CN103547716B

CN103547716B - Elastomeric fibre and production and preparation method thereof

Info

Publication number: CN103547716B
Application number: CN201280024641.XA
Authority: CN
Inventors: R·R·韦杜拉; M-W·李
Original assignee: Lubrizol Advanced Materials Inc
Current assignee: Lubrizol Advanced Materials Inc
Priority date: 2011-04-15
Filing date: 2012-04-10
Publication date: 2016-11-16
Anticipated expiration: 2032-04-10
Also published as: EP2697415A1; US20170127741A1; TWI628327B; JP2017101373A; MX353977B; BR112013026090A2; TW201739974A; CA2832178A1; US20140101825A1; KR20140023363A; KR101928053B1; JP2014511949A; EP2697415B1; WO2012154364A1; JP6173299B2; AU2017201642A1; MY164541A; MX2013011848A; CA2832178C; CN103547716A

Abstract

It is excellent for the present invention relates to have the fiber of the nice and cool sense of touch of excellence, hands and contact skin to the nice and cool sense of touch of fiber, and is prevented from the undesirable sensation when hygrometric state, the most also has excellent elasticity.The invention still further relates to fabric, clothing and underwear, it has the nice and cool sense of touch of excellence, and is to use described fiber to obtain, and manufactures method and the goods thereof of this fiber.

Description

Elastomeric fibre and production and preparation method thereof

Background of invention

The present invention relates to the fiber with the nice and cool sense of touch of excellence, its hands and contact skin are excellent, and can Prevent the undesirable sensation when hygrometric state, the most also there is the elasticity of excellence.The invention still further relates to fabric, clothing and underwear Trousers, it has the nice and cool sense of touch of excellence, and is to use described fiber to obtain, and manufactures method and the system thereof of this fiber Product.

There is the goods for more comfort and clothing, particularly underwear and motion and/or relevant with training Lasting, the endless demand in dress ornament field.Such goods and the user of clothing and/or wearer wish that they to the greatest extent may be used Comfortable and the salubrious sensation of energy, is also such after being included in long use and disadvantageous condition.Such for manufacturing The fiber of article, particularly combinations thereof thing, can produce significantly impact to the performance of the article in these fields.

In addition to more comfortable, also it is desirable to such fiber can keep or even improve their elasticity.

Summary of the invention

The present invention provides the elastic cool fiber that a kind of Tg is not more than 22 DEG C, and more specifically provides and prepared by compositions Fiber, said composition comprises following product: the intermediate that (i) is hydroxy-end capped, it includes polyester, polyethers, poly-carbonic acid Ester or a combination thereof, wherein the Tg of this intermediate is not more than 22 DEG C；(ii) diisocyanate: and (iii) linear alkylene glycol Cahin extension agent.

The invention provides the fabric manufactured by fiber described herein, it is fine that it is mixed with other in some embodiments Dimension.The present invention provides the goods being made up of fabric described herein.

The present invention provides a kind of and provides in the goods being close to, the most directly contacting human body skin The method of nice and cool effect, it includes step: (1) prepares the fabric comprising fiber described herein；(2) preparation comprises described fabric Goods；(3) described goods are close to, the most directly contact human body skin.

The invention provides a kind of method manufacturing fiber, it includes step: (1) prepares elasticity in internal mix device Body resin, wherein said elastomer resin is by making following reaction preparation: the intermediate that (i) is hydroxy-end capped, it includes gathering Ester, polyethers, Merlon or a combination thereof, wherein the Tg of this intermediate is not more than 22 DEG C；(ii) diisocyanate；(iii) Linear alkylene diol chain extender；(2) described elastomer resin melt spinning is become monofilament or multifilament.

The present invention provides a kind of method manufacturing fabric, and it includes step: (1) prepares elastomer in internal mix device Resin, wherein said elastomer resin by make following reaction preparation: the intermediate that (i) is hydroxy-end capped, it include polyester, Polyethers, Merlon or a combination thereof, wherein the Tg of this intermediate is not more than 22 DEG C；(ii) diisocyanate；(iii) linear Aklylene glycol cahin extension agent；(2) described elastomer resin melt spinning is become fiber, in some embodiments become monofilament or Person's multifilament；(3) by described fiber, optional combines with one or more other fibers, is processed into fabric.

Detailed description of the invention

Feature and embodiment that the present invention is different will illustrate to describe below by indefiniteness.

Nice and cool effect

The present invention provides the elastic fiber of nice and cool sense of touch and the excellence with excellence.And this nice and cool effect is typically In the fabric being made up of this fiber and/or goods viewed, it is believed that this nice and cool effect is attributable to fibre property, and Also not dependent on included fabric and/or the type of goods and/or structure, although these parameters certainly can be to observed cool Refreshing effect has relevant impact.In other words, it is believed that this nice and cool effect is provided by this fiber, and more specific, by having The fiber having particular characteristic and/or chemical composition provides.In this application, we often notice and work as and contact skin, or When person is even close to human body skin, say, that between the fiber and human body skin of the present invention one layer or even two-layer On the top of clothing, this fiber can give nice and cool sense of touch.In some embodiments, this fiber is directly to connect with human body skin Touch.It is to be understood that fabric that the evaluation of nice and cool effect with fiber itself, can be made up of such fiber, by such fiber And/or any goods of making of fabric or its different combination evaluate.

Describing below is considered as the key factor causing nice and cool effect provided by the present invention, mainly saves in segment of fiber In.

Fiber

The present invention provides the elastic fiber of nice and cool sense of touch and the excellence with excellence.The meeting when contacting skin of this fiber Produce nice and cool sense of touch.This effect can be felt to being enough to by force in sensory testing.

This fiber can include thermoplastic elastomer (TPE) and can also include inorganic filler, but in certain embodiments, Said composition does not has any inorganic filler.

The Tg of the fiber of the present invention can be not more than 22 DEG C, and and the goods be made up of them be all the most flexible , and the nice and cool sense of touch of excellence is also provided when this fiber is used for clothing.

As used herein, " elasticity " and " elastic " represent that fiber strains with the four to 100% after stretching first Its tensile elongation of few about 50% is will then revert to after (double length).Elasticity can also be with " permanent deformation " of this fiber Describe." permanent deformation " and elastic contrary.Fiber is stretched to certain point, is stretched to this fibre in some embodiments The 50% of the known extension at break percentage rate of dimension, is discharged into the initial position before stretching subsequently, any again stretches.This fiber is opened The point of beginning traction load is referred to as percent set." elastomeric material " is also referred to as " elastomer " and " elastomer in this area ".

The fiber of the present invention can provide the balance of this benefit, also avoid simultaneously and causes due to perspiration etc. when hygrometric state Any adhesion or difference skin feel, and so when this fiber for clothing time, it is unhappy that it frequently results in wearer Sensation.The fiber of the present invention balances these whole factors, and carries in any one or combination of these factors Supply the performance of excellence.

In some embodiments, preparing the thermoplastic elastomer (TPE) used by fiber described herein is to be substantially free of or even There is no elastomer and/or the polyester type elastomer of polyamide type.More specific, the present invention can not have polyether block amide Copolymer, polyether amide copolymer and polyester-amide copolymer or its combine arbitrarily.More specific, included by the present invention group Compound can be substantially free of or even wholly without Pebax (being manufactured by Arkema).As used herein, term polyamide Polyamide-block in elastomer or elastomer is considered different from its chemical sense and differs markedly from polyurethane Carbamate block in elastomer or this elastomer.In some embodiments, polyamide connects and/or block is claimed Make N (R)-C (the O)-R-unit in this elastomer and/or connection, and polyurethane connects and/or block is referred to as this elastomer In N (R)-C (O)-O-R-unit and/or connection.

In other embodiments, the thermoplastic elastomer (TPE) being used for preparing fiber described herein can include polyether block acyl Amine copolymer thing, polyether amide copolymer, polyester-amide copolymer or its combine arbitrarily.

This polyester type elastomer is not specifically limited, and example is polyetherester copolymer and polyester ester copolymer. They can be used alone or they two or more can be applied in combination.

In them, commercially available polyester type elastomer be Grilux (by Dainippon Ink and Chemicals, Inc. manufacture), Nouvelan (being manufactured by Teijin Chemicals Ltd.), Pelprene is (by Toyobo Co., Ltd. system Make), Hytrel (being manufactured by DuPont-Toray Co., Ltd.) and Primalloy is (by Mitsubishi Chemical Corporation manufactures).

Being included in the resin Composition in fiber of the present invention is the nice and cool sense of touch that the invention provides excellence, and this thermoplasticity Elastomer can be used alone.The present invention another benefit is that fiber described herein is made when they only comprise thermoplastic elastomer (TPE) During for resin Composition, it is generally of the sensation of non-adhesive and thus without becoming to be difficult to spinning.Although other resin can be with Resin combination described here uses, but it need not bear any adhesion or offending sensation, and such sensation can be accompanied Along with many conventional fibers.Use other resin in some embodiments.Although inorganic filler resin can be with here Described resin combination uses, but it need not bear any adhesion or offending sensation, and such sensation can be along with Many conventional fibers.

In some embodiments, this fiber and/or prepare its resin and be substantially free of and do not have any inorganic filler. When using inorganic filler, it is not specifically limited, and example can include mineral type pigment, such as calcium carbonate such as Precipitated calcium carbonate and ground calcium carbonate, brium carbonate, magnesium carbonate such as alkaline magnesium carbonate, calcium sulfate, barium sulfate, titanium dioxide, oxygen Change ferrum, stannum oxide, titanium oxide, zinc oxide, magnesium oxide, ferrite powder, zinc sulfide, zinc carbonate, aluminium nitride, silicon nitride, satin white, Kieselguhr such as burns kieselguhr, calcium silicates, aluminium silicate, magnesium silicate, silicon dioxide such as amorphous silica, amorphous conjunction Become silicon dioxide and silica sol, colloidal alumina, pseudobochmite, aluminium hydroxide, magnesium hydroxide, aluminium oxide, hydration oxygen Change aluminum, lithopone (litopon), zeolite, hydration halloysite, clay, brucite, aluminosilicate, Talcum, pyrophillite, montmorillonite Such as saponite, Strese Hofmann's hectorite., sauconite, humite, montmorillonite, beidellite and nontromite, Vermiculitum, Muscovitum such as gold cloud Mother, biotie, zinnwaldite, dolomite, paragonite, celadonite and glauconite, clinochlore, chamosite, nepouite, manganese Mackensite, sudoite, donbasite, holmesite, emerylite, Thulite, antigorite, lizardite, fire stons Cotton, mesite, cronstedtite, berthierine, greenalite, garnierite, Kaolin such as kaolinite, dickite, nacrite With galapectite, layering Kaolin, calcined kaolin, meerschaum, Paligorskite, imogolite (imogolite), light green diamond stone, silicon Iron-stone, penwithite, activated earth, bentonite and sericite.They can be used alone or they two or more Plant and can be applied in combination.In some embodiments, filler be titanium oxide, zinc oxide, Barium monoxide, silicon dioxide or its one A little combinations.The form of inorganic filler is not specifically limited, and example is that finite form is the most spherical, needle-like, plate type form Deng, or non-finite form.

When it is present, this inorganic filler content lower limit can be 1%, 2% or 7% weight, and the upper limit is 30% weight.

The fiber of the present invention can comprise one or more other additives further, and in some embodiments must At least one or multiple other additive (having exceeded existing thermoplastic elastomer (TPE) and any inorganic filler) must be comprised.Separately Outward, this fiber can distort and/or be coated with another fiber, and the factor needed for underwear of improving is such as in the present invention Contact skin in unbarred degree.Another fiber such is not specifically limited, and example is polyamide type Resin such as nylon 6 and nylon 12；Polyester, Cotton Gossypii and artificial silk.

In some embodiments, the fiber of the present invention can use q_maxValue describes.The q of fiber_maxValue lower limit can be 0.20,0.21 or 0.22J/s/cm².If q_maxValue is less than 0.20J/s/cm², then test subject will not feel any nice and cool touching Sense, even if being also such when carrying out sensory testing.In other embodiments, the q of this fiber_maxValue can less than 0.20 or Even greater than 0.22J/s/cm²。

In this manual, q_maxValue is defined as being stored in predetermined heat have the surface area of regulation and predetermined weight In hot plate, and hot plate just contact with sample surfaces after in the case of, low temperature shift to sample storage heat hot-fluid The peak value of amount.Assume q_maxValue simulates when putting on clothing, the body heat that sample is removed from health, and assumes q_max Being worth the highest, the body heat removed from health when putting on clothing is the highest, and nice and cool sense of touch is the most excellent.

In some embodiments, the lower limit of the thermal conductivity of fiber of the present invention can be 1x10^-3℃/Wm².Thermal conductivity also by It is considered one of nice and cool sense of touch important parameter corresponding to it.If thermal conductivity is less than 1x10^-3℃/Wm², the most most of tested person Person is unable to perceive that any nice and cool sense of touch, even if it is also such for carrying out sensory testing.

In this specification, thermal conductivity can be by measuring on the sample placed on sample stage of hot plate the heat after stratification Loss speed calculates, and the temperature of hot plate is at predetermined temperature stabilization, and is counted by following formula (2) Calculate.

Thermal conductivity (W/cm/ DEG C)=WD/A/ Δ T (2)

Here: W: heat flow (J/s)

D: thickness of sample (cm)

A: hotplate surface amasss (cm²)

Δ T: the temperature difference (DEG C) between sample stage and hot plate

The fiber of the present invention can use with the form of composite fibre, and it comprises thermoplastic elastomer (TPE) and another is set Fat, and can have core-shell structure and comprise core segment (containing can dyeing resin) and shell part (containing thermoplastic elastomer (TPE) Resin), the thickness of shell part is 20 microns or thinner (being referred to as core-shell type conjugated yam the most in some cases).This The fiber of bright excellent nice and cool sense of touch can be the fiber with core-shell structure (it has good dyestuff ability), and it will Such can maintain the excellent performance of thermoplastic elastomer (TPE) for core segment and such as feel nice and cool sense of touch by dyeing resin, and have Nice and cool sense of touch and excellent flexible thermoplastic elastomer (TPE) are for shell part.

The form of this core-shell type conjugated yam is not specifically limited, and the horizontal stroke formed in the case of this fiber Cross sectional shape is the longitudinal direction intersecting and being perpendicular to fiber, and it can be positive round, ellipse etc..Equally, this fiber can have concentric Core-shell type structure, core segment and shell part are concentrically formed wherein, or non-concentric core-shell type structure, at it Middle core segment and shell part are non-being concentrically formed.Equally, this fiber can have a structure in which, wherein in the feelings of this fiber Present in condition, multiple core segments are the longitudinal directions intersecting and being perpendicular to fiber.

In some embodiments, the fiber of the present invention is elastic cool fiber, and its Tg is not more than 22 DEG C.

In some of these embodiments, the Tg of this fiber can be not more than 22,15,10,0 ,-10 ,-20 ,-30 or Even-40 DEG C.These Tg limits can apply to this fiber itself, manufacture this fiber compositions (in said composition spinning or Before person is processed into fiber), the preparation intermediate of said composition or its combine arbitrarily.

In some of these embodiments, the percentage elongation that this fiber can realize can be 200%-300%.

The fiber of the present invention is prepared by such compositions, and it includes following product: (i) is hydroxy-end capped Intermediate, (ii) diisocyanate and (iii) linear alkylene diol chain extender.This hydroxy-end capped intermediate can include gathering Ester, polyethers, Merlon or a combination thereof, wherein the Tg of this intermediate is not more than 22 DEG C.In some embodiments, in the middle of this Body derives from Polyethylene Glycol.This diisocyanate can include diphenyl methane-4,4'-diisocyanate.This linear alkylene two Alcohol can include 1,6-butanediol and similar material.In some embodiments, the hydroxy-end capped intermediate used by the present invention It is to be substantially free of or even without polyether block amide copolymer and/or its unit.

In other embodiments still, the fiber of the present invention is prepared by such compositions itself, this combination Thing is to be prepared by following component: (i) intermediate, and it includes and/or be derived from Polyethylene Glycol or adipate ester, and (it derives from One or more aklylene glycols and adipic acid), (ii) diisocyanate, it includes methylenediphenyl diisocyanates；With (iii) linear alkylene diol chain extender, its can include BDO, 1,6-hexanediol or a combination thereof.Real at these Executing in some of scheme, this cahin extension agent includes BDO, and this adipate ester be by BDO, 1,6-hexanediol or Prepared by person's a combination thereof.In some of these embodiments, this adipate ester is by BDO and 1,6-hexanediol Prepared by mixture.Additionally, in some of these embodiments, for preparing the compositions of this fiber be: 40-80,40- 70,50-60 or the intermediate of even 55-58 or 56-57 weight %；20-50,30-40,30-35 or even 31-34 or The diisocyanate of person's 32-33 weight %；With 4-25,5-20,5-15 or the cahin extension agent of even 8-11 or 9-10 weight %.This The fiber of invention can be manufactured by such compositions, and it comprises above-mentioned material, and it can also comprise one or more Polymeric additive, including any following other additive.In some embodiments, said composition can be wrapped further Include antioxidant, lubricant and/or processing aid, and can even have the catalyst containing metal.

In some embodiments, the fiber of the present invention is prepared by compositions itself, and said composition is by following Component prepare: (i) intermediate, it includes and/or is derived from Polyethylene Glycol, and (ii) diisocyanate, it includes methylene Base diphenyl diisocyanate；(iii) linear alkylene diol chain extender, it include BDO, 1,6-hexanediol or Person's a combination thereof.In some of these embodiments, this cahin extension agent includes BDO.Additionally, in these embodiments In some, for preparing the compositions of this fiber it is: 40-80,40-70,40-60 or even 46-49 or 47-48 weight % Intermediate；20-50,30-50,35-45 or the diisocyanate of even 40-43 or 41-42 weight %；With 4-25,5- 20,5-15 or the cahin extension agent of even 9-12 or 10-11 weight %.

It addition, the compositions preparing described fiber can be polymer alloy, comprising: (a) heterophasic copolymer, its be by Polymer and/or other polymer of copolymer segment and at least one and/or copolymer segment react to be prepared；B () is polymerized Thing mixture, it is to be prepared by mixed polymer and/or other polymer of copolymer and at least one and/or copolymer , the most each polymer and/or copolymer are compatible with each other and/or mixable；Or (c) a combination thereof.This polymer Alloy can derive from following reaction: (i) (a) polyhydric alcohol；I () (b) intermediate polyester itself, it derives from polyhydric alcohol and dicarboxyl Acid；(ii) at least one diisocyanate；(iii) at least one cahin extension agent.

Generally, the TPU polymer type used by the present invention can be this area and any conventional TPU of known in the literature gathers Compound, if its (represent this fiber itself, manufacture the compositions of this fiber and/or for preparing the intermediate of said composition) table Reveal above-mentioned Tg, percentage elongation and/or elasticity just.While not wishing to be limited to theory, but applicants contemplate that The compositions meeting these requirements it is expected to provide identical with what the specific embodiment included in the application was confirmed Nice and cool effect, or selectable, be also such when meeting at least one or multiple other parameter described here.

Suitably TPU polymer is typically by by polyester the most hydroxy-end capped to polyisocyanates and intermediate, hydroxyl Prepared by polyethers, hydroxy-end capped Merlon or its mixture and reacting with one or more cahin extension agents of end-blocking, It entirely well known to a person skilled in the art.

This hydroxy-end capped intermediate polyester is typically such linear polyester, and its number-average molecular weight (Mn) is about 500-about 10000, about 700-about 5000 or about 700-about 4000, acid number is typically smaller than 1.3 and is preferably smaller than 0.8.This molecular weight is that the mensuration by terminal functional groups determines, and relevant with number-average molecular weight.This polymer be as Get off to produce: (1) one or more glycol and one or more dicarboxylic acids or the esterification of anhydride, or (2) ester exchange Reaction, i.e. the reaction of the ester of one or more glycol and dicarboxylic acids.Usually more than the glycol more than 1 mole is than the mol ratio of acid It is preferred, it is therefore an objective to obtain the linear chain with the terminal hydroxy group being dominant.Suitably intermediate polyester also includes different lactones Such as polycaprolactone, it is typically manufactured by 6-caprolactone and Bifunctionalized initiator such as diethylene glycol.Desired The dicarboxylic acids of polyester can be aliphatic, cyclic aliphatic, aromatics or a combination thereof.Suitably dicarboxylic acids (its can be used alone or Person is used in mixed way) be generally of 4-15 carbon atom altogether, and include: succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., pungent two Acid, Azelaic Acid, decanedioic acid, dodecanedioic acid, phthalic acid, terephthalic acids, cyclohexane dicarboxylic acid etc..Above-mentioned two can also be used The anhydride of carboxylic acid such as phthalic anhydride, tetrabydrophthalic anhydride etc..Adipic acid is preferred acid.Reaction is formed to be made us The glycol of desired intermediate polyester can be aliphatic, aromatics or a combination thereof, and has 2-12 carbon atom altogether, and Including ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, 2，2-dimethyl-1，3-propanediol, 1,4-CHDM, decamethylene glycol, ten dialkylene glycol etc., Isosorbide-5-Nitrae-fourth two Alcohol is preferred glycol.

Hydroxy-end capped polyether intermediate is polyether polyol, derives from and has the glycol of 2-15 carbon atom altogether or polynary Alcohol, is alkyl diol or dihydroxylic alcohols in some embodiments, and it reacts with ether (or epoxide), this ether (or epoxy Compound) comprise the alkylen groups with 2-6 carbon atom, it is typical that oxirane or expoxy propane or its mixing Thing.Such as hydroxy-functionalized polyether can produce as follows: first by propylene glycol and propylene oxide reaction, subsequently with oxirane Reaction.The primary hydroxyl formed by oxirane has bigger reactivity than secondary hydroxyl, and is therefore preferred.Useful city Sell polyether polyol and include PEG (it comprises the oxirane with glycol reaction), poly-(propylene glycol) (its comprise with The expoxy propane of propylene glycol reaction), poly-(tetramethylene glycol) (it comprises the water reacted with oxolane) (PTMEG).PTMEG It it is preferred polyether intermediate.Polyether polyol farther includes the polyamide addition compound of alkylene oxide, and can include such as Ethylene diamine addition product (it comprises the product of ethylene diamine and expoxy propane), (it comprises two to diethylenetriamine addition product Ethylene triamine and the product of expoxy propane) and similar polyamide type polyether polyol.Copolyether can be used for this Invention.Typical copolyether includes the product of THF and oxirane or THF and expoxy propane.They are as Poly THF B (a kind of block copolymer) and Poly THF R (a kind of random copolymer) is available from BASF.Different polyether intermediate is led to Often have by terminal functional groups detect determined by number-average molecular weight (Mn), it is greater than about 700, and the most about 700-is big About 10000, about 1000-about 5000, or the mean molecule quantity of about 1000-about 2500.A kind of especially it is desirable that Polyether intermediate be the mixture of the molecular weight polyether that two or more are different, such as 2000M_nAnd 1000M_nPTMEG's Mixture.

In some embodiments, the compositions of the present invention is prepared by Polyethylene Glycol (PEG).In other embodiments In, this intermediate is by adipic acid and the BDO and 1 of 50/50 mixing, the polyester that the reaction of 6-hexanediol manufactures.

The polycarbonate-based polyurethane resin of the present invention can be by diisocyanate and hydroxy-end capped Merlon and increasing Prepared by the mixture reaction of chain agent.This hydroxy-end capped Merlon can be prepared with carbonate reaction by glycol.

United States Patent (USP) No.4131731 at this with it about hydroxy-end capped Merlon and their content of preparation It is incorporated herein by reference.Such Merlon is linear, and has terminal hydroxy group, substantially eliminates other end groups.The most anti- Answering thing is glycol and carbonic ester.Suitably glycol is selected from containing 4-40 and or the cycloaliphatic of even 4-12 carbon atom and fat Fat race glycol, and each molecule contains 2-20 alkoxyl, and each alkoxyl contains the polyoxy alkylidene of 2-4 carbon atom Glycol.The glycol being applicable to the present invention includes the such as BDO of the aliphatic diol containing 4-12 carbon atom, Isosorbide-5-Nitrae-penta Glycol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyls 1,6-hexanediol, decamethylene-glycol, the sub-oil base glycol of hydrogenation two, Hydrogenate two oil base glycol；With cycloaliphatic diol such as cyclohexanediol-1,3-hydroxymethyl-cyclohexane-Isosorbide-5-Nitrae-cyclohexanediol, 1, 4-dihydroxymethyl ring 1,3-hexane, Isosorbide-5-Nitrae-interior methylene-2-hydroxyl-5-hydroxymethyl hexamethylene, and poly alkylene glycol.This is anti- Glycol that should be used can be single glycol or the mixture of glycol, and it depends on finally producing desired performance.Poly-carbonic acid Ester intermediate (it is hydroxy-end capped) be typically this area and known in the literature those.Suitably carbonic ester is selected from comprising 5- The alkylene carbonate of 7 rings.Suitable carbonic ester for herein includes vinyl carbonate, trimethylene carbonate, and four is sub- Methyl carbonic, carbonic acid 1,2-Asia propyl ester, carbonic acid 1,2-butylene, carbonic acid 2,3-butylene, carbonic acid 1,2-ethyl, carbonic acid 1, 3-Asia pentyl ester, carbonic acid Isosorbide-5-Nitrae-Asia pentyl ester, carbonic acid 2,3-Asia pentyl ester and carbonic acid 2,4-Asia pentyl ester.

Equally, the most suitably dialkyl carbonate, cycloaliphatic carbonic ester and diaryl carbonate.This dialkyl carbonate Base ester can comprise 2-5 carbon atom in each alkyl, and its specific example is diethyl carbonate and carbonic acid dipropyl Base ester.Cycloaliphatic carbonic ester, particularly bicyclo-aliphatic acid ester carbonate can comprise 4-7 carbon atom in each ring structure, And one or two such structures can be there is.When a group is cycloaliphatic, another can be alkyl or Person's aryl.On the other hand, if a group is aryl, then another can be alkyl or cycloaliphatic.Suitably diaryl The example of carbonic ester (can comprise 6-20 carbon atom in each aryl) is dipheryl carbonate base ester, carboxylol ester and carbon Acid dinaphthyl ester.

This reaction is under ester exchange catalyst presence or absence, at the temperature of 100 DEG C-300 DEG C and 0.1-300mm hydrargyrum Column pressure, by glycol with carbonic ester such as alkylene carbonates with 10:1-1:10, but the molar range of preferably 3:1-1:3 is carried out Reaction is carried out, and can also be removed by distillation lower boiling glycol while carrying out.

More specific, this hydroxy-end capped Merlon is prepared in two stages.In the first stage, glycol is with sub- Alkyl carbonate reaction forms the Merlon of low-molecular-weight hydroxyl end-blocking.Low boiling glycol is by 100 DEG C-300 DEG C, Preferably at 150 DEG C-250 DEG C, the evaporated under reduced pressure at 10-30mmHg, preferably 50-200mmHg removes.Fractional distillation can be used Tower carrys out separating by-products glycol from reactant mixture.This by-product glycol can be taken away from tower top, and unreacted alkylene Base carbonic ester and diol reactant can return reaction vessel as backflow.Noble gas or atent solvent stream may be used for promoting Enter by-product glycol to be removed when it is formed.When the amount of the by-product glycol obtained shows hydroxy-end capped Merlon When the degree of polymerization is 2-10, pressure is gradually lowered to 0.1-10mmHg, and removes unreacted glycol and alkylene carbonate. This indicates the beginning that second stage is reacted, during it, low-molecular-weight hydroxyl end-blocking Merlon be by when it 100-300 DEG C, distill glycol and condense, until obtaining during the pressure initiation of preferably 150-250 DEG C and 0.1-10mmHg The hydroxy-end capped Merlon of desired molecular weight.The molecular weight (Mn) of this hydroxy-end capped Merlon can be about 500 to about 10000 changes, but in a preferred embodiment, it will be in the scope of 500-2500.

The second of the TPU polymer of the manufacture present invention must composition be polyisocyanates.The polyisocyanates of the present invention leads to Often there is formula R (NCO)_n, n is typically 2-4 here, and 2 is very preferably as said composition is thermoplastic.Therefore The polyisocyanates of the degree of functionality with 3 or 4 is to use with considerably less amount, e.g., less than 5% and desirably less than 2 Weight %, gross weights based on whole polyisocyanates, this is because they result in crosslinking.R can be aromatics, cycloaliphatic With aliphatic or a combination thereof, it is generally of about 20 carbon atoms of 2-altogether.The suitably example bag of aromatic diisocyanates Include diphenyl methane-4,4'-diisocyanate (MDI), H₁₂MDI, an eylylene diisocyanate (XDI), a tetramethyl Eylylene diisocyanate (TMXDI), phenylene-Isosorbide-5-Nitrae-diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI) With diphenyl methane-3,3'-dimethoxy-4 ', 4'-diisocyanate (TODI).The suitably example of aliphatic diisocyanate Including isophorone diisocyanate (IPDI), Isosorbide-5-Nitrae-cyclohexyl diisocyanate (CHDI), hexamethylene diisocyanate (HDI), 1,6-diisocyanate root closes-2,2,4,4-tetramethyl hexane (TMDI), 1,10-decane diisocyanate and trans two Diphenylmethane diisocyanate (HMDI).Highly preferred diisocyanate is MDI, and it contains less than about 3 weight % O-to (2,4) isomer.

The 3rd of the TPU polymer of the manufacture present invention must composition be cahin extension agent.Suitably cahin extension agent is to have about 2- The lower aliphatic of about 10 carbon atoms or short-chain diol, and include such as ethylene glycol, diethylene glycol, propylene glycol, dipropyl Glycol, tripropylene glycol, 2,2'-ethylenedioxybis(ethanol)., the cis-trans-isomer of cyclohexane dimethanol, neopentyl glycol, BDO, 1,6- Hexanediol, 1,3 butylene glycol and 1,5-PD.The present invention needs linear alkylene diol chain extender, but some embodiment party In case, other cahin extension agent can be applied in combination with this linear alkylene diol chain extender.In such embodiments, aromatics Glycol can serve as cahin extension agent.Benzenediol (HQEE) and xylylene glycol are used suitable in the TPU manufacturing the present invention Cahin extension agent.Xylylene glycol is 1,4-bis-(methylol) benzene and the mixture of 1,2-bis-(hydroxymethyl) benzene.Benzenediol It is preferred aromatic chain extenders, and specifically includes hydroquinone, i.e. double (beta-hydroxy ethyl) ether, also referred to as Isosorbide-5-Nitrae-two (2-hydroxyl Base oxethyl) benzene；Resorcinol, i.e. double (beta-hydroxy ethyl) ether, also referred to as 1,3-bis-(2-hydroxyethyl) benzene；Catechol, That is, double (beta-hydroxy ethyl) ether, also referred to as 1,2-bis-(2-hydroxyl-oxethyl) benzene；And combinations thereof.Preferably cahin extension agent is 1,4- Butanediol.

Above-mentioned three kinds must can exist at catalyst by composition (hydroxy-end capped intermediate, polyisocyanates and cahin extension agent) Lower reaction.

Generally, the catalyst of any routine may be used for entering diisocyanate with hydroxy-end capped intermediate or cahin extension agent Row reacts, and it is known in prior art and document.The suitably example of catalyst includes different the having of bismuth or stannum Machine compound such as carbonate, wherein moieties has about 20 carbon atoms of 1-, and specific example include Bismuth Octoate, Lauric acid bismuth etc..Preferably catalyst includes different tin catalysts such as tin octoate, two octanoic acid dibutyl tin, tin dilaurate two Butyl tin etc..The amount of such catalyst is the least, the most about 20-about 200 parts/million, is formed based on polyurethane The gross weight of monomer.

The TPU polymer of the present invention can be manufactured by any typical polymerization methods of well known in the art and literature.

In some embodiments, the polyurethane of the present invention manufactures via " step " method, whole components It is to add simultaneously all together or be added substantially simultaneously in heated extruder, and reaction forms polyurethane.Two Carbimide .s Ester is typically about 0.95-about 1.10 with the equivalent proportion of hydroxy-end capped intermediate and the total yield of diol chain extender, preferable About 0.97-about 1.03, and preferably approximately 0.97-about 1.00.In some embodiments, Shao of the TPU formed Family name's A hardness is typically less than 80A, 85A or even 95A.The reaction temperature using urethane catalyst can be about 175 DEG C-about 245 DEG C or the most about 180 DEG C-about 220 DEG C.The molecular weight (Mw) of this thermoplastic polyurethane can be big About 100000-about 800000 dalton or about 150000-about 400000 or the most about 150000-are about 350000, it passes through gpc measurement relative to polystyrene standards.

Useful additive can be to use in TPU described herein in right amount, and the most such additive can be at preparation TPU Before, among or add afterwards.Such other additive include Opacifying pigment, coloring agent, mineral filler, stabilizer, Lubricant, UV absorbent, processing aid and other additives desired.Useful Opacifying pigment includes titanium dioxide, oxidation Zinc and titanate are yellow, and useful coloring pigment includes white carbon black, oxide yellow thing, brown oxide, thick and burnt ochre or palm fibre Soil, chrome oxide green, cadmium pigment, chromium pigment and the metal-oxide of other mixing and organic pigment.Useful filler includes diatom Soil (superfloss) clay, silicon dioxide, Talcum, Muscovitum, silicoglaserite, barium sulfate and calcium carbonate.If it is desire to, it is possible to use Useful stabilizer such as antioxidant, and include phenolic antioxidant, and useful light stabilizer include organophosphorus ester and Organo-tin mercaptide (mercaptides).Useful antioxidant also includes three-dimensional hindered phenol antioxidant.Useful lubricant includes Metallic stearate, paraffin oil and amide waxe such as alkylene bis-stearamides such as N, N ' ethylene bis-stearamide and pelargonate Ester.Useful UV stabilizer includes 2-(2'-hydroxyl phenol) benzotriazole and 2-Viosorb 110.Typical TPU can also be added Fire retardant.

Plasticiser additive can also make for reducing hardness simultaneously, and if they use on a small quantity, the most do not affect performance. In some embodiments, plasticizer is not used.

In some embodiments, the nice and cool effect of this fiber can be expressed with effectively cooling power.Although existing not The same means measuring nice and cool effect provided by the present invention, but the application includes about the two kinds of sides measuring this effect The details of case.First look at the nice and cool effect that the fabric manufactured by fiber described here is provided, here this fabric and and fabric The area of " skin " of contact (test surfaces of skin being that instead of individual in this case is two places, and here Constant wind blows along this fabric.Although included actual conditions is considered as most important for comparative result purpose, But the assessment of these types is it is of course possible to carry out in different ambient temperatures, humidity level, wind speed, " skin " initial temperature, No matter should leave or eliminate by " skin " thermal source, and can carry out at its different dependent variables.It addition, this ginseng Yes for number in specific region measurement.Another program meets above-mentioned basic test method, but adds other perspiration Variable, discharges the different speed of dampness in test process from " skin ".Use these test-types, can measure not Under conditions of Tong, the amount of the energy needed for holding " skin " temperature, or selectable, measure " the skin when not applying thermal source Skin " temperature decline speed, therefore give about included fabric cooling power instruction.Concrete test condition and knot Fruit is to provide in the embodiment part of this specification.It is important to note that testing scheme no matter the most used and used concrete Condition how, and whole tests carried out so far have shown that compared with the contrast material being tested equally, by institute here The fabric exhibits stating fiber manufacture goes out considerably higher cooling power and allows to reduce with bigger temperature faster.

In some embodiments, the fiber of the present invention is when assessing by said method, and concrete is placed in survey at fabric In place of examination skin surface, there is work to keep the active thermal source of skin surface temperature, 30% relative humidity, 3m/s wind speed and 15 DEG C ambient temperature, it is provided that for 629cm²The cooling power of at least 31 watts of test, or at least 49 watts/square metres of regulations Different cooling power.That is, it needs at least 49 watts of power/square metre areas keep skin temperature, these give and other materials Material (nylon and polyester such as can not break through the limit of 31 watts under the conditions of accurate same test) is compared, and this fabric is knitted at this Thing will be supplied to the instruction of the nice and cool effect of individual in place of their skin.This cooling power is for 629cm²Test Area can also is that at least 34 watts, at least 55 watts/square metres, and this fiber is monofilament here, and is not half darkening.Identical Limit can be used at 50% relative humidity and 3m/s wind speed, and in 5m/s wind speed and the test that carries out at 50% relative humidity.

In similar embodiment, the fiber of the present invention, when being evaluated by said method, is particularly placed at fabric Part on test skin surface, has work to keep the active thermal source of skin surface temperature, 50% relative humidity, 0.3m/s wind Speed and the ambient temperature of 15 DEG C, it is provided that for 629cm²The cooling power of at least 13 or 14 watts of test area, at least 21 or 22 watts/square metre.

Produce the feel nice and cool method of fiber of sense of touch of the excellence of the present invention to be not specifically limited, and can use conventionally known Method, such as produce containing thermoplastic elastomer (TPE) and the resin particle of inorganic filler, and use obtained resin particle to melt The method producing it with spinning.

This core-shell type conjugated yam can also be by such as will be containing can dyeing resin, thermoplastic elastomer (TPE) and inorganic The resin particle of filler loads composite spinning equipment and melted and spinning, and they produce.

The present invention provides the method manufacturing fiber, and it includes step: (I) prepares elastomer tree in internal mix device Fat.This elastomer resin by make following reaction preparation: the intermediate that (i) is hydroxy-end capped, (ii) diisocyanate and (iii) linear alkylene diol chain extender.This intermediate can be polyester, polyethers, Merlon or a combination thereof, wherein in this The Tg of mesosome is not more than 22 DEG C.Second step (II) is that this elastomer resin melt spinning is become fiber, such as monofilament or Multifilament.In some embodiments, this fiber is monfil.Above for described fiber with for preparing its combination The whole different feature of thing and the discussion of embodiment are also applied for this.

Fabric

The fiber of the present invention can the textile of the most such as knitting, textile and bonding use.Institute's shape The fabric become has the nice and cool sense of touch of excellence, the most also has the excellent elasticity of this fiber.

The fabric with excellent nice and cool sense of touch of the present invention can only comprise the excellence of the present invention and feel nice and cool the fiber of sense of touch, And this fiber and another entangled fiber can be comprised in other embodiments, be used for improving application-specific The required factor, such as in the clothing of directly contact skin.Such optional fiber that coexists is not specifically limited, and example Attached bag includes polyamide type resin such as nylon 6 and nylon 12, polyester, Cotton Gossypii and artificial silk.

The present invention includes the fabric manufactured by any fiber described herein, including Woven fabric, supatex fabric, braiding Fabric and combinations thereof.In some embodiments, the fabric of the present invention is Woven fabric.In other embodiments, the present invention Fabric be supatex fabric.In other embodiments still, the fabric of the present invention is braided fabric.It addition, the present invention Including fabric, it comprises the other fiber of one or more non-invention fibers further.This fabric can include 10-80 weight These other fibers of amount %, or no more than 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20% or 10% these are another Outer fiber.In some embodiments, there is not other fiber.In embodiments, here fabric also exists one Or multiple other fiber, these other fibers can be that nylon fiber, polyester fiber, rayon fiber, acrylic compounds are fine Dimension and combinations thereof.

Present invention additionally comprises the method manufacturing fabric, it includes step: (I) prepares elastomer tree in internal mix device Fat, wherein said elastomer resin is prepared as described above.The optional addition cross-linking agent that includes of the method, the most poly- Alkylene ether glycols or triol and the product of diisocyanate.Step (II) is to be become by described elastomer resin melt spinning Fiber such as monofilament or multifilament.In some embodiments, this fiber or manufacture the weight average of polymer of this fiber Molecular weight is at least 700000.Step (III) is that optional combines with one or more other fibers, adds by this fiber Work becomes fabric.

The present invention another benefit is that the moldability that the fabric comprising fiber described herein improves.When in fabric with close When suitable level uses, the fabric of the present invention successfully can mould at lower temperature and/or in the relatively low time, therefore changes Entered the weaving of the described fabric of protection, the ability of dyestuff etc., its can by the high temperature needed for more conventional fabric and/or low expose to the open air time Between damage, it is therefore an objective to successfully mould them.In some embodiments, the fabric of the present invention can no more than 150 or Even 140 DEG C temperature molding, and/or here this molding be less than 20,15 or even 10s complete.Some embodiment party In case, the fiber of the present invention must exist with minimum level in fabric, provides these benefits.In some embodiments, This lower limit is 40%, 50%, 60% or even 80%, and this percentage ratio represents weight % of fiber in fabric here, and this fiber must It must be the fiber of the present invention.But, it is also understood that the amount much smaller in fabric of the fiber of the present invention will improve the mould of fabric Ability processed.It should be noted that Spandex^TMIt is non-moldable with similar material at low temperature, and the fiber of these materials is not even Can be woven into fabric, unless used positive feeder, the device sheet of required a kind of costliness, this is owing to Spandex^TMFiber excessive Elastic.

Goods

The fabric of sense of touch that the excellence of the present invention feels nice and cool the fiber of sense of touch and the excellence of the present invention is felt nice and cool may be used for producing bag Include the goods of clothing.In the case of such as clothing as the goods of contact skin, the goods of the present invention show excellence Elasticity, provides cooling feeling for wearer, and does not have offending and/or tacky sensation, when humidity be also even as This.

Because goods and particularly clothing provide the nice and cool sense of touch of excellence, therefore it can cause cooling feeling when dressing Sensation, and produce salubrious sense.Equally, the present invention need not add inorganic filler to make clothing not adhere when humidity Sense, as other fibers with similar nice and cool effect as used by clothing can do.Therefore, the present invention is very suitable for Underwear.

The feel nice and cool clothing of sense of touch of the excellence of the present invention can use the fiber of nice and cool sense of touch of this excellence to produce completely, and And the clothing of particularly preferably excellent cooling feeling, it comprises and has a reversible construction and fabric that excellence is clearly felt, 30-70% The number of total coils of number comprises the fiber of the nice and cool sense of touch of excellence, and the number of turns of the fiber of the nice and cool sense of touch comprising excellence is arranged in skin In contact side (hereafter also called salubrious clothing).

About the clothing of the fabric comprising reversible construction, as the excellence of the present invention is felt nice and cool the clothing of sense of touch, comprise excellence The ratio of the number of turns of the fiber of nice and cool sense of touch is controlled in prescribed limit, and the fiber of such nice and cool sense of touch comprising excellence The number of turns be only arranged just in contact skin side, so that these clothing can have the undesirable sensation that prevents from being caused by hyperhidrosis Effect.

In recent years in, having developed and proposed different types of clothing, it has the function of improvement, as perspired in summer In the case of, in the case of training, motion etc. time put on underwear, and suggested such function clothes, such as by dredging The clothing that water cellulose such as polyester is produced.Equally, have studied and improve by using hydrophilic fibers to combine with Cotton Gossypii The method of breathability and by being formed for the mesh-structured of cloth or by forming flat sennit and warp-knit derivative braiding The method that lower needle knitting (moss knitting) improves breathability, and the open 2003-155669 of Japanese invention discloses and passes through The cloth of the reformation that deposition hydrophilic chemistry is formed to the hydrophobic fiber surface of this cloth of composition.But it is such comprising In the case of the clothing of hydrophobic fiber, although produced heat can effectively discharge, but it result in undesirable sensation, this Owing to causing the feeling of wetness in the case of skin or clothing humidity because of perspiring, and this fabric tends to simultaneously It is adhered on skin, causes the problem that clothing stop movement.

On the other hand, about comprising the salubrious clothing of the fabric with reversible construction, it can cause the cooling feeling when dressing Sensation, and produce salubrious sense, simultaneously it be prevented from the undesirable sensation that causes due to damp when dressing and Preventing fabric to be adhered on skin, this adhesion is owing to the deterioration with the separation property of skin, excellent nice and cool tactile by comprising The ratio of the number of turns of the fiber of sense controls to realize in the scope of defined.Equally, the circle of the fiber of excellent nice and cool sense of touch is comprised Number is only arranged just in skin side so that the fiber of the nice and cool sense of touch of this excellence can directly contact skin with can produce have into Clearly sense and the clothing of nice and cool sense of touch that one step is improved.

In the salubrious goods and clothing of the present invention, the lower limit of the ratio comprising the number of turns of the fiber of excellent nice and cool sense of touch can To be the 30% of number of total coils, and the upper limit can be 70% or the highest, e.g. the 75% of number of total coils, 80%, 90% or very To 100%.If below 30%, cause the effect of salubrious sense and nice and cool sense of touch can become not enough the most in some cases.With this Invention is obtained in that high level, and does not cause any undesirable sensation, this owing to because perspire the skin caused or Feeling of wetness in the case of person's clothing humidity.

As described previously for this fiber and fabric, salubrious goods such as clothing, thermoplastic elastomer (TPE) and inorganic can be comprised Filler, but it is to be substantially free of even without any inorganic filler in other embodiments.

In the goods such as clothing of the present invention, manufactured by the thickness of fabric is the thinnest, the nice and cool sense of touch of this excellence Fiber can use with another fiber combinations.Thermoplastic elastomer (TPE) content lower limit in the fiber of the nice and cool sense of touch of this excellence Can be 50 weight %.If below 50 weight %, enough nice and cool senses of touch will not be caused the most in some cases.Real at other Executing in scheme, the fiber content of the present invention is at least 15%, 25%, 35%, 45%, 55%, 65%, 75%, 85% in fabric and goods Or even 95 weight %.It is not intended to be limited to theory, it is believed that some minimum fiber contents in the fabric discussed and/or goods The nice and cool effect that have to be such that the fiber of the present invention is obvious.This minimum desired content can be according to included by the present invention Different formula and change, but can be substantially uniform for different formula in some embodiments.This Little content can be any of above percentage ratio.

In some embodiments, in the goods and/or clothing of the present invention, comprise the circle of the fiber of excellent nice and cool sense of touch Number is the most only arranged just in skin side.Arrangement in this way makes the number of turns of the fiber comprising excellent nice and cool sense of touch have and skin The dominant touch of skin, and cause nice and cool sense of touch and salubrious sense, and as described later, comprise the number of turns of hydrophobic fiber in outside Arrangement improves the heat and the diffusion of water and volatility that skin discharged.

In the goods and/or clothing of the present invention, the number of turns of the number of turns being different from the fiber comprising excellent nice and cool sense of touch is excellent Choosing is the number of turns comprising hydrophobic fiber.Because the number of turns of the fiber comprising excellent nice and cool sense of touch is only arranged just in skin side, because of This this comprise the number of turns primary alignment of hydrophobic fiber in outside.

In this manual, hydrophobic fiber represents chemical fibre, and it has the formal water percentage ratio of 5.0% or lower.Actual On, can illustrate is to comprise polypropylene (formal water percentage ratio: 0%), polyester (0.4%), acrylic resin (2.0%), nylon And the fiber of vinylon (5.0%) (4.5%).They can be used alone or their two kinds or more kinds of can combination make With.Thus, formal water percentage ratio represents the water percentage ratio at 20 DEG C He 65%RH.

The goods of the present invention and/or clothing can comprise natural fiber such as Cotton Gossypii and Caulis et Folium Lini, and semisynthetic fibre is such as Artificial silk and acetas, essential based in addition to the fiber and hydrophobic fiber of the nice and cool sense of touch of this excellence.

In some embodiments, the goods of the present invention and/or the salubrious clothing breathability of clothing are 200cm³/cm²/ s is high To 500cm³/cm²/s.If below 200cm³/cm²/ s, then breathability can deteriorate, and skin send heat diffusion and The evaporation of antiperspirant may be suppressed, and if it is more than 500cm³/cm²/ s, then hot and water passes through the transfer of clothing can not be abundant Carry out, and contrary, and the air of outside can pass through.Breathability can use air permeability tester, according to JIS L1096A Method is measured.

In fabric, goods and/or the clothing of the present invention, weight/square metre the upper limit can be 120,100 or even 90g/m².It is different from other the means that such cooling feeling is provided, if weight/square metre more than 120,100 or even 90g/m², then the mechanism of action can be suppressed, and therefore cooling feeling may deteriorate.

The method of the goods and/or clothing that produce the present invention is not specifically limited, such as, can use conventionally known side Rule is as felt nice and cool the method that the fiber of sense of touch produces clothing by the excellence of the braiding present invention.These materials can also be by often The methods such as rule known sewing, cutting, use the fabric with the reversible construction obtained by the way to produce.

The underwear of excellent nice and cool sense of touch can use the fiber of the present invention or the fabric of the present invention to produce.With Sample, the feel nice and cool clothing of sense of touch of the excellence of the present invention can serve as underwear.In such embodiments, the present invention can provide Any one or more of above-mentioned benefit, for this fiber, fabric, goods and/or clothing.

In addition to underwear, the present invention includes socks, glove, face shield, acoustic filter etc., and it can use the fibre of the present invention The fabric of the excellent nice and cool sense of touch of dimension or the present invention produces.By them and direct skin contact, and so they can draw Play effect excellent especially.

The present invention includes the goods being made up of above-mentioned fabrics.Such as, different clothing can be by the fabric system of the present invention Make.In some embodiments, being used for this fabric manufacturing underwear or clothing next to the skin, the fabric of the present invention is very suitable for it, This is owing to the comfortable and nice and cool effect provided by this fiber.Underwear such as medicated bra and T-shirt and for motion such as run, The sweat shirt of skiing, bicycle or other motions can benefit from the performance of these fibers.Next Geju City with Body contact Clothing benefit from elasticity provided by the present invention and nice and cool effect.It will be appreciated by those skilled in the art that any clothing can be by this Fabric and the fiber of invention are made.

In other embodiments, fiber described here is used for manufacturing any number of clothing of one or more and system Product, include but not limited to: gym suit such as medicated underpants, including bicycle, pad it, run, compress, train, golf, rod Ball, basketball, cheering squad, dancing, football and/or hockey medicated underpants；Shirt, including above for listed by medicated underpants any specifically Type；Tights, including training tights and compression tights；Swimming suit, including contest and swimming suit of recuperating；Tights, including Wrestling clothes, tights of running and swim；And footwear.Other embodiments include working clothing such as vest and uniform.Additionally Embodiment include underclothes, including medicated bra, underpants, man's underwear, camisole, moulding clothing, nightgown, crawlers, man Scholar's undershirt, tights, socks and fitted garment.Other embodiments include medical science clothing and goods, comprising: knitwear example As compressed knitwear, diabetes socks, static socks and dynamic socks；Treatment burn processing binder and thin film；Wound care applies Material；Medical science clothing.Application additionally includes Military Application, that reflects one or more above-mentioned concrete goods.Enforcement additionally Scheme includes goods on bed, including sheet, blanket, scarf, mattress, bedcover and pillowcase.

In some embodiments, the goods of the present invention are clothing, and the fiber alignment constituting the fabric of these clothing exists In these clothing, the direct skin contact of the next wearer with described clothing.This allows wearer to obtain provided by the present invention cool Whole benefits of refreshing effect.

Present invention also offers a kind of provides nice and cool effect in the goods directly contacted with human body skin such as clothing Method, it comprises step: the fabric of the fiber that (I) preparation comprises claim 1；(II) preparation comprises the goods of described fabric； (II) described goods are directly contacted with human body skin.

It is known that more above-mentioned materials can interact in final dispensing, the component of so final dispensing can not It is same as those being initially added.Such as metal ion (ion of such as detergent) can move to other of other molecules acid or Person anionic site.The product being consequently formed, including by being used for what its intended applications was formed by the compositions of the present invention Product, it is impossible to readily describe.But, whole such changes and product are included within the scope of the invention；The present invention Including by the compositions prepared by mixing said ingredients.

Embodiment

The present invention will be illustrated by the following examples further, and it specifically illustrates favourable embodiment.Although There is provided this embodiment so that the present invention to be described, but they are not intended to limit it.

Embodiment group

Have rated 7 kinds of materials to confirm the benefit of the present invention.These materials collect in the following table.

The explanation of table 1 sample and performance

Ex	Sample explanation¹	Fabric diameter [cm]	Fabric length [cm]	Fabric weight [g/m²]
					1	Baseline: without material (exposed test surfaces)	NA	NA	NA
2	Multifibres redness core polyester fiber	13.9	42.0	27
					3	Multifibres blueness core nylon fiber²	14.7	43.0	25
4	Monfil A³	5.3	37.5	90
					5	Monfil B⁴	8.4	35.5	65
6	Multifilament C⁵	9.2	29.0	66
					7	Monfil D half darkens⁶	10.8	43.0	43

1 each fabric sample is in the form of opening socks/sleeve.Diameter refers to sleeve produced by this fabric Diameter, and length is the physical length of sample.For fabric weight, by each samples weighing, other are then used to be reported Measuring, calculate the weight of each fabric, unit is g/m²。

2 these fibers are available commercially from Invista^TM。

3 fiber A are prepared by poly alkylene glycol, aklylene glycol and MDI.

4 fiber B are prepared by aklylene glycol adipate ester, aklylene glycol and MDI.

5 fiber C are the multifibres forms of fiber B, and chemical composition is identical with fiber B.

6 fiber D are fiber B, but add commercially available darkening agent.

Comparative example 1 is baseline, and represents and do not have fiber and/or fabric.Comparative example 2 and 3 is contrast material, its not generation The table present invention.Embodiment 4,5,6 and 7 represents the different embodiment of the present invention.

It should be noted that the fabric tested has different diameters, and the fabric for test obtained is different Weight.In order to these difference is described, carries out following test, and employed clip by fabric sample by this way Fixing, i.e. suitable tension force and Density to be provided on test surfaces, therefore allows described material effectively to contrast.This Any difference that a little testers do not illustrate is expected and test parameter does not produces significantly impact.

Method of testing and result

Test above-described embodiment to determine their cooling power.This test is aging in controlled temperature and humidity In proof box, the hot body model of diaphoresis is used to carry out as test surfaces.This has the body model of known surface area Test surfaces is equipped with thermocouple, monitors temperature and heating element heater to make test surfaces be heated to real human body skin temperature Degree, is used for testing.It addition, the power demand also having monitored heating element heater is observed keeps concrete skin temperature at test surfaces Required energy fluence.This test surfaces also is able to discharge dampness, the perspiration of simulation human body skin.Use high power fan as wind Source.Area for the test surfaces of whole such tests is 629cm²。

Testing for this, hot for perspiration body model be placed in ageing oven, it is set in 15 DEG C.Test be 30% and 50% relative humidity is carried out, and wind speed is 0.3m/s, 3m/s and 5m/s.The wind speed of 0.3m/s be in ageing oven just Normal condition, and thereby indicate that high speed fan is in and offs normal.The circular braiding of each material, open end sock sample are (also referred to as Make sleeve) it is placed on the test surfaces of the hot body model that perspires, it is the forearm of body model in this case.Sample is placed in For the test surfaces of test, then remove, and replace with next sample.As it has been described above, use clip by each Sample be fixed to perspire hot body model forearm on, and take care to ensure that this sample is close with comparable levels of tension force and fabric Degree is placed.

When each test starts, described case is arranged desired condition.Will be covered with the test of test fabric sample Surface is heated to the initial skin temperature of desired 31 or 34 DEG C, selects close to human skin temperature, and if wind be included in In test condition, then by starting fan to desired setting.Once set at these whole conditions, then first by monitoring heating Part keeps the quantity of power needed for the test surfaces temperature set, and starts test period.This quantity of power be by watt in units of Measure, and be referred to as fabric to be tested cooling power under given test condition.The cooling power reported, The power of system stability under given test condition.At the end of each test, sample fabric is replaced with different samples, and Repeat this test, change condition as required.

For embodiment 1 baseline, this test is carried out with test surfaces exposed, unlapped, it is provided that can From the effect desired by exposed skin.This baring skin baseline is included in comparative purpose test.

Following table summarizes test condition used and the embodiment tested under every set condition:

Table 2 uses collecting of the cooling power test condition of body model

1 these condition groups are to carry out in following test sequence: IV, I, V, II, VI, III.Condition group IV and V phase With, and be not carried out continuously, it is thus provided that the data of double group, which show the repeatability of result and the relative of sample room Difference.

2 target skin temperature always 34 DEG C tested for this, in addition to wherein wind speed is the condition group of 5m/s. Under these conditions, the skin temperature of 31 DEG C is used to guarantee that this system (it has limited heating efficiency) can be maintained at the phase The temperature hoped.

The result of this test collects in the following table:

Table 3 cools down power measurements and collects¹

Embodiment	Condition group I	Condition group II	Condition group III	Condition group IV	Condition group V	Condition group VI
							1-baseline	39.65	41.36	38.92	16.02	13.16	15.40
2-comparative example	28.82	29.43	27.78	11.83	9.54	10.96
							3-comparative example	30.19	30.16	30.36	12.93	10.60	12.25
The 4-present invention	38.18	37.03	37.19	15.42	13.10	15.14
							The 5-present invention	36.12	34.54	34.92	15.24	13.01	15.01
The 6-present invention	31.39	31.91	33.33	14.18	11.55	14.47
							The 7-present invention	31.98	34.18	31.36	14.08	12.43	14.32

The whole results reported in 1 this table are cooling power, are that unit is measured with watt [W].This is in rated condition Under at set point, needed for the hot body model that perspires keeps the temperature of test surfaces (being coated with the forearm surface of test fabric) The quantity of power of heating element heater.The cooling power reported is the highest, and the power needed for keeping this temperature is the biggest, and therefore fabric institute The nice and cool effect produced is the biggest.In other words, the cooling power reported is the biggest, when the clothing that dress is made up of test fabric Time, the nice and cool effect of desired experience is the biggest.These results all amass 629cm with standard test surface²Relevant.Cooling power/ Square metre can be by calculating divided by 0.629 by the result reported.

This result shows the fiber of the present invention, and the fabric being more specifically made up of such fiber, it is provided that with cooling Nice and cool effect measured by power, it is more than conventional synthetic fibers, and more specifically more than by being conventionally synthesized what fiber was made Fabric.Additionally this result shows the fiber of the present invention, and the fabric being more specifically made up of such fiber, it is provided that with at base Line, suitable nice and cool effect (by cooling power measurement) observed in baring skin embodiment.In other words, the present invention provides Fiber, fabric and different clothing, including manufacturing the device of such goods, it will give wearer (his skin and institute State product into contact) cooling feeling, this cooling feeling is similar to when skin is exposed, does not has sensation when fabric and contact skin.

Further comprises the test of another set, it adds from the dampness of test surfaces release additionally in test process Variable.In these tests, employing the hot foot model of perspiration, this model is equipped with similar with above-mentioned body model here Tester.The dampness of release used in this test is designed to simulate when the clothing that dress is made up of test fabric, example The different perspiration speed will experienced such as people in motor process, and observe any this cooling power for fabric Which kind of impact there is.

Here test with table 1 listed by identical 7 embodiments.In this test, condition used collects in the following table. For each test condition, by system stability 30 minutes, discharge without any wind or dampness, during this period, measure the cold of fabric But power.Then start dampness release, and this system is stablized again 30 minutes, during this period, measure cooling power.Finally Add inlet air condition, and system is stablized again 30 minutes, measure cooling power during this period.

Table 4 uses the cooling power test condition of foot model to collect

1 these condition groups are with following order test: VII, VIII, IX, X, XI.

The result of this test collects in the following table.As it has been described above, each test condition include three kinds visibly different cold But the measurement of power, calm or dampness release (A), one has dampness release and calm (B), and one has target Dampness release and both wind (C).For each condition group, measured cooling power is provided below:

Table 5A cooling power measurements collects¹

The whole results reported in 1 this table are cooling power, watt [W].Footnote 1 referring further to table 3.

Table 5B cooling power measurements collects¹

This result shows, the fiber of the present invention, and the fabric being more specifically made up of such fiber, it is provided that with cooling The nice and cool effect of power measurement, it is more than conventional synthetic fibers, and more specifically more than by knitting of being conventionally synthesized that fiber makes Thing, particularly when there is dampness release and wind condition.Because these conditions are common, with really it is contemplated that work as one Individual puts on clothing, and when particularly gym suit is with similar clothing, this result enhances such conclusion, i.e. by the fibre of the present invention The goods made of dimension are by the people for wearing described goods, or otherwise by their skin and described product into contact People, it is provided that nice and cool effect.

Embodiment group 2

It is prepared for different materials, so that they can be further characterized by the present invention.These materials collect in the following table.

The explanation of table 6 sample and performance

Ex	Sample explanation¹	Hydroxy-end capped intermediate	Diisocyanate	Straight-chain alkyl-sub-glycol
					8	Monfil	BDO adipate ester²	MDI	BDO
9	Monfil	HDO adipate ester³	MDI	BDO
					10	Monfil	BDO/HDO adipate ester⁴	MDI	BDO
11	Monfil	PTMEG	MDI	BDO
					12	Monfil	PEG	MDI	BDO
13	Monfil	BDO adipate ester²	HDI	BDO
					14	Monfil	HDO adipate ester³	HDI	BDO
15	Monfil	BDO/HDO adipate ester⁴	HDI	BDO
					16	Monfil	PTMEG	HDI	BDO
17	Monfil	PEG	HDI	BDO
					18	Monfil	BDO adipate ester²	HMDI	BDO
19	Monfil	HDO adipate ester³	HMDI	BDO
					20	Monfil	BDO/HDO adipate ester⁴	HMDI	BDO
21	Monfil	PTMEG	HMDI	BDO
					22	Monfil	PEG	HMDI	BDO
23	Monfil	BDO adipate ester²	MDI	HDO
					24	Monfil	HDO adipate ester³	MDI	HDO
25	Monfil	BDO/HDO adipate ester⁴	MDI	HDO
					26	Monfil	PTMEG	MDI	HDO
27	Monfil	PEG	MDI	HDO
					28	Monfil	BDO adipate ester²	HDI	HDO
29	Monfil	HDO adipate ester³	HDI	HDO
					30	Monfil	BDO/HDO adipate ester⁴	HDI	HDO
31	Monfil	PTMEG	HDI	HDO
					32	Monfil	PEG	HDI	HDO
33	Monfil	BDO adipate ester²	HMDI	HDO
					34	Monfil	HDO adipate ester³	HMDI	HDO
35	Monfil	BDO/HDO adipate ester⁴	HMDI	HDO
					36	Monfil	PTMEG	HMDI	HDO
37	Monfil	PEG	HMDI	HDO

1 each fabric sample is in by the form of the opening socks/sleeve of described fiber weaving.

2 BDO adipate esters are the adipate esters prepared by 1,4-butanediol and adipic acid.

3 HDO adipate esters are the adipate esters prepared by 1,6-HD and adipic acid.

4 BDO/HDO adipate esters be prepare by the mixture of adipic acid and 1,4-butanediol and 1,6-HD oneself two Acid esters.

The explanation of table 7 sample and performance

Ex	Sample explanation¹	Hydroxy-end capped intermediate	Diisocyanate	Straight-chain alkyl-sub-glycol
					38	Multifilament	BDO adipate ester²	MDI	BDO
39	Multifilament	HDO adipate ester³	MDI	BDO
					40	Multifilament	BDO/HDO adipate ester⁴	MDI	BDO
41	Multifilament	PTMEG	MDI	BDO
					42	Multifilament	PEG	MDI	BDO
43	Multifilament	BDO adipate ester²	HDI	BDO
					44	Multifilament	HDO adipate ester³	HDI	BDO
45	Multifilament	BDO/HDO adipate ester⁴	HDI	BDO
					46	Multifilament	PTMEG	HDI	BDO
47	Multifilament	PEG	HDI	BDO
					48	Multifilament	BDO adipate ester²	HMDI	BDO
49	Multifilament	HDO adipate ester³	HMDI	BDO
					50	Multifilament	BDO/HDO adipate ester⁴	HMDI	BDO
51	Multifilament	PTMEG	HMDI	BDO
					52	Multifilament	PEG	HMDI	BDO
53	Multifilament	BDO adipate ester²	MDI	HDO
					54	Multifilament	HDO adipate ester³	MDI	HDO
55	Multifilament	BDO/HDO adipate ester⁴	MDI	HDO
					56	Multifilament	PTMEG	MDI	HDO
57	Multifilament	PEG	MDI	HDO
					58	Multifilament	BDO adipate ester²	HDI	HDO
59	Multifilament	HDO adipate ester³	HDI	HDO
					60	Multifilament	BDO/HDO adipate ester⁴	HDI	HDO
61	Multifilament	PTMEG	HDI	HDO
					62	Multifilament	PEG	HDI	HDO
63	Multifilament	BDO adipate ester²	HMDI	HDO
					64	Multifilament	HDO adipate ester³	HMDI	HDO
65	Multifilament	BDO/HDO adipate ester⁴	HMDI	HDO
					66	Multifilament	PTMEG	HMDI	HDO
67	Multifilament	PEG	HMDI	HDO

3 HDO adipate esters are the adipate esters prepared by 1,6-HD and adipic acid.

Each document mentioned above is hereby incorporated by reference.Except in an embodiment or otherwise explicitly indicated it Outside place, in this specification, whole quantity of prescribed material amount, reaction condition, molecular weight, carbon number etc. is understood to be to use Wording " about " is revised, and unless otherwise directed, whole percent value, ppm value and number value are based on weight.Remove Non-indicated otherwise, otherwise referred herein to each chemicals or compositions should be not construed as a kind of commercial grade material, it can To comprise isomer, by-product, derivant and other such materials, it is generally understood as existing with commercial grade.But, The amount of each chemical constituent is not to include that any solvent or diluent oil propose, and it can generally be deposited with commercially available material , unless otherwise directed. it is to be understood that the group that upper and lower bound amount set forth herein, scope and proportional limit can be independent Close.Be similar to, for each element of the present invention scope and amount can with for other any elements scope or amount together with Use.As used herein, statement " substantially by ... composition " allow to include such material, its not substantial effect considered The basic and novel characteristic of compositions.

Claims

1. the fiber prepared by compositions, said composition comprises following product:

I the hydroxy-end capped intermediate of () 40-70 weight %, it includes polyester, polyethers, Merlon or a combination thereof, wherein The Tg of this intermediate is not more than 22 DEG C；

(ii) diisocyanate of 20-50 weight %；With

(iii) the linear alkylene diol chain extender of 4-25 weight %,

Wherein the Tg of the compositions for preparing described fiber is not more than 22 DEG C.

2. the fiber of claim 1, the intermediate that wherein (i) is hydroxy-end capped does not contains polyether block amide copolymer.

3. the fiber of claim 1, wherein the percentage elongation of this fiber is 200%-300%.

4. the fiber of claim 1, wherein the effectively cooling power of this fiber is at least 49 watts/square metres, and it is in 30% phase To measure under humidity and 3m/s wind speed.

5. the fiber of claim 1, wherein this fiber does not contains inorganic filler.

6. the fiber of any one of claim 1-5, wherein (i) this hydroxy-end capped intermediate includes Polyethylene Glycol, (ii) this two Isocyanates includes methylenediphenyl diisocyanates；(iii) this linear alkylene diol chain extender includes 1,4-fourth two Alcohol, 1,6-HD or a combination thereof.

7. the fiber of any one of claim 1-5, wherein this compositions being used for preparing fiber is polymer alloy, and it comprises:

A () heterophasic copolymer, it is by polymer and/or copolymer segment and at least one other polymer and/or copolymerization Prepared by the reaction of thing segment；

B () blend polymer, it is by by polymer and/or copolymer and at least one other polymer and/or copolymerization Prepared by thing mixing, wherein every kind of polymer and/or copolymer are compatible with each other and/or miscible with one another；Or

Combination more than (c).

8. the fiber of claim 7, wherein said polymer alloy derives from following reaction: (i) (a) polyhydric alcohol；(i) (b) From polyhydric alcohol and the intermediate polyester of dicarboxylic acids；(ii) at least one diisocyanate；(iii) at least one cahin extension agent.

9. a fabric, it comprises the fiber of claim 1.

10. the fabric of claim 9, wherein said fabric comprises one or more further in addition to the fiber of claim 1 Other fiber, wherein 10-80 weight % of this fabric is these other fibers.

The fabric of 11. claim 10, wherein this other fiber is selected from nylon fiber, polyester fiber, rayon fiber, propylene Acids fiber and combinations thereof.

12. 1 kinds of goods, it comprises the fabric of claim 9.

The goods of 13. claim 12, wherein these goods are clothing, and the fiber of wherein this fabric be arranged in described clothing with Direct skin contact with the wearer of described clothing.

14. 1 kinds of methods that nice and cool effect is provided in the goods directly contacted with human body skin, it comprises the following steps:

I. the fabric of the fiber comprising claim 1 is prepared；

II. the goods comprising described fabric are prepared；

III. described goods are directly contacted with human body skin.

15. 1 kinds of methods manufacturing fiber, it comprises the following steps:

I. preparing elastomer resin in internal mix device, wherein said elastomer resin is by following reaction preparation:

(ii) diisocyanate of 20-50 weight %, and

(iii) the linear alkylene diol chain extender of 4-25 weight %,

Wherein the Tg of the compositions for preparing described fiber is not more than 22 DEG C；

II. described elastomer resin melt spinning is become monfil or multifilament.

16. 1 kinds of methods manufacturing fabric, it comprises the following steps:

(ii) diisocyanate of 20-50 weight %, and

(iii) the linear alkylene diol chain extender of 4-25 weight %,

II. described elastomer resin melt spinning is become monfil or multifilament；

III. by described fiber, optional combines with one or more other fibers, is processed into fabric.