent/PL4087962T3/pl unknown
- 2021-01-06 ES ES21700368T patent/ES2980901T3/es active Active
- 2021-01-06 JP JP2022541777A patent/JP2023510254A/ja active Pending
- 2021-01-06 CA CA3164162A patent/CA3164162A1/en active Pending
- 2021-01-06 PT PT217003680T patent/PT4087962T/pt unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US3816486A (en) | 1969-11-26 | 1974-06-11 | Du Pont | Two stage drawn and relaxed staple fiber |
DE69826457T2 (de) * | 1997-05-02 | 2005-10-13 | Cargill, Inc., Minneapolis | Abbaubare polymerfasern: herstellung, produkte und verwendungsverfahren |
US6177193B1 (en) | 1999-11-30 | 2001-01-23 | Kimberly-Clark Worldwide, Inc. | Biodegradable hydrophilic binder fibers |
JP2003336124A (ja) * | 2002-05-16 | 2003-11-28 | Nippon Ester Co Ltd | ポリ乳酸ノークリンプショートカット繊維 |
WO2007070064A1 (en) | 2005-12-15 | 2007-06-21 | Kimberly - Clark Worldwide, Inc. | Biodegradable multicomponent fibers |
WO2015164447A2 (en) * | 2014-04-22 | 2015-10-29 | Fiber Innovation Technology, Inc. | Fibers comprising an aliphatic polyester blend, and yarns, tows, and fabrics formed therefrom |
Also Published As
Publication number | Publication date |
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CN115315545A (zh) | 2022-11-08 |
PT4087962T (pt) | 2024-05-24 |
FI4087962T3 (en) | 2024-04-24 |
BR112022013645A2 (pt) | 2022-09-13 |
US20230031661A1 (en) | 2023-02-02 |
EP4087962B8 (de) | 2024-06-19 |
EP4087962B1 (de) | 2024-03-13 |
ES2980901T3 (es) | 2024-10-03 |
JP2023510254A (ja) | 2023-03-13 |
MX2022008527A (es) | 2022-08-08 |
HUE066858T2 (hu) | 2024-09-28 |
EP4087962A1 (de) | 2022-11-16 |
PL4087962T3 (pl) | 2024-07-01 |
DK4087962T3 (da) | 2024-06-10 |
CA3164162A1 (en) | 2021-07-15 |
KR20220119674A (ko) | 2022-08-30 |
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