EP2697415B1 - Fibres d'élastomère et leurs procédés de fabrication et d'utilisation - Google Patents

Fibres d'élastomère et leurs procédés de fabrication et d'utilisation Download PDF

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Publication number
EP2697415B1
EP2697415B1 EP12714913.6A EP12714913A EP2697415B1 EP 2697415 B1 EP2697415 B1 EP 2697415B1 EP 12714913 A EP12714913 A EP 12714913A EP 2697415 B1 EP2697415 B1 EP 2697415B1
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EP
European Patent Office
Prior art keywords
fiber
fabric
fibers
prepared
diisocyanate
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EP12714913.6A
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German (de)
English (en)
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EP2697415A1 (fr
Inventor
Ravi R. Vedula
Mouh-Wahng Lee
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Lubrizol Advanced Materials Inc
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Lubrizol Advanced Materials Inc
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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
    • A41D13/0015—Sports garments other than provided for in groups A41D13/0007 - A41D13/088
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B17/00—Selection of special materials for underwear
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/18—Elastic
    • 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
    • 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
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/82—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides
    • 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
    • D01F6/94—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 other polycondensation products
    • 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
    • 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
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B2500/00—Materials for shirts, underwear, baby linen or handkerchiefs not provided for in other groups of this subclass
    • A41B2500/50—Synthetic resins or rubbers
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00—Materials for garments
    • A41D2500/50—Synthetic resins or rubbers
    • 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
    • D10B2501/00—Wearing apparel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component

Definitions

  • the invention relates to a fiber excellent in cool contact feeling which is excellent in hand and skin touch and capable of preventing unpleasant feeling in the wet state while also having excellent elasticity.
  • the invention also relates to fabric, clothing, and underwear excellent in cool contact feeling and obtainable by using said fiber as well as the methods of making the fibers and articles thereof.
  • US 5,167,899 discloses a melt-blowing process for producing a fiber of an extrudable polyurethane having a large amount of hard segment.
  • EP 2 292 822 discloses a mixed fiber spun bonded nonwoven fabric suitable for use in absorbent articles such as sanitary napkins, pantry liners, incontinence pads and disposable diapers.
  • the present invention provides an elastic cooling fiber with a Tg of no more than 22 degrees C and more specifically a fiber prepared from a composition comprising the reaction product of: (i) a hydroxyl terminated intermediate, comprising a polyester, a polyether, a polycarbonate or a combination thereof, wherein the intermediate has a Tg of no more than 22 degrees C; (ii) a diisocyanate: and (iii) a chain extender comprising a linear alkylene glycol wherein the Tg of the composition from which the fiber is prepared is no more than 22 degrees C.
  • the invention provides a fabric that is made from the fibers described herein, which in some embodiments are mixed with other fibers.
  • the invention provides an article that is made from the fabric described here.
  • the invention provides a method of providing a cooling effect in an article that comes into close proximity with, in some embodiments even direct contact with, human skin, including the steps of: (1) preparing a fabric comprising the fibers described herein; (2) preparing an article that comprises said fabric; (3) bringing said article into close proximity with, in some embodiments even direct contact with, human skin.
  • the invention provides a method of making a fabric including the steps of: (1) preparing an elastomer resin in an internal mixing device wherein said elastomer resin is prepared by reacting: (i) a hydroxyl terminated intermediate, comprising a polyester, a polyether, a polycarbonate or a combination thereof, wherein the intermediate has a Tg of no more than 22 degrees C; (ii) a diisocyanate; and (iii) a chain extender comprising a linear alkylene glycol; wherein the Tg of the composition from which the fiber is prepared is no more than 22 degrees C; (2) melt-spinning said elastomer resin into a fiber, in some embodiments a monofilament or multifilament fiber; and (3) processing said fiber, optionally in combination with one or more other fibers, into a fabric.
  • the invention provides a fiber excellent in cool contact feeling and also excellent in elasticity.
  • the fiber can give a cooling contact feeling when in contact with the skin. The effect can be strong enough to be sensed in a sensory test.
  • the fibers of the invention may have a Tg of no more than 22 degrees C and are, as well as article made from them, exceptionally elastic and are also excellent in providing a cool contact feeling when using the fiber for clothing.
  • Elastic and “Elasticity” as used herein means that a fiber will recover at least 50 percent of its stretched length after the first pull and after the fourth to 100% strain (doubled the length). Elasticity can also be described by the "permanent set” of the fiber. "Permanent Set” is the converse of elasticity. A fiber is stretched to a certain point, in some embodiments 50% of the fiber's known percent elongation at break, and subsequently released to the original position before stretch, and then stretched again. The point at which the fiber begins to pull a load is designated as the percent permanent set. "Elastic materials” are also referred to in the art as “elastomers” and “elastomeric”.
  • the fibers of the present invention can provide this balance of benefits while also avoiding any sticky or inferior skin touch feelings, in the wet state owing to sweat and the like and therefore, which often leads to unpleasant feelings for the wearer when the fiber is used in a garment.
  • the fibers of this invention balance all of these factors and provide superior performance in any one or any combination of these factors.
  • the thermoplastic elastomer utilized in the preparation of the fibers described herein is substantially free of, or even free of, a polyamide type elastomer and/or a polyester type elastomer. More specifically, the present invention may be free of polyether block amide copolymers, polyether amide copolymers, and polyester amide copolymers, or any combination thereof. More specifically, the compositions involved in the present invention may be substantially free of, or even completely free of, Pebax (manufactured by Arkema).
  • polyamide elastomer As used herein, the term polyamide elastomer, or polyamide block within an elastomer, is considered in its chemical sense to be different and distinct from a polyurethane elastomer, or a urethane block within an elastomer.
  • polyamide links and/or block refer to -N(R)-C(O)-R- units and/or linkages in the elastomer while polyurethane links and/or blocks refer to -N(R)-C(O)-O-R- units and/or linkages in the elastomer.
  • thermoplastic elastomer utilized in the preparation of the fibers described herein may include polyether block amide copolymers, polyether amide copolymers, polyester amide copolymers, or any combination thereof.
  • polyester type elastomer is not particularly limited and examples are polyether ester copolymers and polyester ester copolymers. They may be used alone or two or more of them may be used in combination.
  • the resin component contained in the fibers of the invention provides the excellent cool contact feeling of the invention, and so the thermoplastic elastomers alone may be used.
  • Another benefit of the invention is that the fibers described here, when they contain only a thermoplastic elastomer as the resin component, generally have no sticky feeling and so do not become difficult for spinning.
  • additional resins may be used in combination with the resin described here, it is not required to address any stickiness or unpleasant feeling that may otherwise accompany more conventional fibers.
  • an additional resin is used.
  • inorganic fillers resins may be used in combination with the resin described here, it is not required to address any stickiness or unpleasant feeling that may otherwise accompany more conventional fibers.
  • the fiber, and/or the resin from which it is prepared is substantially free, to free of, any inorganic filler.
  • an inorganic filler it is not particularly limited and examples may include mineral type pigments, such as calcium carbonate such as light calcium carbonate and heavy calcium carbonate, barium carbonate, magnesium carbonate such as basic magnesium carbonate, calcium sulfate, barium sulfate, titanium dioxide, iron oxide, tin oxide, titanium oxide, zinc oxide, magnesium oxide, ferrite powder, zinc sulfide, zinc carbonate, aluminum nitride, silicon nitride, Satin White, diatomaceous earth such as fired diatomaceous earth, calcium silicate, aluminum silicate, magnesium silicate, silica such as amorphous silica, amorphous synthesized silica, and colloidal silica, colloidal alumina, pseudo boehmite, aluminum hydroxide, magnesium hydroxide, alumina, hydrated alumina, litopon, zeo
  • the filler is titanium oxide, zinc oxide, barium oxide, silica, or some combination thereof.
  • the form of the inorganic fillers is not particularly limited and examples are finite forms such as spherical, needle-like, plate type forms and the like, or nonfinite forms.
  • the lower limit of the content of the inorganic filler may be 1%, 2% or 7% by weight, and the upper limit of that is 30% by weight.
  • the fibers of the invention may be described by a q max value.
  • the lower limit of a q max value of the fiber may be 0.20, 0.21 or 0.22 J/sec/cm 2 . If the q max value is less than 0.20 J/sec/cm 2 , subjects may not feel any cool contact feeling even if a sensory test is performed. In other embodiments, the q max value of the fiber may be less than 0.20 or even more than 0.22 J/sec/cm 2 .
  • the q max value is defined as a peak value of the heat flow quantity of stored heat transferring to a sample at a lower temperature in the case a prescribed heat is stored in a heat plate with a specified surface area and a specified weight and immediately after the heat plate is brought into contact with the sample surface. It is supposed that the q max value simulates the body heat removed from the body by the sample when clothing is put on and it is supposed that as the q max value is higher, the body heat removed from the body is higher and the cool contact feeling is more excellent when the clothing is put on.
  • the lower limit of the heat conductivity of the fiber of the invention may be 1x10 -3 degrees C/Wm 2 .
  • the heat conductivity is also considered to be one of the important parameters to which the cool contact feeling is corresponding. If the heat conductivity is less than 1x10 -3 degrees C./Wm2, most subjects may not feel any cool contact feeling even if a sensory test is performed.
  • the heat conductivity can be calculated by measuring the heat loss speed after a heat plate is layered on a sample put on a sample stand and the temperature of the heat plate is stabilized at a prescribed temperature and performing calculation by the following formula (2).
  • Heat conductivity W / cm / degrees C . WD / A / ⁇ T
  • the fiber of the invention may be used in the form of a composite fiber comprising the thermoplastic elastomer and another resin and may have a core-sheath structure and comprises a core part containing a dyeable resin and a sheath part containing a thermoplastic elastomer resin, a thickness of the sheath part being 20 micrometers or thinner (hereinafter referred to as a core-sheath type composite yarn in some cases).
  • the fiber excellent in cool contact feeling of the invention can be a fiber having the core-sheath structure having good dyeability, keeping excellent properties of the thermoplastic elastomer such as cool contact feeling by using such a dyeable resin for the core part and the thermoplastic elastomer having the cool contact feeling and excellent in the flexibility for the sheath part.
  • the form of the core-sheath type composite yarn is not particularly limited and the cross-sectional shape formed in the case the fiber is cut perpendicularly to the longitudinal direction of the fiber may be true round, elliptical and the like.
  • the fiber may have a concentric core-sheath type structure in which the core part and sheath part are formed concentrically or an eccentric core-sheath type structure in which the core part and sheath part are formed eccentrically.
  • the fiber may have a structure in which multiple core parts exist in the case the fiber is cut perpendicularly to the longitudinal direction of the fiber.
  • the fiber of the invention is an elastic cooling fiber that has a Tg of no more than 22°C.
  • the Tg of the fiber may be no more than 22, 15, 10, 0, -10, -20, -30 or even -40 degrees C. These Tg limits may apply to the fiber itself, the composition from which the fiber is made (before the composition is spun or otherwise processed into fibers), the intermediate from which the composition is prepared, or any combination thereof.
  • the percent elongation achieved by the fiber may be from 200% to 300%.
  • the fibers of the invention are prepared from a composition that includes a reaction product of (i) a hydroxyl terminated intermediate, (ii) a diisocyanate and (iii) a linear alkylene glycol chain extender.
  • the hydroxyl terminated intermediate may include a polyester, a polyether, a polycarbonate or a combination thereof, wherein the intermediate has a Tg of no more than 22 degrees C.
  • the intermediate is derived from polyethylene glycol.
  • the diisocyanate may include diphenyl methane-4,4'-diisocyanate.
  • the linear alkylene glycol may include 1,6-butanediol and similar materials.
  • the hydroxyl terminated intermediate used in the invention is substantially free of, or even free of, polyether block amide copolymers and/or units of the same.
  • the fibers of the invention are prepared from a composition itself prepared from (i) an intermediate that includes and/or is derived from polyethylene glycol or an adipate derived from one or more alkylene diols and adipic acid, (ii) a diisocyanate that includes methylene diphenyl diisocyanate; and (iii) a linear alkylene glycol chain extender that may include 1,4-butanediol, 1,6-hexanediol, or a combination thereof.
  • the chain extender includes 1,4-butanediol
  • the adipate is prepared from 1,4-butanediol, 1,6-hexanediol, or a combination thereof.
  • the adipate is prepared from a mixture of 1,4-butanediol and 1,6-hexanediol.
  • the compositions used to prepare the fiber are: from 40 to 80, 40 to 70, 50 to 60, or even 55 to 58 or 56 to 57 percent by weight intermediate; from 20 to 50, 30 to 40, 30 to 35, or even 31 to 34 or 32 to 33 percent by weight diisocyanate; and from 4 to 25, 5 to 20, 5 to 15, or even from 8 to 11, or 9 to 10 percent by weight chain extender.
  • the fibers of the invention may be made from compositions that contain the material described above and which may also contain one or more polymer additives, including any of the additional additives described below.
  • the compositions may further include an antioxidant, a lubricant and/or processing aid, and may even have a metal containing catalyst.
  • the fibers of the invention are prepared from a composition itself prepared from (i) an intermediate that includes and/or is derived from polyethylene glycol, (ii) a diisocyanate that includes methylene diphenyl diisocyanate; and (iii) a linear alkylene glycol chain extender that includes 1,4-butanediol, 1,6-hexanediol, or a combination thereof.
  • the chain extender includes 1,4-butanediol.
  • compositions used to prepare the fiber are: from 40 to 80, 40 to 70, 40 to 60, or even 46 to 49 or 47 to 48 percent by weight intermediate; from 20 to 50, 30 to 50, 35 to 45, or even 40 to 43 or 41 to 42 percent by weight diisocyanate; and from 4 to 25, 5 to 20, 5 to 15, or even from 9 to 12, or 10 to 11 percent by weight chain extender.
  • composition from which the fiber is prepared may be a polymer alloy that includes: (a) a multiphase copolymer prepared by reacting a polymer and/or copolymer segment with at least one other polymer and/or copolymer segment; (b) a polymer blend prepared mixing a polymer and/or copolymer with at least one other polymer and/or copolymer, wherein each of the polymers and/or copolymers is compatible and/or miscible in one another; or (c) combinations thereof.
  • the polymer alloy may be derived from the reaction of: (i)(a) a polyol; (i)(b) a polyester intermediate itself derived from a polyol and a dicarboxylic acid; (ii) at least one diisocyanate; and (iii) at least one chain extender.
  • the TPU polymer type used in this invention can be any conventional TPU polymer that is known to the art and in the literature as long as it (meaning the fiber itself, the composition from which the fiber is made, and/or the intermediate used to prepare the composition) exhibits the Tg, percent elongation, and/or elasticity described above. While not wishing to be bound by theory, Applicants consider that compositions which meet these requirements are expected to provide the same cooling effect demonstrated by the specific examples included in this application, or in the alternative, when at least one or more of the additional parameters described herein is met.
  • Suitable TPU polymers are generally prepared by reacting a polyisocyanate with an intermediate such as a hydroxyl terminated polyester, a hydroxyl terminated polyether, a hydroxyl terminated polycarbonate or mixtures thereof, with one or more chain extenders, all of which are well known to those skilled in the art.
  • Suitable polyester intermediates also include various lactones such as polycaprolactone typically made from ⁇ -caprolactone and a bi-functional initiator such as diethylene glycol.
  • the dicarboxylic acids of the desired polyester can be aliphatic, cycloaliphatic, aromatic, or combinations thereof.
  • Suitable dicarboxylic acids which may be used alone or in mixtures generally have a total of from 4 to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cyclohexane dicarboxylic, and the like.
  • Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used.
  • Adipic acid is a preferred acid.
  • the glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, and have a total of from 2 to 12 carbon atoms, and include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like, 1,4-butanediol is a preferred glycol.
  • Hydroxyl terminated polyether intermediates are polyether polyols derived from a diol or polyol having a total of from 2 to 15 carbon atoms, in some embodiments an alkyl diol or glycol which is reacted with an ether (or an epoxide) which comprises an alkylene oxide group having from 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide or mixtures thereof.
  • ether or an epoxide
  • hydroxyl functional polyether can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide. Primary hydroxyl groups resulting from ethylene oxide are more reactive than secondary hydroxyl groups and thus are preferred.
  • Useful commercial polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, poly(propylene glycol) comprising propylene oxide reacted with propylene glycol, poly(tetramethylene glycol) comprising water reacted with tetrahydrofuran (PTMEG).
  • PTMEG is the preferred polyether intermediate.
  • Polyether polyols further include polyamide adducts of an alkylene oxide and can include, for example, ethylenediamine adduct comprising the reaction product of ethylenediamine and propylene oxide, diethylenetriamine adduct comprising the reaction product of diethylenetriamine with propylene oxide, and similar polyamide type polyether polyols.
  • Copolyethers can also be utilized in the current invention.
  • Typical copolyethers include the reaction product of THF and ethylene oxide or THF and propylene oxide. These are available from BASF as Poly THF B, a block copolymer, and poly THF R, a random copolymer.
  • the various polyether intermediates generally have a number average molecular weight (Mn) as determined by assay of the terminal functional groups which is an average molecular weight greater than 700, such as from 700 to 10,000, from 1000 to 5000, or from 1000 to 2500.
  • a particular desirable polyether intermediate is a blend of two or more different molecular weight polyethers, such as a blend of 2000 M n and 1000 M n PTMEG.
  • compositions of the present invention are prepared from polyethleneglycol (PEG).
  • the intermediate is a polyester made from the reaction of adipic acid with a 50/50 blend of 1,4-butanediol and 1,6-hexanediol.
  • the polycarbonate-based polyurethane resin of this invention may be prepared by reacting a diisocyanate with a blend of a hydroxyl terminated polycarbonate and a chain extender.
  • the hydroxyl terminated polycarbonate can be prepared by reacting a glycol with a carbonate.
  • U.S. Patent No. 4,131,731 discloses of hydroxyl terminated polycarbonates and their preparation. Such polycarbonates are linear and have terminal hydroxyl groups with essential exclusion of other terminal groups.
  • the essential reactants are glycols and carbonates. Suitable glycols are selected from cycloaliphatic and aliphatic diols containing 4 to 40, and or even 4 to 12 carbon atoms, and from polyoxyalkylene glycols containing 2 to 20 alkoxy groups per molecule with each alkoxy group containing 2 to 4 carbon atoms.
  • the diols used in the reaction may be a single diol or a mixture of diols depending on the properties desired in the finished product.
  • Polycarbonate intermediates which are hydroxyl terminated are generally those known to the art and in the literature.
  • Suitable carbonates are selected from alkylene carbonates composed of a 5 to 7 member ring. Suitable carbonates for use herein include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-ethylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 2,3-pentylene carbonate, and 2,4-pentylene carbonate.
  • dialkylcarbonates can contain 2 to 5 carbon atoms in each alkyl group and specific examples thereof are diethylcarbonate and dipropylcarbonate.
  • Cycloaliphatic carbonates, especially dicycloaliphatic carbonates can contain 4 to 7 carbon atoms in each cyclic structure, and there can be one or two of such structures.
  • the other can be either alkyl or aryl.
  • the other can be alkyl or cycloaliphatic.
  • suitable diarylcarbonates which can contain 6 to 20 carbon atoms in each aryl group, are diphenylcarbonate, ditolylcarbonate, and dinaphthylcarbonate.
  • the reaction is carried out by reacting a glycol with a carbonate, for example an alkylene carbonate in the molar range of 10:1 to 1:10, but preferably 3:1 to 1:3 at a temperature of 100°C to 300°C and at a pressure in the range of 0.1 to 300 mm of mercury in the presence or absence of an ester interchange catalyst, and may also be carried out while removing low boiling glycols by distillation.
  • a carbonate for example an alkylene carbonate in the molar range of 10:1 to 1:10, but preferably 3:1 to 1:3
  • a temperature of 100°C to 300°C and at a pressure in the range of 0.1 to 300 mm of mercury in the presence or absence of an ester interchange catalyst
  • the hydroxyl terminated polycarbonates are prepared in two stages.
  • a glycol is reacted with an alkylene carbonate to form a low molecular weight hydroxyl terminated polycarbonate.
  • the lower boiling point glycol is removed by distillation at 100°C to 300°C, preferably at 150°C to 250°C, under a reduced pressure of 10 to 30 mm Hg, preferably 50 to 200 mm Hg.
  • a fractionating column may be used to separate the by-product glycol from the reaction mixture.
  • the by-product glycol can be taken off the top of the column and the unreacted alkylene carbonate and glycol reactant may be returned to the reaction vessel as reflux.
  • a current of inert gas or an inert solvent can be used to facilitate removal of by-product glycol as it is formed.
  • amount of by-product glycol obtained indicates that degree of polymerization of the hydroxyl terminated polycarbonate is in the range of 2 to 10
  • the pressure is gradually reduced to 0.1 to 10 mm Hg and the unreacted glycol and alkylene carbonate are removed.
  • Molecular weight (Mn) of the hydroxyl terminated polycarbonates can vary from 500 to 10,000 but in a preferred embodiment, it will be in the range of 500 to 2500.
  • the second necessary ingredient to make the TPU polymer of this invention is a polyisocyanate.
  • the polyisocyanates of the present invention generally have the formula R(NCO) n where n is generally from 2 to 4 with 2 being highly preferred inasmuch as the composition is a thermoplastic.
  • R can be aromatic, cycloaliphatic, and aliphatic, or combinations thereof generally having a total of from 2 to 20 carbon atoms.
  • aromatic diisocyanates examples include diphenyl methane-4, 4'-diisocyanate (MDI), H 12 MDI, m-xylylene diisocyanate (XDI), m-tetramethyl xylylene diisocyanate (TMXDI), phenylene-1, 4-diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI), and diphenylmethane-3, 3'-dimethoxy-4, 4'-diisocyanate (TODI).
  • MDI diphenyl methane-4, 4'-diisocyanate
  • H 12 MDI H 12 MDI
  • XDI m-xylylene diisocyanate
  • TMXDI m-tetramethyl xylylene diisocyanate
  • PPDI 4-diisocyanate
  • NDI 1,5-naphthalene diisocyanate
  • TODI diphenyl
  • Suitable aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), hexamethylene diisocyanate (HDI), 1,6-diisocyanato-2,2,4,4-tetramethyl hexane (TMDI), 1,10-decane diisocyanate, and trans-dicyclohexylmethane diisocyanate (HMDI).
  • IPDI isophorone diisocyanate
  • CHDI 1,4-cyclohexyl diisocyanate
  • HDI hexamethylene diisocyanate
  • TMDI 1,6-diisocyanato-2,2,4,4-tetramethyl hexane
  • HMDI trans-dicyclohexylmethane diisocyanate
  • a highly preferred diisocyanate is MDI containing less than about 3% by weight of ortho-para (2,4) iso
  • the third necessary ingredient to make the TPU polymer of this invention is the chain extender.
  • Suitable chain extenders are lower aliphatic or short chain glycols having from 2 to 10 carbon atoms and include for instance ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, cis-trans-isomers of cyclohexyl dimethylol, neopentyl glycol, 1,4-butanediol, 1,6-hexandiol, 1,3-butanediol, and 1,5-pentanediol.
  • the present invention requires a linear alkylene glycol chain extender, but in some embodiments additional chain extenders may be used in combination with the linear alkylene glycol chain extender. In such embodiments, aromatic glycols can be used as the chain extender. Benzene glycol (HQEE) and xylylene glycols are suitable chain extenders for use in making the TPU of this invention. Xylylene glycol is a mixture of 1,4-di(hydroxymethyl) benzene and 1,2-di(hydroxymethyl) benzene.
  • Benzene glycol is the preferred aromatic chain extender and specifically includes hydroquinone, bis(beta-hydroxyethyl) ether also known as 1,4-di(2-hydroxyethoxy) benzene; resorcinol, bis(beta-hydroxyethyl) ether also known as 1,3-di(2-hydroxyethyl) benzene; catechol, i.e., bis(beta-hydroxyethyl) ether also known as 1,2-di(2-hydroxyethoxy) benzene; and combinations thereof.
  • the preferred chain extender is 1,4-butanediol.
  • the above three necessary ingredients may be reacted in the presence of a catalyst.
  • TPU polymers of this invention can be made by any of the conventional polymerization methods well known in the art and literature.
  • Useful additives can be utilized in suitable amounts in the TPU's described herein, where such additives may be added either before, during, or after the preparation of the TPU.
  • additional additives include opacifying pigments, colorants, mineral fillers, stabilizers, lubricants, UV absorbers, processing aids, and other additives as desired.
  • Useful opacifying pigments include titanium dioxide, zinc oxide, and titanate yellow
  • useful tinting pigments include carbon black, yellow oxides, brown oxides, raw and burnt sienna or umber, chromium oxide green, cadmium pigments, chromium pigments, and other mixed metal oxide and organic pigments.
  • Useful fillers include diatomaceous earth (superfloss) clay, silica, talc, mica, wallastonite, barium sulfate, and calcium carbonate.
  • useful stabilizers such as antioxidants can be used and include phenolic antioxidants
  • useful photostabilizers include organic phosphates, and organotin thiolates (mercaptides).
  • Useful antioxidants also include stearically hindered phenolic antioxidants.
  • Useful lubricants include metal stearates, paraffin oils and amide waxes, for example, alkylene bisstearamides such as N,N' ethylene bisstearamide and esters of nonanic esters.
  • Useful UV absorbers include 2-(2'-hydroxyphenol) benzotriazoles and 2-hydroxybenzophenones. Typical TPU flame retardants can also be added.
  • the cooling effect of the fiber may be expressed in terms of effective cooling power. While there are various means of measuring the cooling effect provided by the invention, this application includes details on two approaches to measure this effect. The first looks at the cooling effect provided by fabrics made from the fibers described herein, where the fabric and the area of "skin" in contact with the fabric, in this case a test surface taking the place of a person's skin, are both and where a constant wind is blowing across the fabric. While the specific conditions involved are considered to be important primarily for the purposes of comparing results, these type of evaluations can be of course be done at various ambient temperatures, levels of humidity, wind speed, starting temperature of the "skin", whether the "skin” heat source is left on or removed, and various other variables.
  • this parameter is of course measured with respect to a specific area.
  • Another approach follows the basic test methodology described above but adds the additional variable of sweat, various rates of moisture release from the "skin" over the course of the test. Using these types of tests, one can measure the amount of energy it takes to maintain the temperature of the "skin” under various conditions, or in the alternative, measure the rate at which the "skin” temperature drops if no heat source is applied, thus giving an indication of the cooling power of the fabric involved.
  • Specific test conditions and results are provided in the examples section of this specification. It is important to note that regardless of the testing approach used, and the specific conditions selected, all testing conducted to date has shown that fabrics made from the fibers described herein exhibit significantly higher cooling powers and allow for faster and greater temperature drops than the comparative materials also tested.
  • the fibers of the present invention when evaluated by the methods described above, specifically where the fabric is placed on the test skin surface, with an active heat source working to maintain skin surface temperature, 30% relative humidity, a 3 m/s wind speed, and an ambient temperature of 15 degrees C, provide a cooling power of at least 31 watts for a test are of 629 cm 2 , or stated differently a cooling power of at least 49 watts per square meter. That is, at least 49 watts of power per square meter of area is required to maintain skin temperature, giving an indication of the cooling effect the fabric would provide to a person where the fabric against their skin, compared to other materials (nylon and polyester, for example, could not break the 31 watt limit under the exact same test conditions).
  • This cooling power may also be at least 34 watts for a test area of 629 cm 2 , at least 55 watts per square meter, where the fiber is a monofilament and is not semi-dull. The same limits apply to testing conducted at 50% relative humidity and 3 m/s wind speed, as well as at 5 m/s wind speed at 50% relative humidity.
  • the fiber of the present invention when evaluated by the methods described above, specifically where the fabric is placed on the test skin surface, with an active heat source working to maintain skin surface temperature, 50% relative humidity, a 0.3 m/s wind speed, and an ambient temperature of 15 degrees C, provide a cooling power of at least 13 or 14 watts for a test area of 629 cm 2 , at least 21 or 22 watts per square meter.
  • a method of producing the fiber excellent in cool contact feeling of the invention is not particularly limited and conventionally known methods such as a method of producing it by producing resin pellets containing the thermoplastic elastomer and the inorganic filler and melting and spinning, using the obtained resin pellets, may be employed.
  • the core-sheath type composite yarn may also be produced by, for example, loading resin pellets containing the dyeable resin, the thermoplastic elastomer, and the inorganic filler into a composite spinning apparatus and melting and spinning them.
  • the invention provides a method of making a fiber that includes the steps of: (I) preparing an elastomer resin in an internal mixing device.
  • the elastomer resin is prepared by reacting: (i) a hydroxyl terminated intermediate, (ii) a diisocyanate and (iii) a linear alkylene glycol chain extender.
  • the intermediate may be a polyester, a polyether, a polycarbonate or a combination thereof, wherein the intermediate has a Tg of no more than 22 degrees C.
  • the second step, (II) is melt-spinning the elastomer resin into a fiber, for example, a monofilament or multifilament fiber. In some embodiments, the fiber is a monofilament fiber. All of the various features and embodiments discussed above with regards to the fiber and the composition used to prepare it apply here as well.
  • the fiber of the invention may be used in form of a fabric such as a knit, a textile, and a bonded textile.
  • the resulting fabric is excellent in cool contact feeling while also possessing the excellent elasticity of the fiber.
  • the fabric excellent in cool contact feeling of the invention may solely comprise the fiber excellent in cool contact feeling of the invention and in other embodiments may comprise the fiber and another fiber twisted together for improving the factors required for specific applications.
  • Such optional co-fibers are not particularly limited and examples include polyamide type resins such as nylon 6 and nylon 12, polyesters, cotton, and rayon.
  • the invention includes fabrics made from any of the fibers described herein, including woven fabric, non-woven fabric, knitted fabric, and combinations thereof.
  • the fabrics of the invention are woven fabrics.
  • the fabrics of the invention are non-woven fabrics.
  • the fabrics of the invention are knitted fabrics.
  • the invention includes fabrics that further contain one or more additional fibers, other than the fibers of the invention.
  • the fabric may be from 10 to 80 percent by weight of these additional fibers, or no more than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, or 10% of these additional fibers.
  • no additional fibers are present.
  • these additional fibers may be nylon fibers, polyester fibers, rayon fibers, acrylic fibers, and combinations thereof.
  • an additional benefit of the invention is the improved mold-ability of fabrics that contain the fibers described herein.
  • the fabric of the invention can be successful molded at lower temperatures and/or in less time, thus improving the ability to protect the fabric, dye, etc of the fabric which may be damaged by the high temperatures and/or low exposure time required by more conventional fabrics in order to successfully mold them.
  • the fabrics of the invention may be molded at temperatures of no more than 150 or even 140 degrees C, and/or where the molding is complete in less than 20, 15 or even 10 seconds.
  • a minimum level of the fibers of the invention must be present in the fabric for it to provide these benefits.
  • this lower limit is 40%, 50%, 60% or even 80% where the percentage represent the percent by weight of the fibers in the fabric that must be the fibers of the present invention.
  • this lower limit is 40%, 50%, 60% or even 80% where the percentage represent the percent by weight of the fibers in the fabric that must be the fibers of the present invention.
  • a much smaller amount of the fibers of the invention in a fabric will improve that fabric's mold-ability.
  • SpandexTM and similar materials are not moldable at low temperatures, and that fibers of these materials are not even knittable into fabrics unless a positive feeder is used, an expensive piece of equipment required due to the over-elasticity of SpandexTM fibers.
  • the fiber excellent in cool contact feeling of the invention and the fabric excellent in cool contact feeling of the invention may be used for producing articles including clothing.
  • the articles of the invention exhibit excellent elasticity, provide a cooling sensation to the wearer, and have no unpleasant and/or sticky feeling even at times of wetting.
  • the present invention does not require the addition of the inorganic filler to make the clothing free from a sticky feeling at the time of wetting, as other fibers used in clothing with similar cooling effects may do.
  • the present invention is extremely suitable for underwear.
  • the clothing excellent in cool contact feeling of the invention may be produced using the fiber excellent in cool contact feeling entirely and it is particularly preferable to be clothing excellent in cool feeling comprising a fabric having a reversible structure and excellent in refreshing feeling, 30 to 70% by number of total loops comprising the fiber excellent in cool contact feeling, the loops comprising the fiber excellent in cool contact feeling being arranged in a skin contact side (hereinafter, also referred to as refreshing clothing).
  • the ratio of the number of loops comprising the fiber excellent in cool contact feeling is controlled within a prescribed range and such loops comprising the fiber excellent in cool contact feeling are arranged only in the skin contact side, so that the clothing can have an effect of preventing unpleasant feeling caused by much sweating.
  • the refreshing clothing comprising the fabric having a reversible structure
  • it can cause sensation of cool feeling at the time of wearing and give refreshing feeling and simultaneously it can prevent unpleasant feeling due to wet feeling at the time of sweating and prevent sticking of the fabric to the skin due to deterioration of the separation from the skin by controlling the ratio of the number of loops comprising the fiber excellent in cool contact feeling to be within a prescribed range.
  • the loops comprising the fiber excellent in cool contact feeling are arranged only in the skin side, so that the fiber excellent in cool contact feeling can be brought into direct contact with the skin and clothing with further improved refreshing feeling and cool contact feeling can be produced.
  • the lower limit of the ratio of the loops of the fiber excellent in cool contact feeling may be 30% of the total number of loops, and the upper limit may be 70% or even higher, such as 75%, 80%, 90% or even 100% of the total number of loops. If it is less than 30%, the effect to cause refreshing feeling and cool contact feeling may become insufficient in some cases.
  • the high level can be obtained with the present invention without causing any unpleasant feeling due to wet feeling in the case the skin or the clothing is wetted because of sweating.
  • the refreshing article for example, the clothing, may contain the thermoplastic elastomer and an inorganic filler, but in other embodiments is substantially free of, to even free of, any inorganic filler.
  • the fiber excellent in cool contact feeling may be used in combination with another fiber.
  • the lower limit of the content of the thermoplastic elastomer in the fiber excellent in cool contact feeling may be 50% by weight. If it is less than 50% by weight, sufficient cool contact feeling may not be caused in some cases.
  • the content of the fiber of the invention is present in the fabric and articles is at least 15%, 25%, 35%, 45%, 55%, 65%, 75%, 85%, or even 95% by weight. While not wishing to be bound by theory, it is believed that some minimum fiber content in the fabric and/or article in question must be the fiber of the invention for the cooling effect to be noticeable. This minimum required content may vary across the various formulations included in the present invention, but in some embodiments may be fairly consistent across the various formulations. This minimum content may be any of the percentages described above.
  • the loops comprising the fiber excellent in cool contact feeling are preferable to be arranged only in the skin side. Arrangement in such a manner makes the loops comprising the fiber excellent in cool contact feeling have mainly contact with the skin and causes the cool contact feeling and refreshing feeling, and as described later, arrangement of loops comprising a hydrophobic fiber in the outside improves the diffusion and evaporating property of the heat and water emitted from the skin.
  • the loops other than the loops comprising the fiber excellent in cool contact feeling are preferably the loops comprising a hydrophobic fiber. Since the loops comprising the fiber excellent in cool contact feeling are arranged only in the skin side, the loops comprising a hydrophobic fiber are arranged mainly in the outside.
  • the hydrophobic fiber means a chemical fiber having a official water percentage of 5.0% or less.
  • fibers comprising polypropylenes (official water percentage: 0%), polyesters (0.4%), acrylic resins (2.0%), nylon (4.5%), and vinylon (5.0%) can be exemplified. They may be used alone or two or more kinds of them may be used in combination.
  • the official water percentage means water percentage at 20 degrees C. and 65% RH.
  • the articles and/or clothing of the invention may contain natural fibers such as cotton and flax, and semi-synthesized fibers such as rayon and acetate based on the necessity besides the fiber excellent in cool contact feeling and the hydrophobic fiber.
  • the articles and/or clothing of the invention has an air permeability of the refreshing clothing from 200 cm 3 /cm 2 /sec up to 500 cm 3 /cm 2 /sec. If it is less than 200 cm 3 /cm 2 /sec, the air permeability may be deteriorated and the diffusion of heat and evaporation of sweat emitted from the skin may possibly be inhibited and if it is more than 500 cm 3 /cm 2 /sec, transfer of the heat and water through the clothing may not be carried out sufficiently and contrarily the outer air may penetrate.
  • the air permeability can be measured by using a air permeability tester according to JIS L 1096 A method.
  • the upper limit of the weight per square-meter may be 120, 100 or even 90 g/m 2 .
  • the mechanism at work may be stifled and so the cooling feeling may possibly be deteriorated.
  • a method of producing the articles and/or clothing of the invention is not particularly limited and for example, conventionally known methods such as a method of producing clothing by weaving the fiber excellent in cool contact feeling of the invention can be employed. These materials may also be produced by the conventionally known methods of sewing, cutting and the like, using the fabrics with the reversible structure obtained by the above-mentioned manner.
  • Underwear excellent in cool contact feeling can be produced by using the fiber of the invention or the fabric of the invention.
  • the clothing excellent in cool contact feeling of the invention can be used as underwear.
  • the invention may provide any one or more of the benefits described above for the fiber, fabric, article, and/or clothing.
  • the present invention includes stockings, gloves, face masks, mufflers and the like that may be produced by using the fiber of the invention or the fabric excellent in cool contact feeling of the invention. They are brought into direct contact with the skin and therefore, they can cause a particularly excellent effect.
  • the invention includes an article made from the fabrics described above.
  • various garments can be made with the fabrics of this invention.
  • the fabric is used in making undergarments or tight fitting garments, for which the fabrics of this invention are well-suited due to the comfort and cooling effect provided by the fiber.
  • Undergarments such as bras and T-shirts as well as sport garments used for activities such as running, skiing, cycling, or other sports, can benefit from the properties of these fibers.
  • Garments worn next to the body benefit from the elasticity and cooling effect the invention provides. It will be understood by those skilled in the art that any garment can be made from the fabric and fibers of this invention.
  • the fibers described herein are used to make one or more of any number of garments and articles including but not limited to: sports apparel, such as shorts, including biking, hiking, running, compression, training, golf, baseball, basketball, cheerleading, dance, soccer and/or hockey shorts; shirts, including any of the specific types listed for shorts above; tights including training tights and compression tights; swimwear including competitive and resort swimwear; bodysuits including wrestling, running and swimming body suits; and footwear. Additional embodiments include work wear such as shirts and uniforms. Additional embodiments include intimates including bras, panties, men's underwear, camisoles, body shapers, nightgowns, panty hose, men's undershirts, tights, socks and corsetry.
  • sports apparel such as shorts, including biking, hiking, running, compression, training, golf, baseball, basketball, cheerleading, dance, soccer and/or hockey shorts
  • shirts including any of the specific types listed for shorts above
  • tights including training tights and compression tights
  • swimwear including
  • Additional embodiments include medical garments and articles including: hosiery such as compression hosiery, diabetic socks, static socks, and dynamic socks; therapeutic burn treatment bandages and films; wound care dressings; medical garments. Additional applications include military applications that mirror one or more of the specific articles described above. Additional embodiments include bedding articles including sheets, blankets, comforters, mattress pads, mattress tops, and pillow cases.
  • hosiery such as compression hosiery, diabetic socks, static socks, and dynamic socks
  • therapeutic burn treatment bandages and films therapeutic burn treatment bandages and films
  • wound care dressings medical garments.
  • Additional applications include military applications that mirror one or more of the specific articles described above.
  • Additional embodiments include bedding articles including sheets, blankets, comforters, mattress pads, mattress tops, and pillow cases.
  • the article of the invention is a garment and the fibers that make up the fabric in the garment are arranged in the garment as to be in direct contact with the skin of a wearer of said garment. This allows the wearer to gain the full benefit of the cooling effect provided by the invention.
  • the invention also provides a method of providing a cooling effect in an article, such as a garment, that comes into direct contact with human skin, comprising the steps of: (I) preparing a fabric comprising the fiber of claim 1; (II) preparing an article that comprises said fabric; and (II) bringing said article into direct contact with human skin.
  • the diameter refers to the diameter of the sleeve the fabric creates while the length is the actual length of the sample. For the fabric weight, each sample was weighed and then, using the other measurements reported, a weight in terms of grams per meter squared was calculated for each fabric.
  • 2 - This fiber is commercially available from Invista TM .
  • 3 - Fiber A is prepared from a polyalkylene glycol, an alkylene diol, and MDI.
  • 4 - Fiber B is prepared from alkylene diol adipate, an alkylene diol, and MDI.
  • 5 - Fiber C is a multifilament version of Fiber B, and is chemically identical to Fiber B.
  • 6 - Fiber D is Fiber B but with a commercially available dulling agent added.
  • Comparative Example 1 is a baseline and represents no fiber and/or fabric. Comparative Examples 2 and 3 are comparative materials that do not represent the invention. Examples 4, 5, 6 and 7 represent various embodiments of the invention.
  • the sweating thermal mannequin is placed inside the climatic chamber, which is set to 15 degrees C. Testing was carried out at 30% and 50% relative humidity, with winds speeds of 0.3 m/s, 3 m/s and 5 m/s. A wind speed of 0.3 m/s is the normal condition inside the climatic chamber and so indicates the high speed fan is in the off position.
  • Circular knitted, open-ended sock samples of each material also referred to as sleeves, are placed on the test surface of the sweating thermal mannequin, in this case the forearm of the mannequin. Samples are placed on the test surface for testing and then are removed and replaced with the next sample. As noted above, clamps are used to secure each sample to the forearm of the sweating thermal mannequin and care is taken to ensure the samples are placed with comparable levels of tension and fabric density.
  • the chamber is brought up to the desired conditions.
  • the test surface covered with the sample of fabric being testing, is heated to the desired starting skin temperature of either 31 or 34 degrees C, selected to approximate human skin temperature, and if wind is included in the test conditions, the fan is turned on to the desired setting.
  • the test period begins by monitoring the amount of power required by the heating element to maintain the set test surface temperature. This amount of power is measured in Watts and is referred to as the cooling power of the fabric being tested under the given conditions of the test. The reported cooling power the power the system stabilized at under the given test conditions.
  • the sample fabric was replaced with a different sample and the testing was repeated, changing conditions as needed.
  • Example 1 For the Example 1 baseline, the test was carried out with a bare, uncovered test surface, providing the effect one could expect from bare skin. This bare skin baseline was included in the testing for purposes of comparison.
  • Table 2 Summary of Cooling Power Test Conditions using the Mannequin Condition Set 1 Chamber Temp [C] Chamber Humidity [%] Wind Speed [m/s] Target Skin Temp 2 [C] Examples Tested at these Conditions I 15 50 3.0 34 1,2,3,4,5,6,7 II 15 50 5.0 31 1,2,3,4,5,6,7 III 15 30 3.0 34 1,2,3,4,5,6,7 IV 15 50 0.3 34 1,2,3,4,5,6,7 V 15 50 0.3 34 1,2,3,4,5,6,7 VI 15 30 0.3 34 1,2,3,4,5,6,7 1 - These condition sets were carried out in the testing in the following order: IV, I, V, II, VI, III.
  • Condition Sets IV and V are identical, and were not run consecutively, thus providing a duplicate set of data that shows the repeatability of the results and relative difference between samples.
  • the target skin temperature for this testing is always 34 degrees C except for the Condition Set where the wind is at 5 m / s. Under these conditions a 31 degrees C skin temperature is used to ensure the system, which has limited heating capabilities, can maintain the desired temperature.
  • the results show that the fibers of the invention, and more specifically fabric made from such fibers, provide a cooling effect, as measured by cooling power, greater than that of conventional synthetic fibers, and more specifically fabric made from conventional synthetic fibers.
  • the results show that the fibers of the invention, and more specifically fabric made from such fibers, provide a cooling effect, as measured by cooling power, comparable to that seen in the baseline, bare skin example.
  • the present invention provides fibers, fabrics and various garments, including the means of making such articles that would give a wearer whose skin comes into contact with said articles, a cooling sensation similar to that felt when no fabric is in contact with the skin that is when the skin is bare.
  • An additional set of testing is also included that adds the additional variable of moisture release from the test surface during the testing.
  • a sweating thermal foot model was used, where the model was equipped with similar controls to the mannequin described above.
  • the moisture releases used in this testing are designed to simulate different sweat rates that a person would experience when wearing a garment made of the test fabric, for example, during exercise, and to see what impact if any this has on the cooling power of the fabric.
  • Table 1 The same seven examples listed in Table 1 were tested here. The conditions used in this testing are summarized in the table below. For each test condition, the system was allowed to stabilize for 30 minutes without any wind or moisture release, during which time the cooling power of the fabric was measured. The moisture release was then started and the system was again allowed to stabilize over 30 minutes, during which the cooling power was measured. Finally, the wind condition was added and the system was again allowed to stabilize over 30 minutes, during which the cooling power was measured.
  • each test condition included three distinct measurements of the cooling power, one with no wind or moisture release (A), one with moisture release and no wind (B), and one with both the target moisture release and wind (C).
  • Table 5A - Summary of Cooling Power Test Results 1 Example Condition Set VII Condition Set VIII Condition Set IX (A) (B) (C) (A) (B) (C) (A) (B) (C) 2 - Comparative 3.9 4.9 11.0 4.2 6.5 13.0 4.1 7.8 15.3 3 - Comparative 4.3 5.3 11.6 4.3 6.9 13.4 4.7 8.6 16.2 4 - Inventive 5.2 6.4 15.2 5.2 8.1 16.8 4.9 8.6 19.7 5 - Inventive 4.9 6.1 14.6 4.9 6.5 16.2 5.0 6.6 17.5 6 - Inventive 4.6 5.5 12.6 4.8 7.6 15.5 4.7 10.9 19.5 7 - Inventive 4.5 5.8 1
  • the fibers of the invention and more specifically fabric made from such fibers, provide a cooling effect, as measured by cooling power, greater than that of conventional synthetic fibers, and more specifically fabric made from conventional synthetic fibers, particularly when the both moisture release and wind conditions are present.
  • cooling power greater than that of conventional synthetic fibers, and more specifically fabric made from conventional synthetic fibers, particularly when the both moisture release and wind conditions are present.
  • the results reinforce the conclusion that articles made from the fibers of the invention would provide a person wearing said articles, or otherwise bring their skin into contact with said articles, a cooling effect.
  • 2 - BDO Adipate is an adipate prepared from 1,4-butanediol and adipic acid.
  • 3 - HDO Adipate is an adipate prepared from 1, 6-hexandiol and adipic acid.
  • 4 - BDO / HDO Adipate is an adipate prepared from adipic acid and a mixture of 114-butanediol and 1, 6-hexandiol.
  • 2 - BDO Adipate is an adipate prepared from 1,4-butanediol and adipic acid.
  • 3 - HDO Adipate is an adipate prepared from 1,6-hexandiol and adipic acid.
  • 4 - BDO / HDO Adipate is an adipate prepared from adipic acid and a mixture of 114-butanediol and 1,6-hexandiol.

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Claims (16)

  1. Fibre préparée à partir d'une composition comprenant le produit de réaction de :
    (i) un intermédiaire terminé par hydroxyle, comprenant un poly(ester), un poly(éther), un poly(carbonate) ou l'une de leurs combinaisons, dans laquelle l'intermédiaire a une Tg de pas plus de 22 degrés C ;
    (ii) un diisocyanate ; et
    (iii) un allongeur de chaîne comprenant un alkylène glycol linéaire,
    dans laquelle la Tg de la composition à partir de laquelle la fibre est préparée n'est de pas plus de 22 degrés C.
  2. Fibre selon la revendication 1, dans laquelle (i) l'intermédiaire terminé par hydroxyle est sensiblement dépourvu de copolymères amide à bloc poly(éther).
  3. Fibre selon l'une quelconque des revendications 1 ou 2, dans laquelle la fibre a un allongement en pourcentage de 200 % à 300 %.
  4. Fibre selon l'une quelconque des revendications 1 à 3, dans laquelle la fibre a une puissance de refroidissement effective d'au moins 49 watts par mètre carré, mesurée à 30 % d'humidité relative et à une vitesse du vent de 3 m/s.
  5. Fibre selon la revendication 1, dans laquelle la fibre est sensiblement dépourvue de charges inorganiques.
  6. Fibre selon l'une quelconque des revendications 1 à 5, dans laquelle (i) l'intermédiaire terminé par hydroxyle comprend du poly(éthylène glycol), (ii) le diisocyanate comprend du diisocyanate de méthylène diphényle ; et (iii) l'allongeur de chaîne alkylène glycol linéaire comprend du 1,4-butanediol, du 1,6-hexanediol, ou leurs combinaisons.
  7. Fibre selon l'une quelconque des revendications 1 à 6, dans laquelle la composition à partir de laquelle la fibre est préparée est un alliage de polymère comprenant :
    (a) un copolymère multiphasique préparé en faisant réagir un polymère et/ou un segment de copolymère avec au moins un autre polymère et/ou segment de copolymère ;
    (b) un mélange de polymères préparé en mélangeant un polymère et/ou un copolymère avec au moins un autre polymère et/ou copolymère, chacun des polymères et/ou copolymères étant compatible et/ou miscible les uns avec les autres ; ou
    (c) leurs combinaisons.
  8. Fibre selon la revendication 7, dans laquelle ledit alliage de polymère est dérivé de la réaction de (i) (a) un polyol ; (i) (b) un intermédiaire poly(ester) dérivé d'un polyol et d'un acide dicarboxylique ; (ii) au moins un diisocyanate ; et (iii) au moins un allongeur de chaîne.
  9. Etoffe comprenant la fibre selon la revendication 1.
  10. Etoffe selon la revendication 9, dans laquelle ladite étoffe comprend en outre une ou plusieurs fibres additionnelles, autres que la fibre selon la revendication 1, l'étoffe représentant 10 à 80 pour cent en poids de ces fibres additionnelles.
  11. Etoffe selon la revendication 10, dans laquelle les fibres additionnelles sont choisies dans le groupe constitué des fibres de nylon, des fibres de poly(ester), des fibres de rayonne, des fibres acryliques, et de leurs combinaisons.
  12. Article comprenant l'étoffe selon la revendication 9.
  13. Article selon la revendication 12, dans lequel l'article est un vêtement et dans lequel les fibres de l'étoffe sont agencées dans ledit vêtement pour être en contact direct avec la peau d'un porteur dudit vêtement.
  14. Procédé permettant de conférer un effet de refroidissement dans un article qui vient en contact direct avec la peau humaine, comprenant les étapes de :
    I. préparation d'une étoffe comprenant la fibre selon la revendication 1 ;
    II. préparation d'un article qui comprend ladite étoffe ;
    III. mise en contact dudit article directement avec la peau humaine.
  15. Procédé de fabrication d'une fibre comprenant les étapes de :
    I. préparation d'une résine élastomère dans un dispositif de mélange interne dans lequel ladite résine élastomère est préparée en faisant réagir :
    (i) un intermédiaire terminé par hydroxyle, comprenant un poly(ester), un poly(éther), un poly(carbonate) ou l'une de leurs combinaisons, dans lequel l'intermédiaire a une Tg de pas plus de 22 degrés C ;
    (ii) un diisocyanate ; et
    (iii) un allongeur de chaîne comprenant un alkylène glycol linéaire,
    dans lequel la Tg de la composition à partir de laquelle la fibre est préparée n'est de pas plus de 22 degrés C ; et
    II. filage à l'état fondu de ladite résine élastomère en une fibre monofilament ou multifilament.
  16. Procédé de fabrication d'une fibre comprenant les étapes de :
    I. préparation d'une résine élastomère dans un dispositif de mélange interne dans lequel ladite résine élastomère est préparée en faisant réagir :
    (i) un intermédiaire terminé par hydroxyle, comprenant un poly(ester), un poly(éther), un poly(carbonate) ou l'une de leurs combinaisons, dans lequel l'intermédiaire a une Tg de pas plus de 22 degrés C ;
    (ii) un diisocyanate ; et
    (iii) un allongeur de chaîne comprenant un alkylène glycol linéaire,
    dans lequel la Tg de la composition à partir de laquelle la fibre est préparée n'est de pas plus de 22 degrés C ; et
    II. filage à l'état fondu de ladite résine élastomère en une fibre monofilament ou multifilament ;
    III. traitement de ladite fibre, facultativement en combinaison avec une ou plusieurs autres fibres, en une étoffe.
EP12714913.6A 2011-04-15 2012-04-10 Fibres d'élastomère et leurs procédés de fabrication et d'utilisation Active EP2697415B1 (fr)

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US201161475727P 2011-04-15 2011-04-15
PCT/US2012/032861 WO2012154364A1 (fr) 2011-04-15 2012-04-10 Fibres d'élastomère et leurs procédés de fabrication et d'utilisation

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US9936751B1 (en) 2013-03-14 2018-04-10 Francesco Mignone Towel/absorptive arm sleeve and means of hands free toweling
AU2017229328B2 (en) * 2016-03-08 2019-05-16 KOB GmbH Sock
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US10557219B1 (en) * 2018-12-28 2020-02-11 Brrr! Inc. Methods and compositions for cooling yarns and fabrics comprising a cellulosic fiber, and articles comprising same
KR102459780B1 (ko) * 2020-06-30 2022-10-28 (주)메디코어 비강용 스펀지형 창상피복재 및 그 제조방법

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AU2017201642B2 (en) 2019-08-01
TW201739974A (zh) 2017-11-16
CA2832178A1 (fr) 2012-11-15
MY164541A (en) 2018-01-15
US20170127741A1 (en) 2017-05-11
MX353977B (es) 2018-02-07
AU2012254081A1 (en) 2013-10-24
SG194055A1 (en) 2013-11-29
MX2013011848A (es) 2013-11-01
WO2012154364A1 (fr) 2012-11-15
AU2017201642A1 (en) 2017-03-30
KR101928053B1 (ko) 2018-12-11
EP2697415A1 (fr) 2014-02-19
TWI628327B (zh) 2018-07-01
JP6173299B2 (ja) 2017-08-02
TW201247952A (en) 2012-12-01
KR20140023363A (ko) 2014-02-26
BR112013026090A2 (pt) 2019-12-31
CN103547716B (zh) 2016-11-16
JP2014511949A (ja) 2014-05-19
CN103547716A (zh) 2014-01-29
ES2577980T3 (es) 2016-07-19
US20140101825A1 (en) 2014-04-17
BR112013026090B1 (pt) 2020-08-18
TWI643987B (zh) 2018-12-11
JP2017101373A (ja) 2017-06-08

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