JP2014511949A - Elastomer fibers and methods for making and using the same - Google Patents

Abstract

The present invention relates to a fiber that has excellent elasticity, has a cool touch that is excellent in contact with the hand and skin, and can prevent an undesirable sensation in a wet state. The present invention further relates to fabrics, garments, and undergarments that are excellent in a cool touch and can be obtained by using the fibers, and methods for making these fibers and articles. The present invention relates to an elastic cooling fiber having a Tg of 22 ° C. or lower, more specifically, (i) an intermediate having a hydroxyl group at the end and containing a polyester, polyether, polycarbonate, or a combination thereof, and having a Tg of 22 ° C. or lower , (Ii) a fiber prepared from a composition comprising the reaction product of a diisocyanate and (iii) a linear alkylene glycol chain extender.

Description

BACKGROUND OF THE INVENTION The present invention relates to a fiber that has excellent resilience, has a cool touch that is excellent in contact with hands and skin, and can prevent undesirable sensations in a wet state. The present invention further relates to fabrics, garments, and undergarments that are excellent in a cool touch and can be obtained by using the fibers, and methods for making these fibers and articles.

  In particular, there is a continuing never-ending demand for articles and garments that feel more comfortable in underwear and apparel areas related to sports and / or exercise. Users and / or wearers of such articles and clothing want such articles and clothes to be as comfortable and refreshing as possible, including after prolonged wear and adverse conditions. The fibers used to make such items, specifically these compositions, can significantly affect the performance of the items in these areas.

  In addition to being more comfortable, there is also a desire to maintain or further increase the elasticity of such fibers.

SUMMARY OF THE INVENTION The present invention relates to an elastic cooling fiber having a Tg of 22 ° C. or lower, more specifically, (i) a polyester, polyether, polycarbonate, or a combination thereof, and a terminal having a Tg of 22 ° C. or lower and having a hydroxyl group. Fibers prepared from compositions comprising the reaction product of an intermediate, (ii) diisocyanate, and (iii) a linear alkylene glycol chain extender are provided.

  The present invention provides fabrics made from the fibers described herein and, in some embodiments, mixed with other fibers. The present invention provides articles made from the fabrics described herein.

  The present invention includes (1) preparing a fabric comprising the fibers described herein, (2) preparing an article comprising the fabric, and (3) making the article very close to human skin. Or, in some embodiments, providing a cooling effect to an article that is in close contact with human skin, and in some embodiments, an article that is in direct contact with human skin. Provide a method.

  The present invention is a method for making a fiber, comprising: (1) preparing an elastomeric resin in an internally mixed device, wherein the elastomeric resin comprises (i) a polyester, a polyether, a polycarbonate, or a combination thereof; Prepared by reacting a hydroxyl-terminated intermediate having a temperature of 22 ° C. or lower, (ii) a diisocyanate, and (iii) a linear alkylene glycol chain extender; (2) the elastomer resin is a monofilament Or melt spinning into multifilament fibers.

  The present invention is a method of making a fabric comprising: (1) preparing an elastomeric resin in an internally mixed device, wherein the elastomeric resin comprises (i) a polyester, polyether, polycarbonate, or combination thereof, and Tg A step of preparing an intermediate having a hydroxyl group at 22 ° C. or less, (ii) a diisocyanate, and (iii) a linear alkylene glycol chain extender; and (2) the elastomer resin as a fiber. And, in some embodiments, melt spinning into monofilament or multifilament fibers, and (3) processing the fibers into a fabric, optionally in combination with one or more other fibers. Including a method.

DETAILED DESCRIPTION OF THE INVENTION Various features and embodiments of the present invention are described below by way of non-limiting description.

(Cooling effect)
The present invention provides a fiber that is excellent in a cool touch and further excellent in elasticity. This cooling effect is generally observed with fabrics and / or articles made from this fiber, but the cooling effect is due to the properties of the fibers and thus the fabric and / or article involved. Although not dependent on type and / or configuration, it is believed that these parameters can of course have a relative influence on the observed cooling effect. In other words, it is believed that the cooling effect is provided by this fiber, and more specifically by a fiber having specific properties and / or chemical composition. In the present application, the present inventors can give a cool touch when this fiber is in contact with the skin or when approaching the human skin, between the fiber of the present invention and the human skin. It is frequently noted that this can be said on the top of one or two layers of clothing in In some embodiments, the fibers are in direct contact with human skin. Evaluation of the cooling effect may be performed using the fibers themselves, fabrics made from such fibers, any article made from such fibers and / or fabrics, or various combinations thereof. Is understood.

  The key factors believed to be responsible for the cooling effect provided by the present invention are described below, primarily in the fiber section.

(fiber)
The present invention provides a fiber that is excellent in a cool touch and further excellent in elasticity. This fiber can give a cool touch when in contact with the skin. This effect can be strong enough to be perceived by sensory tests.

  The fiber may include a thermoplastic elastomer and may further include an inorganic filler, but in certain embodiments, the composition does not include an inorganic filler.

  The fiber of the present invention may have a Tg of 22 ° C. or less, and an article made from this fiber is extraordinarily elastic. Further, when this fiber is used in clothes, it has a cool touch. It is also excellent to give.

  “Elastic” and “elastic”, as used herein, means that the fiber stretches after the first pull to 100% strain (doubled length) and after the fourth pull. Means that at least about 50% of the length is recovered. Elasticity can also be described by “permanent deformation” of the fiber. “Permanent deformation” is the opposite of elasticity. The fiber is stretched to a certain point, in some embodiments, to 50% of the elongation at break known for the fiber, then released to its original position before stretching and then stretched again. The point at which the fiber begins to pull the load is called the permanent deformation rate. “Elastic materials” are also referred to in the art as “elastomers” and “elastomeric”.

  The fibers of the present invention are caused by sweat, etc. in a wet state, and therefore, when the fibers are used in clothing, the sticky or bad touch, which often gives an unpleasant sensation to the wearer, is also avoided. Profit can be given in a balanced manner. The fiber of the present invention provides all these factors in a well-balanced manner, and provides excellent performance with any one or any combination of these factors.

  In some embodiments, the thermoplastic elastomer utilized in the preparation of the fibers described herein is substantially free or free of polyamide-type elastomers and / or polyester-type elastomers. More specifically, the present invention may not include polyether block amide copolymers, polyether amide copolymers, polyester amide copolymers, or any combination thereof. More specifically, the compositions included in the present invention may be substantially free or completely free of Pebax (manufactured by Arkema). As used herein, the term polyamide elastomer, or polyamide block within an elastomer, is distinct from a polyurethane elastomer or urethane block within an elastomer because of its chemical meaning and distinct. In some embodiments, polyamide linkages and / or blocks refer to —N (R) —C (O) —R— units and / or linkages in the elastomer, while polyurethane linkages and / or blocks are Refers to -N (R) -C (O) -R- units and / or linkages in the elastomer.

  In other embodiments, the thermoplastic elastomer utilized in the preparation of the fibers described herein may comprise a polyether block amide copolymer, a polyether amide copolymer, a polyester amide copolymer, or any combination thereof. Good.

  The polyester type elastomer is not particularly limited, and examples are polyether ester copolymers and polyester ester copolymers. A polyester type elastomer may be used independently and may be used combining two or more types of polyester type elastomers.

  Among the above, commercialized polyester-type elastomers are Grilux (manufactured by Dainippon Ink and Chemicals, Inc.), Neuvelan (manufactured by Teijin Chemicals Ltd.), Pelrene (manufactured by Toyobo Co., Ltd.). Hytrel (manufactured by DuPont-Toray Co., Ltd.), and Primary (manufactured by Mitsubishi Chemical Corporation).

  The resin element contained in the fiber of the present invention provides the excellent cool touch of the present invention, and therefore, a thermoplastic elastomer may be used alone. Another benefit of the present invention is that when the fibers described herein contain only a thermoplastic elastomer as the resin element, there is generally no sticky sensation, so spinning is not difficult. Additional resins may be used in combination with the resins described herein, but there is no need to deal with stickiness or other undesirable sensations that are more likely to be associated with conventional resins. In some embodiments, additional resins are used. Inorganic filler resins may be used in combination with the resins described herein, but there is no need to deal with stickiness or other undesirable sensations that are more likely to be associated with conventional resins.

  In some embodiments, the fibers and / or resins prepared from the fibers are substantially free or free of inorganic fillers. When an inorganic filler is used, the inorganic filler is not particularly limited, but examples include mineral type pigments such as calcium carbonate, such as light calcium carbonate and heavy calcium carbonate, barium carbonate, magnesium carbonate, such as basic carbonate. Magnesium, 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, for example, calcined diatomaceous earth , Calcium silicate, aluminum silicate, magnesium silicate, silica such as amorphous silica, amorphous synthetic silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, magnesium hydroxide, alumina, hydrated alumina, Toppon, zeolite, hydrated halloysite, clay, hydrotalcite, aluminosilicate, talc, pyrophyllite, smectite, such as saponite, hectorite, sauconite, stevensite, montmorillonite, beidellite and nontronite ), Vermiculite, mica, such as phlogopite, biotite, chinwaldite, muscovite, paragonite, ceradonite and groconite, clinochlore, chamosite, nimite, penantite, sudoishi, donbasite, clintnite, margarite , Peach meteorite, antigolite, lizardite, chrysotile, amethite, cronstedite, burcherin, Linalite, garnierite, kaolin, eg kaolinite, dicite, naclite and halosite, exfoliated kaolin, calcined kaolin, sepiolite, palygorskite, imogolite, allophane, hisingerite, penwithite, activated clay, bentonite, sericite Can be mentioned. These may be used alone or in combination of two or more. In some embodiments, the filler is titanium oxide, zinc oxide, barium oxide, silica, or some combination thereof. The form of the inorganic filler is not particularly limited, and examples thereof are a tangible form such as a spherical form, a needle form, and a flat form, or an intangible form.

  When the inorganic filler is present, the lower limit of the content of the inorganic filler may be 1% by weight, 2% by weight or 7% by weight, and the upper limit is 30% by weight.

  The fibers of the present invention may further include one or more additional additives, and in some embodiments must include at least one or more additional additives (the thermoplastic elastomer of the present invention). And any inorganic filler). In addition, the fiber may be twisted and / or covered with another fiber so as not to hinder the enhancement of factors required for underwear such as skin contact, which is included in the intended degree of the present invention. Also good. Such other fibers are not particularly limited and examples are polyamide-type resins such as nylon 6 and nylon 12; polyester, cotton, rayon.

In some embodiments, the fibers of the present invention may be described by a q _max value. The lower limit of the 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 , the subject cannot feel a cool touch even when the sensory test is performed. In another embodiment, _{q max} value of the fibers may be less than 0.20J / sec / cm ^2, may further exceed 0.22J / sec / cm ^2.

In this description, the q _max value is determined when the predetermined heat is stored in a heating plate having a specific surface area and a specific weight, and immediately after the heating plate is brought into contact with the sample surface, it moves to the sample at a low temperature. It is defined as the peak value of the heat flow of accumulated heat. The q _max value is considered to simulate the body heat removed from the body by the sample when the garment is worn, and the higher the q _max value, the less the body heat removed from the body when the garment is worn. It is considered to be larger and have a cool touch.

In some embodiments, the lower limit of thermal conductivity of the fibers of the present invention may be 1 × 10 ⁻³ ° C./Wm ² . Thermal conductivity is also considered to be one of the important parameters for a cool touch. When the thermal conductivity is less than 1 × 10 ⁻³ ° C./Wm 2, most subjects cannot feel a cool touch even when a sensory test is performed.

  In this description, thermal conductivity is measured by placing the heating plate in layers on the sample on the sample stand, measuring the heat loss rate after stabilizing the temperature of the heating plate to a predetermined temperature, It can be calculated by performing the calculation according to (2).

Thermal conductivity (W / cm / ° C.) = WD / A / ΔT (2)
Where W: heat flow rate (J / sec)
D: Sample thickness (cm)
A: Surface area of the heating plate (cm ² )
ΔT: Temperature difference between the sample stand and heating plate (° C)
The fiber of the present invention may be used in the form of a composite fiber containing a thermoplastic elastomer and another resin, may have a core-sheath structure, a core portion containing a colorable resin, A sheath portion containing a plastic elastomer resin, and the thickness of the sheath portion is 20 micrometers or less (hereinafter, referred to as a core-sheath type composite yarn). By using such a colorable resin for the core portion and a cool feel for the sheath portion and using a thermoplastic elastomer having excellent flexibility, the fiber having excellent cool feel of the present invention is used. It may also be a fiber having a core-sheath structure that has good colorability and maintains the excellent properties of a thermoplastic elastomer, such as a cool touch.

  The form of the core-sheath type composite yarn is not particularly limited, and the cross-sectional shape produced when the fiber is cut perpendicular to the longitudinal direction of the fiber may be a perfect circle, an ellipse, or the like. Further, the fiber has a concentric core-sheath structure in which the core part and the sheath part are made concentrically, or an eccentric core-sheath structure in which the core part and the sheath part are made eccentric. May be. Furthermore, the fiber may have a structure in which a plurality of core portions are present when the fiber is cut perpendicular to the longitudinal direction of the fiber.

  In some embodiments, the fibers of the present invention are elastic cooling fibers having a Tg of 22 ° C. or less.

  In some of these embodiments, the fiber Tg is 22 ° C. or lower, 15 ° C. or lower, 10 ° C. or lower, 0 ° C. or lower, −10 ° C. or lower, −20 ° C. or lower, −30 ° C. or lower, or even −40 ° C. It may be the following. These Tg boundary values may be applied to the fiber itself or to a composition made from the fiber (before the composition is spun or otherwise processed into the fiber). May be applied to the intermediate from which the composition is prepared, or any combination thereof.

  In some of these embodiments, the elongation achieved by the fiber may be between 200% and 300%.

  The fibers of the present invention are prepared from a composition comprising the reaction product of (i) a terminal hydroxyl intermediate, (ii) a diisocyanate, and (iii) a linear alkylene glycol chain extender. The hydroxyl terminated intermediate may comprise a polyester, polyether, polycarbonate, or combinations thereof, the intermediate having a Tg of 22 ° C. or less. In some embodiments, the intermediate is derived from polyethylene glycol. The diisocyanate may contain diphenylmethane-4,4'-diisocyanate. The linear alkylene glycol may contain 1,6-butanediol and similar substances. In some embodiments, the terminal hydroxyl intermediate used in the present invention is substantially free or free of polyether block amide copolymer and / or polyether block amide copolymer units.

  In still other embodiments, the fibers of the present invention comprise (i) polyethylene glycol, or an adipate derived from and / or derived from one or more alkylene diols and adipic acid, A composition prepared from a straight chain alkylene glycol chain extender that may include (ii) a diisocyanate comprising methylene diphenyl diisocyanate; and (iii) 1,4-butanediol, 1,6-hexanediol, or combinations thereof. Prepared from the product itself. In some of these embodiments, the chain extender comprises 1,4-butanediol and the adipate is prepared from 1,4-butanediol, 1,6-hexanediol, or combinations thereof. In some of these embodiments, the adipate is prepared from a mixture of 1,4-butanediol and 1,6-hexanediol. Further, in some of these embodiments, the composition used to prepare the fiber comprises 40-80, 40-70, 50-60, or 55-58 or 56-57% by weight intermediate. 20-50, 30-40, 30-35, or even 31-34 or 32-33 wt% diisocyanate; 4-25, 5-20, 5-15, or even 8-11, or 9-10 % By weight chain extender. The fibers of the present invention may be made from a composition that includes the materials described above and may further contain one or more polymer additives, including any of the additional additives described below. In some embodiments, the composition may further include an antioxidant, a lubricant and / or a processing aid, and may further include a metal-containing catalyst.

  In some embodiments, the fibers of the present invention comprise (i) an intermediate comprising and / or derived from polyethylene glycol, (ii) a diisocyanate comprising methylene diphenyl diisocyanate; and (iii) 1,4 -Prepared from the composition itself prepared from linear alkylene glycol chain extenders comprising butanediol, 1,6-hexanediol, or combinations thereof. In some of these embodiments, the chain extender comprises 1,4-butanediol. Further, in some of these embodiments, the composition used to prepare the fibers is 40-80, 40-70, 40-60, or even 46-49 or 47-48% by weight intermediate. And 20-50, 30-50, 35-45, or even 40-43 or 41-42% by weight diisocyanate; 4-25, 5-20, 5-15, or even 9-12, or 10 11% by weight chain extender.

  In addition, the composition from which the fiber is prepared comprises: (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 by mixing a polymer and / or copolymer and at least one other polymer and / or copolymer, each polymer and / or copolymer being compatible and / or miscible with each other; or (c) It may be a polymer alloy containing these combinations. The polymer alloy comprises: (i) (a) a polyol; (i) (b) a polyester intermediate derived from a polyol and a dicarboxylic acid; (ii) at least one diisocyanate; and (iii) at least one chain extender. May be derived from the reaction with

  In general, the TPU polymer type used in the present invention means it (which means the fiber itself, the composition from which the fiber was made, and / or the intermediate used to prepare the composition) Any conventional TPU polymer known in the art and literature may be used as long as it exhibits a Tg, elongation, and / or elasticity. Without wishing to be bound by theory, Applicants include herein compositions that meet these requirements when they meet at least one or more additional parameters described herein. Consider the same cooling effect shown by a specific example or an alternative effect.

  Suitable TPU polymers generally include a polyisocyanate, an intermediate (eg, a hydroxyl terminated polyester, a hydroxyl terminated polyether, a hydroxyl terminated polycarbonate, or a mixture thereof) and one or more chain extensions. Which are prepared by reacting with agents, all well known to those skilled in the art.

  The hydroxyl terminated polyester intermediate generally has a number average molecular weight (Mn) of about 500 to about 10,000, about 700 to about 5,000, or about 700 to about 4,000, and has an acid number of A linear polyester that is generally less than 1.3, preferably less than 0.8. Molecular weight is determined by terminal functional group assays and is related to number average molecular weight. The polymer can be (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) a transesterification reaction, ie, one or more glycols and a dicarboxylic acid ester. Produced by reaction. The molar ratio is generally preferred to be greater than 1 mole of excess glycol relative to the acid so as to obtain a linear chain in which the terminal hydroxyl groups are predominant. Suitable polyester intermediates further include various lactones such as, for example, polycaprolactone typically made from ε-caprolactone and a bifunctional initiator (eg, diethylene glycol). Desirable polyester dicarboxylic acids may be aliphatic, cycloaliphatic, aromatic, or combinations thereof. Suitable dicarboxylic acids that may be used alone or in a mixture generally contain a total of 4 to 15 carbon atoms and include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Examples include acid, dodecanedioic acid, isophthalic acid, terephthalic acid, and cyclohexanedicarboxylic acid. The anhydrides of the above dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride, etc. can also be used. Adipic acid is the preferred acid. The glycol that reacts to produce the desired polyester intermediate may be aliphatic, aromatic, or a combination thereof, containing a total of 2 to 12 carbon atoms, 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, and 1,4-butanediol is a preferred glycol.

The hydroxyl terminated polyether intermediate is a polyether polyol derived from a diol or polyol containing a total of 2 to 15 carbon atoms, in some embodiments an alkylene oxide containing 2 to 6 carbon atoms. Polyether polyols derived from alkyl diols or glycols which react with groups, typically ethers (or epoxides) containing ethylene oxide or propylene oxide or mixtures thereof. For example, hydroxyl functional polyethers can be made by first reacting propylene glycol and propylene oxide followed by subsequent reaction with ethylene oxide. Primary hydroxyl groups obtained from ethylene oxide are preferred because they are more reactive than secondary hydroxyl groups. Useful commercially available polyether polyols include poly (ethylene glycol) containing ethylene oxide reacted with ethylene glycol, poly (propylene glycol) containing propylene oxide reacted with propylene glycol, poly (tetramethylene) containing water reacted with tetrahydrofuran Glycol) (PTMEG). PTMEG is a preferred polyether intermediate. The polyether polyol further comprises a polyamide adduct of alkylene oxide, such as an ethylenediamine adduct containing a reaction product of ethylenediamine and propylene oxide, a diethylenetriamine adduct containing a reaction product of diethylenetriamine and propylene oxide, and the like Mention may be made of polyamide-type polyether polyols. Copolyethers can also be utilized in the present invention. Typical copolyethers include the reaction product of THF and ethylene oxide or the reaction product of THF and propylene oxide. These are available from BASF as Poly THF B (block copolymer), poly THF R (random copolymer). Various polyether intermediates generally have an average molecular weight of greater than about 700, such as from about 700 to about 10,000, about 1000, when the number average molecular weight (Mn) is determined by terminal functional group assays. To about 5000, or about 1000 to about 2500. A particularly 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.

  In some embodiments, the compositions of the present invention are prepared from polyethylene glycol (PEG). In other embodiments, 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 the present invention may be prepared by reacting a diisocyanate with a blend of a hydroxyl terminated polycarbonate and a chain extender. A terminal hydroxyl polycarbonate can be prepared by reacting glycol and carbonate.

  U.S. Pat. No. 4,131,731 is hereby incorporated by reference for its disclosure regarding polycarbonates terminated with hydroxyl and their preparation. Such polycarbonates are linear, have terminal hydroxyl groups, and are essentially free of other end groups. The essential reactants are glycol and carbonate. Suitable glycols include alicyclic and aliphatic diols containing 4 to 40, and / or further 4 to 12 carbon atoms, and also contain 2 to 20 alkoxy groups per molecule, each alkoxy group Is selected from polyoxyalkylene glycols containing 2 to 4 carbon atoms. Suitable diols for use in the present invention include aliphatic diols containing 4 to 12 carbon atoms such as butanediol-1,4, pentanediol-1,4, neopentyl glycol, hexanediol-1. , 6,2,2,4-trimethylhexanediol-1,6, decanediol-1,10, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol; and alicyclic diols such as cyclohexanediol-1, 3, dimethylolcyclohexane-1,4, cyclohexanediol-1,4, dimethylolcyclohexane-1,3, 1,4-endomethylene-2-hydroxy-5-hydroxymethylcyclohexane, and polyalkylene glycol. The diol used in the reaction may be a single diol or a mixture of diols, depending on the properties desired for the final product. Terminally hydroxylated polycarbonate intermediates are generally those known in the art and literature. Suitable carbonates are selected from alkylene carbonates composed of 5 to 7 membered rings. 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. Examples include carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 2,3-pentylene carbonate, and 2,4-pentylene carbonate.

  Also suitable for the present invention are dialkyl carbonates, alicyclic carbonates, and diaryl carbonates. Dialkyl carbonates may contain 2 to 5 carbon atoms in each alkyl group, specific examples of which are diethyl carbonate and dipropyl carbonate. An alicyclic carbonate, in particular a dialicyclic carbonate, may contain 4 to 7 carbon atoms in each cyclic structure and may be one or two such structures. When one group is alicyclic, the other group may be either alkyl or aryl. On the other hand, when one group is aryl, the other group may be alkyl or alicyclic. Examples of suitable diaryl carbonates that may contain 6 to 20 carbon atoms in each aryl group are diphenyl carbonate, ditolyl carbonate, dinaphthyl carbonate.

  The reaction is carried out in the presence or absence of a transesterification catalyst with glycol and carbonate (eg alkylene carbonate) in a molar ratio of 10: 1 to 1:10, but preferably 3: 1 to 1: 3. The reaction may be performed at a temperature of 100 ° C. to 300 ° C. and a mercury pressure of 0.1 to 300 mm, and may be performed while removing low-boiling glycol by distillation.

  More specifically, a hydroxyl-terminated polycarbonate is prepared in two stages. In the first stage, glycol is reacted with alkylene carbonate to produce a low molecular weight end-terminated polycarbonate. The low-boiling glycol is removed by distillation at a reduced pressure of 100 to 300 ° C, preferably 150 to 250 ° C and 10 to 30 mmHg, preferably 50 to 200 mmHg. A separation column may be used to separate the by-product glycol from the reaction mixture. By-product glycol may be collected from the top of the column, and unreacted alkylene carbonate and glycol reactant may be returned to the reaction vessel as reflux. A stream of inert gas or inert solvent may be used and removed when the by-product glycol is produced. If the amount of by-product glycol obtained indicates that the hydroxyl-terminated polycarbonate has a degree of polymerization of 2-10, the pressure is gradually reduced to 0.1 mmHg-10 mmHg to remove unreacted glycol and alkylene carbonate. To do. This is achieved by distilling off the glycol once it is formed at a pressure of 100 ° C. to 300 ° C., preferably 150 ° C. to 250 ° C., 0.1 to 10 mmHg, until a polycarbonate having the desired molecular weight is hydroxylated. During the reaction of the hydroxyl-terminated hydroxyl polycarbonate, the beginning of the second stage of the reaction is indicated. The molecular weight (Mn) of the terminal hydroxyl polycarbonate may vary between about 500 and about 10,000, but in a preferred embodiment it ranges from 500 to 2500.

The second necessary component for making the TPU polymer of the present invention is a polyisocyanate. The polyisocyanates of the present invention generally have the formula R (NCO) _n , where n is generally 2-4 and 2 is very preferred so long as the composition is thermoplastic. Thus, a polyisocyanate having 3 or 4 functional groups is utilized in a very small amount, for example less than 5% by weight, desirably less than 2% by weight, based on the total weight of all polyisocyanates, as long as it is crosslinked. R may be aromatic, alicyclic, and aliphatic, or combinations thereof, generally containing a total of 2 to about 20 carbon atoms. Examples of suitable aromatic diisocyanates include diphenylmethane-4,4′-diisocyanate (MDI), H ₁₂ MDI, m-xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI), phenylene-1, Examples include 4-diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI), diphenylmethane-3, 3′-dimethoxy-4, 4′-diisocyanate (TODI). Examples of suitable aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), hexamethylene diisocyanate (HDI), 1,6-diisocyanato-2,2,4,4-tetramethylhexane. (TMDI), 1,10-decane diisocyanate, trans-dicyclohexylmethane diisocyanate (HMDI). A highly preferred diisocyanate is MDI containing less than about 3% by weight of ortho-para (2,4) isomer.

  A third necessary component for making the TPU polymers of the present invention is a chain extender. Suitable chain extenders are lower aliphatic or short chain glycols containing from about 2 to about 10 carbon atoms, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, Examples include cis-trans-isomers of cyclohexyldimethylol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butanediol, and 1,5-pentanediol. Although the present invention requires a linear alkylene glycol chain extender, in some embodiments, additional chain extenders may be used in combination with the linear alkylene glycol chain extender. In such embodiments, aromatic glycols may be used as chain extenders. Benzene glycol (HQEE) and xylylene glycol are suitable chain extenders for use in making the TPUs of the present invention. Xylylene glycol is a mixture of 1,4-di (hydroxymethyl) benzene and 1,2-di (hydroxymethyl) benzene. Benzene glycol is a preferred aromatic chain extender, specifically bis (β-hydroxyethyl) ether, resorcinol, 1,3, also known as hydroquinone, 1,4-di (2-hydroxyethoxy) benzene. -Bis (β-hydroxyethyl) ether, also known as di (2-hydroxyethyl) benzene, catechol, ie bis (β-hydroxyethyl) ether, also known as 1,2-di (2-hydroxyethoxy) benzene , And combinations thereof. A preferred chain extender is 1,4-butanediol.

  The above three required components (terminated hydroxyl intermediate, polyisocyanate, and chain extender) may be reacted in the presence of a catalyst.

  In general, any conventional catalyst may be utilized to react the diisocyanate with a terminal hydroxyl intermediate or chain extender, as is well known in the art and literature. Examples of suitable catalysts include various organic compounds of bismuth or tin (eg, carbonates), where the alkyl moiety contains 1 to about 20 carbon atoms, and specific examples include bismuth octene. And bismuth laurate. Preferred catalysts include various tin catalysts such as stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate and the like. The amount of such catalyst is generally as small as about 20 to about 200 parts per million (ppm), etc., based on the total weight of monomers forming the polyurethane.

  The TPU polymers of the present invention can be made by any conventional polymerization method known in the art and literature.

  In some embodiments, the polyurethanes of the present invention are made by a “one-shot” process in which all elements are added simultaneously or substantially simultaneously to a heated extruder and reacted to form the polyurethane. . The equivalent ratio of diisocyanate to the total equivalent weight of the terminal hydroxyl intermediate and the diol chain extender is generally from about 0.95 to about 1.10, desirably from about 0.97 to about 1.03, preferably , About 0.97 to about 1.00. In some embodiments, the shore A hardness of the formed TPU is typically less than 80A, less than 85A, or even less than 95A. The reaction temperature utilizing the urethane catalyst may be from about 175 ° C to about 245 ° C, or even from about 180 ° C to about 220 ° C. The molecular weight (Mw) of the thermoplastic polyurethane is from about 100,000 to about 800,000 daltons, or from about 150,000 to about 400,000, or even from about 150,000 to about 350, as determined by GPC against polystyrene standards. , 000.

  In the TPUs described herein, useful additives can be used in appropriate amounts, where such additives are added before, during, or after preparing the TPU. May be added. Such further 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, while useful tinting pigments include carbon black, yellow oxide, brown oxide, Losenna and Burnschenna or Low amber and burnt amber, chromium oxide green, cadmium pigments, chromium pigments, and other mixed metal oxides and organic pigments. Useful fillers include diatomaceous earth (superfloss) clay, silica, talc, mica, wollastonite, barium sulfate, and calcium carbonate. If desired, useful stabilizers such as antioxidants may be used, including phenolic antioxidants, while useful light stabilizers include organic phosphates and organotin thiolates (mercaptides). Can be mentioned. Useful antioxidants further include sterically bulky phenolic antioxidants. Useful lubricants include metal stearates, paraffin oils, and amide waxes such as alkylene bis-stearic acid amides such as N, N 'ethylene bis-stearic acid amides and esters of nonanoic acid esters. Useful UV absorbers include 2- (2'-hydroxyphenol) benzotriazole and 2-hydroxybenzophenone. Typical TPU flame retardants can also be added.

  When the plasticizer additive is advantageously used and used in a small amount, the hardness can be lowered without affecting the properties. In some embodiments, no plasticizer is used.

  In some embodiments, the cooling effect of the fibers may be expressed in terms of effective cooling power. Although there are various means of measuring the cooling effect provided by the present invention, this application includes details of two techniques for measuring this effect. The initial cooling effect provided by a fabric made from the fibers described herein is that the fabric and the “skin” area in contact with the fabric (in this case, a test surface that utilizes the location of human skin) Look at both) and let a constant wind through the cloth. Although the specific conditions involved are considered to be important primarily for the purpose of comparing results, these types of assessments of course include various ambient temperatures, degrees of humidity, wind speed, “skin” onset temperature ( The “skin” heat source may remain or be removed) and various other variables. In addition, this parameter is of course measured for a specific area. Another approach follows the basic test method described above, but adds additional variables over the series of tests, such as sweat, various rates of water release from the “skin”. This type of test can be used to measure the amount of energy that maintains the temperature of the “skin” under various or alternative conditions, and the “skin” temperature decreases when no heat source is applied. The speed can be measured, which gives an indication of the cooling power of the fabric involved. Specific test conditions and results are given in the Examples section of this specification. Regardless of the test technique used and the specific conditions chosen, all tests conducted to date have shown that fabrics made from the fibers described herein exhibit significantly higher cooling power and are tested together. It is important to note that the temperature can be reduced more quickly and significantly than the comparative materials.

In some embodiments, when the fibers of the present invention are evaluated by the methods described above, specifically when the fabric is placed on the test skin surface, the skin surface temperature, 30% relative humidity, 3 m / s wind speed. , And operating an effective heat source to maintain an ambient temperature of 15 ° C. provides at least 31 watts of cooling power for a 629 cm ² test area, or alternatively at least 49 watts / square meter The cooling power of was described. That is, a force of at least 49 watts / square meter is required to maintain skin temperature, which means that other materials (nylon and polyester, for example, actually exceed the 31 watt boundary value under the same test conditions) Provides an indication of the cooling effect that the fabric has on the human when the fabric is present against the skin. This cooling power may be at least 34 watts for a 629 cm ² test area and may be at least 55 watts / square meter, where the fibers are monofilaments and not semi-dal. The same boundary values apply to tests performed at 50% relative humidity, wind speed 3 m / s, and wind speed 5 m / s and 50% relative humidity.

In a similar embodiment, the fibers of the present invention, when evaluated by the method described above, specifically when the fabric is placed on the test skin surface, skin surface temperature, 50% relative humidity, 0.3 m / s wind speed. Activating an effective heat source to maintain an ambient temperature of 15 ° C. provides a cooling power of at least 13 or 14 watts, at least 21 or 22 watts / square meter for a 629 cm ² test area.

  The method for producing a fiber having excellent cool touch according to the present invention is not particularly limited, and a resin pellet containing a thermoplastic elastomer and an inorganic filler is produced, and the obtained resin pellet is melted and spun. Conventionally known methods such as a method for producing fibers by may be used.

  The core-sheath type composite yarn may be manufactured, for example, by placing resin pellets containing a colorable resin, a thermoplastic elastomer, and an inorganic filler on a composite spinning apparatus, melting it, and spinning.

  The present invention provides a method for making fibers comprising the step of (I) preparing an elastomeric resin in an internally mixed device. Elastomeric resins are prepared by reacting (i) a terminal hydroxyl intermediate, (ii) a diisocyanate, and (iii) a linear alkylene glycol chain extender. The intermediate may be polyester, polyether, polycarbonate, or a combination thereof, and the intermediate has a Tg of 22 ° C. or lower. In the second step (II), the elastomer resin is melt-spun into fibers (eg, monofilament or multifilament fibers). In some embodiments, the fiber is a monofilament fiber. All of the various features and embodiments described above for the fibers and compositions used to prepare the fibers apply here as well.

(cloth)
The fibers of the present invention may be used in the form of fabrics such as knitted fabrics, textiles, and bonded textiles. The obtained cloth has excellent elasticity of the fiber and has a cool feel.

  The cool-feeling fabric of the present invention may simply contain the cool-feeling fabric of the present invention, and in other embodiments, improve the factors required for a specific application. For this purpose, the fiber and another fiber may be included together in a twisted state. For example, in clothing that is in direct contact with the skin. Such optional co-fibers are not particularly limited, and examples include polyamide-type resins such as nylon 6 and nylon 12, polyester, cotton, and rayon.

  The present invention includes fabrics made from any of the fibers described herein, including woven fabrics, nonwoven fabrics, knitted fabrics, and combinations thereof. In some embodiments, the fabric of the present invention is a woven fabric. In other embodiments, the fabric of the present invention is a non-woven fabric. In yet another embodiment, the fabric of the present invention is a knitted fabric. In addition, the present invention includes fabrics that further include one or more additional fibers in addition to the fibers of the present invention. The fabric is 10 to 80% by weight of these additional fibers, or 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10% These additional fibers may be included: In some embodiments, there are no additional fibers. In embodiments where one or more additional fibers are present in the fabric, these additional fibers may be nylon fibers, polyester fibers, rayon fibers, acrylic fibers, and combinations thereof.

  The present invention further includes a method of making a fabric comprising the steps of (I) preparing an elastomeric resin in an internally mixed device, wherein the elastomeric resin is prepared as described above. This process may optionally include the addition of a cross-linking agent (eg, a reaction product of polyalkylene ether glycol or triol and diisocyanate). Step (II) is to melt-spin the elastomer resin into fibers (for example, monofilament or multifilament fibers). In some embodiments, the fiber or the polymer comprising the fiber has a weight average molecular weight of at least 700,000. Step (III) is to process the fibers into a fabric, optionally in combination with one or more other fibers.

  A further benefit of the present invention is the improved moldability of fabrics containing the fibers described herein. When utilizing an appropriate amount in the fabric, the fabric of the present invention can be successfully molded at low temperatures and / or in a short time, and is therefore required in conventional fabrics for successful molding. Increased ability to protect fabrics, fabric dyes, and the like that can be damaged by high temperatures and / or low exposure times. In some embodiments, the fabric of the present invention can be used at temperatures of 150 ° C. or lower, or even 140 ° C. or lower, and / or when molding is completed in less than 20 seconds, less than 15 seconds, or even less than 10 seconds. It may be molded. In some embodiments, a minimum amount of the inventive fiber must be present in the fabric to provide these benefits. In some embodiments, this lower limit is 40%, 50%, 60%, or even 80%, where the percentage represents the weight percent of fibers in the fabric that should be fibers of the present invention. . However, it is also understood that a smaller amount of the fiber of the present invention in the fabric enhances the fabric's molding ability. Spanex® and similar materials are not moldable at low temperatures, and the fibers of these materials are positive feeders that require expensive equipment parts due to the elasticity of Spanex ™ fibers being too great Note that it cannot even be knitted in the fabric unless (positive feeder) is used.

(Goods)
In order to manufacture articles including clothes, the fiber having excellent cool touch according to the present invention and the cloth having excellent cool touch according to the present invention may be used. In the case of articles that come into contact with the skin (again, clothing), the articles of the present invention exhibit excellent elasticity, give the wearer a cool sensation, and even when wet, unpleasant sensations and There is no sticky feeling.

  Since articles (especially clothes) give an excellent and cool touch, a cool feeling can be generated when worn, and a refreshing feeling can be given. In addition, the present invention does not require the addition of an inorganic filler so that the garment does not feel sticky when wet like other fibers used in garments that can provide a similar cooling effect. Therefore, the present invention is very suitable for underwear.

  The cool-feeling garment of the present invention may be manufactured using fibers that are completely cool-feeling, including a fabric that has a reversible structure and excellent refreshing feel. It is particularly preferable that the garment has an excellent sensation, and 30 to 70% of the total number of yarn loops includes fibers with excellent cool feel, and the yarn loops with fibers with excellent cool feel Arrange on the side in contact with the skin (hereinafter also referred to as refreshing clothing).

  Regarding the garment including a cloth having a reversible structure as a garment having excellent cool feel of the present invention, the ratio of the number of loop yarns including fibers having an excellent crisp feel is controlled within a predetermined range. , Loop yarns that contain such a cool textured fiber align only on the side that contacts the skin, so that the garment prevents the unpleasant sensation caused by a lot of sweating Can have an effect.

  In recent years, in the case of exercise, sports, etc., various types of clothes having excellent functions as underwear worn in sweaty situations in the summer have been developed and proposed, and such functional clothes include, for example, Suggests garments made from hydrophobic fibers (eg polyester). In addition, the method of increasing air permeability by using hydrophilic fibers in combination with cotton, and the knitting of knitted fabrics by creating a mesh structure in the fabric or by plain and warp knitted fabrics. ) To improve the air permeability, and Japanese Patent Publication No. 2003-155669 discloses a fabric modified by depositing a hydrophilic chemical on the surface of hydrophobic fibers constituting the fabric. Is disclosed. However, in the case of clothes containing such hydrophobic fibers, the generated heat can be released efficiently, but if the skin or clothes are wet because of sweat, it is due to the wet feeling With undesirable sensations, the cloth tends to stick to the skin and cause problems with restricted movement of clothes.

  On the other hand, for a refreshing garment including a cloth having a reversible structure, the ratio of the number of loop yarns containing fibers with a cool texture is controlled within a predetermined range, thereby creating a crisp feeling when worn. Can give a refreshing sensation, and at the same time can prevent unwanted sensations due to wet sensation when sweating, due to the worse separation from the skin, the cloth on the skin It can prevent sticking. In addition, loop yarns that contain fibers that are cool and have excellent texture align only on the side of the skin, so that the fibers that are cool and have good texture can be in direct contact with the skin and clothing, further improved A refreshing sensation and a cool feel can be created.

  In the refreshing article and garment of the present invention, the lower limit value of the ratio of the loop yarn of the fiber that is excellent in the cool touch may be 30% of the total number of loop yarns, and the upper limit value is the total of the loop yarns. It may be 70% of the number or higher, for example 75%, 80%, 90%, or 100%. Below 30%, the effect of producing a refreshing sensation and a cool touch can be insufficient in some cases. If the skin or clothes are wet because of sweat, a high level can be obtained using the present invention without causing an undesirable sensation due to the wet sensation.

  As noted above, in the case of fibers and fabrics, a refreshing article (eg, garment) may include a thermoplastic elastomer and an inorganic filler, but in other embodiments, is substantially free of inorganic filler. Or not.

  In the article of the present invention (for example, clothes), the thickness of the cloth should be as thin as possible, and a fiber that is excellent in a cool touch may be used in combination with another fiber. The lower limit value of the content of the thermoplastic elastomer in the fiber having excellent cool feel may be 50% by weight. If it is less than 50% by weight, in some cases, a sufficiently cool touch may not occur. In other embodiments, the fiber content of the present invention is at least 15%, 25%, 35%, 45%, 55%, 65%, 75%, 85%, or even 95% by weight in fabrics and articles. Present in the amount of. While not wishing to be bound by theory, it is believed that the minimum fiber content in the fabrics and / or articles discussed herein must have a significant cooling effect for the fibers of the present invention. . This minimum required content may vary for different formulations included in the present invention, but in some embodiments may be fairly consistent across the various formulations. This minimum content may be any percentage described above.

  In some embodiments, in the articles and / or garments of the present invention, it is preferred that the loop yarns containing fibers with a cool texture be aligned only on the skin side. When aligned in this manner, the loop yarn containing fibers with a cool texture mainly comes in contact with the skin, creating a cool texture and a refreshing sensation, as described later on the outside The alignment of loop yarns containing hydrophobic fibers improves the property of diffusing and evaporating the heat and water released from the skin.

  In the article and / or garment of the present invention, the loop yarn other than the loop yarn containing a fiber having a cool texture is preferably a loop yarn containing a hydrophobic fiber. Since the loop yarn including the fiber having a cool and excellent touch is aligned only on the skin side, the loop yarn including the hydrophobic fiber is mainly aligned outside.

  In this description, hydrophobic fiber means a chemical fiber having an official water percentage of 5.0% or less. In fact, including polypropylene (official water percentage: 0%), polyester (0.4%), acrylic resin (2.0%), nylon (4.5%), and vinylon (5.0%) An example is fiber. These may be used alone or in combination of two or more. In this context, official water percentage means the percentage of water at 20 ° C. and 65% RH.

  The articles and / or garments of the present invention may be made of natural fibers (eg cotton and flax) and semi-synthetic fibers (eg rayon and Acetate).

In some embodiments, the articles and / or garments of the present invention have a refreshing garment air permeability of from 200 cm ³ / cm ² / sec to 500 cm ³ / cm ² / sec. If it is less than 200 cm ³ / cm ² / sec, the air permeability may be poor, and the diffusion of heat released from the skin and the evaporation of sweat may be suppressed in some cases, and 500 cm ³ / cm ² / sec. In more cases, heat and water movement through the garment may not be sufficient, whereas the outside air can permeate. The air permeability can be measured using an air permeability tester according to the method of JIS L 1096 A.

In the fabric, article and / or garment of the present invention, the upper limit of weight per square meter may be 120 g / m ² , 100 g / m ² or even 90 g / m ² . Unlike other means that give such a cool feeling, when the weight per square meter exceeds 120 g / m ² , 100 g / m ² or even 90 g / m ² , the working mechanism is suppressed. So that the chilly sensation may worsen in some cases.

  The method for producing the article and / or garment of the present invention is not particularly limited, and for example, a conventionally known method (for example, a method for producing garment by weaving a fiber with excellent cool feel according to the present invention) is used. May be used. Further, these materials may be manufactured by a conventionally known method such as sewing and cutting using a cloth having a reversible structure obtained in the above-described manner.

  An underwear having a cool feel can be produced by using the fiber of the present invention or the fabric of the present invention. Furthermore, the garment excellent in the cool touch of this invention can be used as underwear. In such embodiments, the present invention may provide any one or more of the benefits described above for fibers, fabrics, articles, and / or garments.

  In addition to underwear, the present invention includes stockings, gloves, face masks, mufflers, and the like that can be manufactured by using the fibers of the present invention or the fabric of the present invention with a cool touch. Since these are in direct contact with the skin, particularly excellent effects can be produced.

  The present invention includes articles made from the fabrics described above. For example, various garments can be produced using the cloth of the present invention. In some embodiments, the fabric is used to make undergarments or clothing that fits snugly, where the fabric of the present invention is sufficient due to the comfort and cooling effect provided by the fibers. Is suitable. Underwear, such as bras and T-shirts and sports clothing used in activities such as running, skiing, cycling or other sports, will benefit from the properties of these fibers. The elasticity and cooling effect of the present invention benefits garments worn near the body. One skilled in the art will appreciate that any garment can be made from the fabrics and fibers of the present invention.

  Other embodiments use the fibers described herein, including but not limited to sports apparel such as shorts (bicycle driving, hiking, running, compression exercise, training, golf, baseball, basketball, cheerleading, dancing , Including soccer and / or hockey shorts), shirts (including any of the specific types listed above for shorts), tights (including training tights and compression tights), swimsuits (competitive swimsuits) And any number of clothing and articles, such as bodysuits (including wrestling, running, swimsuit bodysuits) and footwear. Further embodiments include work clothes such as shirts and uniforms. Further embodiments include those that directly touch the skin including bras, panties, men's underwear, camisole, orthodontic underwear, nightgowns, pantyhose, men's undershirts, tights, socks and corsets. Further embodiments include socks (eg, compressible socks, diabetic socks, fixation socks, and dynamic socks), therapeutic burn treatment bands and films, wound healing bandages, medical clothing Such medical clothing and articles. Further applications include military applications that are very similar to one or more of the specific articles described above. Further embodiments include bedding articles such as sheets, blankets, comforters, mattress pads, mattress tops, and pillow cases.

  In some embodiments, the article of the present invention is a garment, and the fibers that make up the fabric in the garment align within the garment so as to be in direct contact with the skin of the wearer of the garment. This allows the wearer to obtain the full benefit of the cooling effect provided by the present invention.

  The present invention further comprises (I) preparing a fabric comprising the fiber of claim 1, (II) preparing an article comprising the fabric, and (II) bringing the article into direct contact with human skin. A method of providing a cooling effect to an article (eg, clothing) in direct contact with human skin, comprising the steps of:

  It is known that some of the materials described above may interact in the final formulation, so that the final formulation elements may differ from those originally added. For example, metal ions (eg, detergent metal ions) can migrate to other acidic or anionic sites of other molecules. The products produced thereby may be difficult to describe simply, including products produced when the compositions of the present invention are used in their intended applications. Nevertheless, any such modifications and reaction products are within the scope of the present invention, which includes compositions prepared by admixing the elements described above.

  The invention is further illustrated by the following examples describing particularly useful embodiments. While examples are provided to illustrate the present invention, these examples are not intended to limit the invention.

(Example group)
To illustrate the benefits of the present invention, seven materials were evaluated. These materials are summarized in the following table.

1-Each fabric sample is in the form of an open sock / sleeve. The diameter refers to the diameter of the sleeve that the fabric creates, while the length is the actual length of the sample. Each fabric was weighed for fabric weight and then the weight was calculated in grams / square meter for each fabric using other reported measurements.
2- This fiber is commercially available from Invista (TM).
3-Fiber A is prepared from polyalkylene glycol, alkylene diol, and MDI.
4-Fiber B is prepared from alkylene diol adipate, alkylene diol, and MDI.
5-fiber C is a multifilament embodiment of fiber B and is chemically identical to fiber B.
6-fiber D is fiber B except that a commercially available matting agent is added.

  Comparative Example 1 is a baseline and does not represent fibers and / or fabrics. Comparative Examples 2 and 3 are comparative materials that do not represent the present invention. Examples 4, 5, 6 and 7 represent various embodiments of the present invention.

  It should be noted that the fabrics to be tested have different diameters and the fabrics obtained for testing have different weights. To account for these differences, the tests described below allow for a reasonable comparison of materials using clamps that hold fabric samples in a manner that provides significant tension and fabric density on the test surface. Went. Differences not accounted for by these controls are not expected to have a significant effect on the parameters tested.

(Test method and results)
The example described above was tested to determine its cooling power. The test was conducted at a temperature and humidity controlled in a climate chamber using a sweaty heat mannequin as the test surface. A mannequin test surface of known surface area was fitted with a thermocouple for monitoring temperature and a heating element for heating the test surface to realistic human skin temperature for testing. In addition, the heating element power requirements could be monitored to see the amount of energy required to maintain a specific skin temperature on the test surface. The test surface can also simulate the release of sweat from human skin and release moisture. A high power fan was used as the wind source. The area of the test surface used in all these tests is 629 cm ² .

  For this test, a sweaty heat mannequin is placed in a climate chamber set at 15 ° C. Tests were conducted at 30% and 50% relative humidity, wind speeds of 0.3 m / s, 3 m / s and 5 m / s. A wind speed of 0.3 m / s is a normal condition of the artificial climate chamber, and thus indicates that the high-speed fan is turned off. A circularly knitted open sock sample (also called a sleeve) of each material is placed on the test surface of the mannequin with sweat and heat, in this case on the forearm of the mannequin. The sample is placed on the test surface for testing and then removed and replaced with the next sample. Note that using clamps as described above, each sample is secured to a sweaty, heated mannequin forearm, and the samples are placed with a significant degree of tension and fabric density. Pay.

  At the beginning of each test, the climate chamber is brought to the desired conditions. If the test surface covered with the fabric sample to be tested is heated to a desired starting skin temperature of 31 ° C. or 34 ° C. selected to be approximately human skin temperature, and wind is included in the test conditions, Turn on the fan and set it to the desired setting. Once all these conditions have been set, the test period begins by monitoring the amount of power required to maintain the test surface temperature setting by the heating element. This amount of power is measured in watts and is referred to as the cooling power of the fabric tested at a given test condition. The reported cooling power is the output of the system stabilized under given test conditions. At the end of each test, replace the sample cloth with a different sample and repeat the test, changing the conditions if necessary.

  The baseline of Example 1 was tested using a bare uncovered test surface to obtain an effect that could be expected from bare skin. This bare skin baseline was included in the comparative study.

  The table below summarizes the test conditions used and the examples tested under each set of conditions.

1- These condition sets were tested in the following order. IV, I, V, II, VI, III. Condition sets IV and V were the same and were not performed sequentially, thus giving two sets of data showing the reproducibility of results and the relative differences between samples.
2-The target skin temperature for this test is always 34 ° C, except for the set of conditions when the wind is 5 m / s. In these conditions, the heating capacity is limited and a skin temperature of 31 ° C. is used to ensure a system that can be maintained at the desired temperature.

  The results of this test are summarized in the following table.

1—All results reported in this table are cooling power measured in Watts [W]. This is the power of the heating element in the sweaty mannequin required to maintain the temperature of the test surface (foreman surface covered with the test cloth) at the set temperature at the specified conditions. Amount. The greater the reported cooling power, the more power is required to maintain the temperature, and the greater the cooling effect that the fabric creates. In other words, the greater the reported cooling power, the greater the cooling effect expected to be experienced when wearing clothing made from the tested fabric. All of these results is related to the standard test surface area of 629cm ^2. The cooling power per square meter can be calculated by dividing the reported result by 0.629.

  The result is that the fibers of the present invention, and more specifically, fabrics made from such fibers, when measured by cooling power, are made from conventional synthetic fibers (more specifically, made from conventional synthetic fibers). It is shown that it gives a cooling effect greater than that of the cloth. In addition, the results show that the fibers of the present invention, and more specifically the fabrics made from such fibers, are found in the baseline bare skin example as measured by cooling power. It shows that it provides a cooling effect comparable to power. In other words, the present invention creates an article that gives the wearer whose skin is in contact with the article a cool sensation similar to that felt when a cloth with bare skin is not in contact with the skin. Fiber, fabric and various garments are provided, including means.

  A further test set with additional variables for water release from the test surface under test is also included. In these tests, a foot model with sweaty heat was used, and a control device similar to the above-described mannequin was attached to this model. The moisture release used in this test simulates the different sweat rates experienced by humans during exercise, for example when garments made from test cloth are worn, and has an effect on the cooling power of the fabric. In some cases it is designed to see what it looks like.

  The same seven examples listed in Table 1 were tested here. The conditions used in this test are summarized in the following table. For each test condition, the system was allowed to stabilize for 30 minutes without any wind or moisture release during which the fabric cooling power was measured. The release of moisture was then started and the system was allowed to stabilize again for 30 minutes, during which time the cooling power was measured. Finally, wind conditions were added and the system was allowed to stabilize again for 30 minutes, during which time the cooling power was measured.

1—These condition sets were performed in the test in the following order: VII, VIII, IX, X, XI.

  The results of this test are summarized in the following table. As described above, each test condition included three separate measurements of cooling power. When there is no wind or moisture release (A), when moisture is released and there is no wind release (B), when there is both target moisture release and wind (C). For each set of conditions, the measured cooling power is presented below.

1—All results reported in this table are cooling power in watts [W]. See also footnote 1 in Table 3.

1—All results reported in this table are cooling power in watts [W]. See also footnote 1 in Table 3.

  This result shows that the fibers of the present invention, and more specifically fabrics made from such fibers, are conventional when measured by cooling power, particularly when both moisture release and wind conditions exist. It shows that the synthetic fiber (more specifically, a cloth made from a conventional synthetic fiber) has a larger cooling effect. Since these conditions are common and are actually expected, when a person wears clothing (especially sports apparel and similar clothing), the result is that an article made from the fibers of the present invention Strengthens the conclusion that a person who wears the article, or who otherwise contacts the skin with the article, has a cooling effect.

(Example group 2)
Various materials are prepared so that the invention can be further described. These materials are summarized in the following table.

1-Each fabric sample is in the form of an open sock / sleeve woven from the described fibers.
2-BDO adipate is an adipate prepared from 1,4-butanediol and adipic acid.
3-HDO adipate is an adipate prepared from 1,6-hexanediol and adipic acid.
4-BDO / HDO adipate is an adipate prepared from adipic acid and a mixture of 114-butanediol and 1,6-hexanediol.

1-Each fabric sample is in the form of an open sock / sleeve knitted from the fibers described.
2-BDO adipate is an adipate prepared from 1,4-butanediol and adipic acid.
3-HDO adipate is an adipate prepared from 1,6-hexanediol and adipic acid.
4-BDO / HDO adipate is an adipate prepared from adipic acid and a mixture of 114-butanediol and 1,6-hexanediol.

  Each document referred to above is incorporated herein by reference. Except for the examples or otherwise explicitly indicated, all quantities herein that specify quantities such as materials, reaction conditions, molecular weight, number of carbon atoms, etc. are referred to as “about” It should be understood that it is modified by terminology. Unless otherwise indicated, all percentage, ppm and part values are on a weight basis. Unless otherwise indicated, each chemical or composition referred to for the present invention is a commercial grade material and includes isomers, by-products, derivatives and commercial grades. It should be construed that other materials that are normally understood to be present may be included. However, the amount of each chemical component is expressed in an amount excluding any solvent or diluent oil that may conventionally exist in commercial grade materials, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any other element. As used herein, the expression “consisting essentially of” permits inclusion of substances that do not significantly affect the basic and novel characteristics of the composition under consideration. .

Claims (17)

(I) a polyester, polyether, polycarbonate or a combination thereof, an intermediate having a hydroxyl group at the end and having a Tg of 22 ° C. or lower;
(Ii) diisocyanate;
(Iii) A fiber prepared from a composition comprising a reaction product with a linear alkylene glycol chain extender. The fiber according to claim 1, wherein Tg of the composition from which the fiber is prepared is 22 ° C. or less. (I) The fiber according to any one of claims 1 to 2, wherein the end-hydroxyl intermediate is substantially free of a polyether block amide copolymer. The fiber according to any one of claims 1 to 3, wherein the fiber has an elongation of 200% to 300%. The fiber according to any one of claims 1 to 4, wherein the fiber has an effective cooling power of at least 49 watts / square meter when measured at a relative humidity of 30% and a wind speed of 3 m / s. The fiber according to claim 1, wherein the fiber is substantially free of an inorganic filler. (I) the terminal hydroxyl-terminated intermediate comprises polyethylene glycol, (ii) the diisocyanate comprises methylene diphenyl diisocyanate, (iii) the linear alkylene glycol chain extender is 1,4-butanediol, 1, The fiber according to any one of claims 1 to 6, comprising 6-hexanediol or a combination thereof. The composition from which the fiber is prepared;
(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 by mixing a polymer and / or copolymer and at least one other polymer and / or copolymer, each said polymer and / or copolymer being compatible and / or miscible with each other; Or (c) The fiber according to any one of claims 1 to 7, which is a polymer alloy containing a combination thereof. The polymer alloy comprises (i) (a) a polyol; (i) (b) a polyester intermediate derived from a polyol and a dicarboxylic acid; (ii) at least one diisocyanate; and (iii) at least one chain extension. 9. The fiber of claim 8, derived from reaction with an agent. A fabric comprising the fiber of claim 1. 11. The fabric of claim 10, wherein the fabric further comprises one or more additional fibers other than the fibers of claim 1, wherein the fabric is 10-80% by weight of these additional fibers. 12. The fabric of claim 11, wherein the additional fibers are selected from the group consisting of nylon fibers, polyester fibers, rayon fibers, acrylic fibers, and combinations thereof. An article comprising the fabric of claim 10. 14. The article of claim 13, wherein the article is a garment and wherein the fabric fibers are aligned in the garment so as to be in direct contact with the skin of the wearer of the garment. A method of providing a cooling effect to an article in direct contact with human skin,
I. Preparing a fabric comprising the fibers of claim 1;
II. Preparing an article comprising the fabric;
III. Directly contacting the article with human skin. A method of making a fiber,
I. An elastomer resin is prepared in an internal mixing device, and the elastomer resin is
(I) a polyester, polyether, polycarbonate or a combination thereof, an intermediate having a hydroxyl group at the end and having a Tg of 22 ° C. or lower;
(Ii) diisocyanate;
(Iii) a step prepared by reacting with a linear alkylene glycol chain extender;
II. Melt-spinning the elastomeric resin into monofilament or multifilament fibers. A method of making a cloth,
I. An elastomer resin is prepared in an internal mixing device, and the elastomer resin is
(I) a polyester, polyether, polycarbonate or a combination thereof, an intermediate having a hydroxyl group at the end and having a Tg of 22 ° C. or lower;
(Ii) diisocyanate;
(Iii) a step prepared by reacting with a linear alkylene glycol chain extender;
III. Melt spinning the elastomer resin into monofilament or multifilament fibers;
IV. Processing the fibers into a fabric, optionally in combination with one or more other fibers.