Classifications

• • 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
  • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
• • 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
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties
• • 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
• • 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
  • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
  • D01F4/04—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from casein

Definitions

• Object of the invention is a method of producing molded bodies consisting of native polymers forming networks and phase change materials included therein, which in the form of fibers can be processed to textile fabrics having enhanced thermoregulation properties and which convey an improved wearability to the textiles produced therefrom, as well as a high functionality with respect to heat storage and heat removal when used in other applications.
• phase change materials are applied on to or inserted into a polymer matrix.
• phase change materials can absorb and emit, respectively, large amounts of heat at constant temperatures.
• an increased heat capacity can be noticed which finds its physical measurable expression in the occurring melting enthalpy and permits the storage or delivery of greater amounts of heat than would correspond to the normal heat capacity of the material outside of the temperature range of the phase change or the conformation change.
• the absorption of heat at a change of the phasing or of the conformation is, on the one hand, due to the absorption of thermal energy at a heat supply from outside, which subjectively is felt as a cooling effect, and on the other hand, when there is a cooling, reversibly supplies in the reverse direction the same amount of heat, which is felt as warming.
• Paraffin or salts and solutions of suitable salts, respectively can be used as phase change materials.
• the temperature range of the phase transition from the solid state into the molten state can be, due to varying the chain length, controllably matched to each desired temperature at which the heat is to be delivered or stored. Salts or the solutions thereof can be selected at will to the desired temperature range of the conformation change.
• the micro-encapsulated form is suited for use in the textile technology.
• the phase change material is encased in ceramic spheres and polymer spheres, respectively, having diameters within the ⁇ m-range and in this manner are brought into a form that can be manipulated and that permits the inclusion in matrix materials of cross-linked polymers, whereby the degree of the thermo regulation potential depends on the kind and the amount of the enclosed PCM material.
• Synthetic polymers as well as native network forming polymers can be used as matrix materials.
• Fibers having thermo-regulating properties and textile fabrics made therefrom are already known per se. So the teaching of EP 0306202 and U.S. Pat. No. 4,756,958 is that synthetic fibers from melt-spinnable polymers can be provided with temperature stabilizing behaviour by including therein temperature regulating materials. A disadvantage thereby is the low amount of temperature regulating materials that can be inserted into the fibers. Furthermore, clothing is described in U.S. Pat. No. 5,885,475 which is composed of fibers made of a mixture of polymers which additionally includes phase change material. Also here the fiber-forming substances are selected from the group of synthetic thermoplastic polymers which can be spun when molten.
• Multi-component fibers with enhanced and reversible thermal properties and textile fabrics manufactured therefrom are described in WO 03027365, US 200212079, and US 200129648.
• the fiber bodies which consist of a plurality of elongated components contain at least in one of said elongated components one temperature regulating material distributed therein.
• This material may be a phase change material and may optionally be selected from the class of the hydrocarbons, the hydrated salts, paraffin, oil, water, fatty acids, fatty acid ester, dibasic acids and ester, halide, clusters and semi-clusters, gas-cluster, stearin anhydride, carbonate ethylene, higher alcohols, polymers, and metals and mixtures thereof.
• the arrangement of the different components of the fiber can be optionally arranged in a core-sheath-structure, polysectionally, in bundles or in stripes with variously formed cross-sections.
• the matrix material of the multi-component fiber described may consist of different linear chain molecules.
• WO 02095314 and CH 0200245 there are also methods described in which the temperature regulation properties are to be obtained by textile printing of a textile fabrics structure with micro-encapsulated phase change material.
• the temperature regulation effect is obtained by applying a coating which contains a phase change material.
• Such a method involves the disadvantage that only a comparatively low amount of phase change material can be fixed to the surface of the structures, in particular when only a part of the surface is printed with a suspension of micro-encapsulated phase change material and, hence, the temperature regulation effect, related to the amount of material, is comparatively locally limited.
• the printing of the textile surface with a suspension of micro-encapsulated phase change material applied in a comparatively thick layer has a disadvantageous effect on the flexibility of the textile products manufactured therefrom and, hence, on the wearability.
• the suspensions of micro-encapsulated phase change materials applied to textile surfaces are only restrictedly mechanically stable and fast to washing.
• PCM-fibers described herein before are manufactured on the basis of synthetic melt-spinnable polymer fibers.
• network forming matrix material which occurs in nature and can be obtained in a simple way such as cellulose and/or globular proteins has neither been mentioned before, nor have exemplary PCM-fibers been produced therefrom.
• cross-linked structures can be, for example, manufactured from cellulose form matter and spinning matter in that cellulose is dissolved in tertiary amino oxides, preferably in n-methylmorpholin-n-oxide and a non-solvent agent, preferably water.
• a spinning solution consisting of cellulose in n-methylmorpholin-n-oxide and water is molded after a dry/wet-spinning process, coagulated for example in an aqueous spinning bath, the solvent is completely removed by repeated washing and the solidified molded bodies are dried.
• the molded bodies obtained in this manner exhibit a network structure characterized by a hydrogen bridge linkage.
• DE 10059111 teaches the cross-linking of proteins via the existing functional groups which results in mechanically stable molded bodies.
• the globular proteins exhibit, as the name already tells, a spherical tertiary structure and can be found in nature in a comparatively great number. Examples for these are casein (a lactic protein), zein (corn protein) and ardenine (arachis protein).
• the object of the invention is to provide a method for producing thermo regulating molded bodies, in particular fibers and nonwoven textile fabrics thereof from native network forming polymers having phase change material included in the network which in contrast to PCM-fibers produced on a synthetic basis have an increased portion of incorporated phase change materials and thus, in avoiding the mentioned disadvantages of the prior art, exhibit an enhanced thermo regulation potential.
• an aspect will be the application of parent materials occurring in nature and the environmental-friendly production of fibers having the described properties by the fewest possible process steps under exploitation of natural resources.
• phase change materials up to an amount of 200 weight percent are included into network forming polymers, wherein the network is formed by chemically coupling functional groups, hydrogen bridges or polymer and oligomer, respectively, structures helically connected to one another.
• a suitable network forming polymer matrix material is native cellulose.
• the latter forms bonds which, on the one hand, effect a cross-linkage of the polymer structure and, on the other hand, result in the formation of a super lattice structure due to the developing of hydrogen bridge linkages.
• This structure formation permits the embedment of even larger amounts of micro-encapsulated phase change materials.
• the micro-encapsulation results in a separation of the phase change material from the polymer matrix.
• paraffins of different chain lengths will be used as phase change materials, whereby the temperature of the phase transition depends on the chain length of the molecules and can be adapted to the required temperature range of the phase transition by varying the chain lengths.
• inorganic hydrated salts can also be utilized which can be selected in dependence on the desired temperature range of the phase change. Due to their higher density compared to paraffins it is possible in particular, to insert far more than 50 weightpercent of phase change material into the polymer matrix.
• Globular proteins which are present in nature in a great number and which can be extracted in a simple manner are further network forming polymer materials, which are suitable for realizing the object of the invention.
• a three-dimensionally interlinked tertiary structure results in these proteins via a secondary structure in the form of the folded-up amino acid chain, based on a hydrogen bridge linkage.
• Said tertiary structure will be stabilized, for example, via disulphide bridges, hydrogen bridge linkages or by ion- or hydrophobic interactions.
• pre-interlinked globular proteins are also soluble in tertiary amino-oxides and could be molded in a dry/wet-process.
• a polysaccharide as, for example cellulose, as a further component to the solution of the pre-interlinked globular proteins.
• phase change materials up to an amount of 200 weightpercent, related to the mass of the contained cellulose, are, for example, added to a cellulose solution in an aqueous tertiary aminoxide, and this solution drafted via an air gap and subsequently the cellulose with the phase change material contained therein is precipitated in a coagulating bath consisting of, for example, water or a water/alcohol mixture under formation of physical networks.
• a coagulating bath consisting of, for example, water or a water/alcohol mixture under formation of physical networks.
• micro-encapsulated phase change material is added to pre-crosslinked globular proteins in n-methylmorpholin-n-oxide, if necessary under addition of polysaccharides such as cellulose, are transferred into a spinning solution and spun to filaments by using known methods.
• the produced PCM-fibers according to the invention based on native polymers find a wide range of applications such as, for example, in material for producing textiles, fleeces, textiles for the automobile industry, and in yarns and blended yarns.
• phase change heat characterizing the thermo regulation properties of the inventional native PCM-fibers exhibits, compared to the PCM-fibers based on synthetic polymers a value which is up to a factor of 8 higher.
• the micro-encapsulated phase change material has been screened before to a grain size of maximally 50 ⁇ m.
• the dissolving vessel will be evacuated to 20 mbar and is heated from 20° C. to 94° C.
• the spinning solution obtained exhibits a viscosity of 1560 PAS and a refractive index of 1.484.
• RPM 25 min ⁇ 1
• the spinning solution is at 80° C. extruded through a spinneret having a number of nozzles of 150 and a nozzle diameter of 200 ⁇ m via an air slot into a coagulating bath consisting of water.
• the drain speed is 25 m/min so that a draught of 3.75 results at the air slot.
• the spun fibers exhibit a titre of about 14 dtex and will subsequently washed in washing baths and then are cut to staple.
• the phase change temperature of the obtained fibers is 30 J/g.
• cellulose fibers without embedded phase change materials exhibit a heat capacity of 6 J/g.
• the breaking strength related to the count of the obtained fibers is about 15 cN/tex.
• the modified fibers could be processed to a needle fleece having a flat mass of 300 g/m 2 after carding in a carding engine.
• 100 g casein are dispersed in 250 ml water and crosslinked by addition of 2 g glutaraldehyde and 0.1 g MgCl 2 at 25° C. After squeezing out to a moisture content of 50%, the casein is suspended in 430 g of 60%-NMMNO. 0.5 g propylgallate are added as a stabilizer. 100 g of a micro-encapsulated phase change material such as, for example, Lurapret® TX PMC 28 from BASF AG are added to the suspension what corresponds to an amount of 100 weightpercent of phase change material related to the protein in the solution.
• a micro-encapsulated phase change material such as, for example, Lurapret® TX PMC 28 from BASF AG are added to the suspension what corresponds to an amount of 100 weightpercent of phase change material related to the protein in the solution.
• the suspension is transferred into a spinning solution in a kneading machine with a jacket heating under a vacuum of 30 mbar and at a temperature of 90° C. by distilling off of 130 g water.
• the homogeneity of the spinning solution is checked with an optical microscope and turns out, as a rule, 15 minutes after the end of the distillation.
• the spinning solution is extruded at a spinning temperature of 80° C. in filaments through a spinneret having 150 nozzles each of a diameter of 90 ⁇ m via an air slot into an aqueous coagulating bath and subsequently is washed in distilled water without residue and then cut to a staple length of 40 mm.
• the drying of the fibers is carried out at 60° C.
• the strength of the spun fibers is about 15 cN/tex at an elastic stretch of 10% and a titre of about 15 dtex.
• the heat absorption capacity of the obtained fibers is about 60 J/g compared to 8 J/g of the non-modified fibers.
• casein 50 g casein are dispersed in 250 ml water and crosslinked by addition of 1 g glutaraldehyde and 0.1 g MgCl 2 at 25° C. After squeezing out to a moisture content of 50%, the casein is suspended in 430 g of 60%-NMMNO. Additionally 25 g of dry ground sulphite cellulose (DP 760) as well as 100 g of a micro-encapsulated phase change material such as, for example, Lurapret® TX PMC 28 from BASF AG are added. This corresponds to an amount of 133% PCM related to cellulose. 0.5 g propylgallate are added as a stabilizer.
• This suspension is transferred into a spinning solution in a kneading machine with a jacket heating under a vacuum of 30 mbar and at a temperature of 90° C. by distilling off of 140 g water.
• the homogenisation of the spinning solution is achieved 15 minutes after the end of the distillation and is checked with an optical microscope.
• the resulting spinning solution is extruded through a spinneret having 150 nozzles each of a diameter of 90 ⁇ m via an air slot into an aqueous coagulating bath and the formed fiber skein is washed in distilled water without residue and then cut to a staple length of 40 mm.
• the drying of the fibers is carried out at 60° C. in a through-circulation drier.
• the fibers exhibit a strength of 30 cN/tex at an elastic stretch of 8%.
• the titre is about 20 dtex.
• the heat absorption capacity of the modified fibers is about 70 J/g compared to 7 J/g of the non-modified
• 7607 g of a 60%-solution of n-methylmorpholin-n-oxide are given together with 784 g cellulose of an average polymerisation degree 500 under addition of 4.6 g propylgallate into a dissolving vessel with agitator of 37 l volume.
• the dissolving vessel will be evacuated to 20 mbar and is heated from 20° C. to 94° C. in the course of 6 hours at a stirrer RPM of 18 min ⁇ 1 and the evaporating water is condensed in a condenser. Thereby 2361 g water are, in total, condensed.
• the spinning solution obtained exhibits a viscosity of 8072 PAS, the refractive index of the spinning solution is about 1.487.
• a stock solution will be produced from 1500 g of an 80%-solution of n-methylmorpholin-n-oxide and 750 g of a micro-encapsulated phase change material such as, for example, Lurapret® TX PMC 28 from BASF AG and 45 g xanthane.
• Both solutions are, after intimate mixing in a dynamic mixer, extruded at 80° C. through a spinneret having a number of nozzles of 150 and a nozzle diameter of 200 ⁇ m, drafted through an air gap, regenerated in an aqueous coagulating bath and is washed in distilled water to be entirely free of solvents.
• the setting of the mixing ratio is carried out such that the extruded fibers exhibit a concentration of micro-encapsulated phase change material of 60% related to the cellulose.
• the spun fibers have a fiber count of about 10 dtex and are cut to staple after washing.
• the phase change heat of the achieved fibers is 80 J/g.
• the cellulose fibers without an inserted phase change material exhibit in the corresponding temperature range a heat capacity of 6 J/g.
• the tenacity related to the fineness of the obtained fibers is about 15 cN/tex.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Artificial Filaments (AREA)
• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
• Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Polyesters Or Polycarbonates (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Nonwoven Fabrics (AREA)

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• 2004
  • 2004-08-25 WO PCT/DE2004/001893 patent/WO2005024102A1/de active IP Right Grant
  • 2004-08-25 US US10/570,374 patent/US20060279017A1/en not_active Abandoned
  • 2004-08-25 EP EP04786178A patent/EP1658395B1/de not_active Expired - Lifetime
  • 2004-08-25 PL PL04786178T patent/PL1658395T3/pl unknown
  • 2004-08-25 DE DE502004001972T patent/DE502004001972D1/de not_active Expired - Lifetime
  • 2004-08-25 AT AT04786178T patent/ATE344844T1/de active
  • 2004-08-25 DE DE102004041684A patent/DE102004041684A1/de not_active Withdrawn
  • 2004-08-25 DE DE112004002148T patent/DE112004002148D2/de not_active Withdrawn - After Issue

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