CN105696101B - The high strength fabric being made of thin gauge constant compression elastomer - Google Patents
The high strength fabric being made of thin gauge constant compression elastomer Download PDFInfo
- Publication number
- CN105696101B CN105696101B CN201610074529.7A CN201610074529A CN105696101B CN 105696101 B CN105696101 B CN 105696101B CN 201610074529 A CN201610074529 A CN 201610074529A CN 105696101 B CN105696101 B CN 105696101B
- Authority
- CN
- China
- Prior art keywords
- fiber
- fabric
- melt
- crosslinking agent
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
- D03D1/0017—Woven household fabrics
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/56—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads elastic
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/02—Underwear
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
- Knitting Of Fabric (AREA)
- Nonwoven Fabrics (AREA)
- Undergarments, Swaddling Clothes, Handkerchiefs Or Underwear Materials (AREA)
- Corsets Or Brassieres (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses the elastomers with the modulus curve of opposing straight between 100% to 200% elongation.The clothes with very comfort can be made in the fiber.Preferred elastomer, which is made of thermoplastic polyurethane polymer and passes through unique melt-spinning method, to be prepared, and the fiber is wound with being only slightly higher than the rate for the meltflow ability that polymer leaves spinneret into bobbin in the method.
Description
Technical field
The application is the divisional application of Chinese patent application 201080027998.4.The present invention relates to by the constant pressure of thin gauge
Contract high strength fabric made of (thin gauge constant compression) elastomer.By constant compression elasticity
Clothes made of fiber, which have, enables the feeling of wearer as snug as a bug in a rug.Furthermore clothes tolerance is the height made of the elastomer
Diapirism caused by strength tissue.
Background technique
In recent years, due to the life style of the variation of global range, surmount basic isolation features and in addition to being substantially isolated
Other than function, the demand to the higher function of fabric is constantly in high level.It is to have to a kind of above-mentioned functional demand
Thin gauge but do not sacrifice the intensity of fabric and the fabric of globality.It is this compared with the fabric of thin gauge allow lower packing volume, "
Bulk " reduction of sense and the external visibility that coat is not transmitted through for underwear.
Synthesis elastomer (SEF) is usually made of the polymer with soft chain segment and hard segment to generate elasticity.Have
The polymer of hard segment and soft chain segment is typically poly- (ether-amide), such asOr copolyesters, such asOr thermoplastic polyurethane, such asHowever the SEF of very high elongation rate is typically hard using having
The polymer of segment and soft chain segment, such as dry-spinning polyurethaneOr melt spinning thermoplastic's polyurethane
Although the elongation at break of these SEF is different from low-level to high level, all can normally be described as having
There is the modulus (strain) exponentially increased as elongation (stress) increases.
Melt spinning TPU fibers provide some advantages compared with dry-spinning polyurethane fiber, because in melt spinning process
Without using solvent, and in dry spinning process, polymer is dissolved in a solvent and carries out spinning.Then make the solvent from described
Fiber middles point are evaporated.It is difficult to completely remove all solvents from the dry-spinning fiber.In order to promote from dry-spinning fiber
It is middle to remove the solvent, small size typically is made in these fibers and makes it at being bundled together to generate multifilament (multi-
Filament) (band-like) fiber.Compared with melt spun fibre, for given danier, this will lead to biggish physical size.This
A little physical characteristics cause the person's character of the more bulk and described multifilament bundled in fabric to promote the loss of comfort.
Melt spinning TPU fibers are manufactured and TPU polymer is carried out melt spinning.TPU polymer is by following three kinds of components
Reaction and be made: i.e. (a) hydroxy-end capped intermediate is typically hydroxy-end capped polyethers or polyester；(b) polyisocyanate cyanogen
Acid esters, such as diisocyanate；(c) chain extender of short-chain hydroxyl sealing end.The hydroxy-end capped intermediate forms TPU polymerization
The soft chain segment of object and the polyisocyanates and chain extender form the hard segment of TPU polymer.The soft chain segment and hard segment
Combination assigns TPU polymer elasticity.TPU polymer is also frequently by using polyisocyanate blocked prepolymer and lightly crosslinked
To provide the performance of enhancing.The crosslinking substance is added in melting TPU polymer during the melt spinning of fiber.
Wish to obtain and there is relative constant compression (relatively constant of the elongation between zero and 250%
Compression TPU elastomer and it is desirable that constant compression clothes and/or fabric of the preparation comprising the TPU fiber).Separately
It is outer to wish that these constant compression fabrics are thin gauges and with high puncture resistance (puncture resistance).By upper
Higher comfort and confidence can be provided for wearer by stating textile clothes.
Detailed description of the invention
Fig. 1 is the microphoto of 70 denier multifilament yarns of commercially available dry-spinning polyurethane fiber.
Fig. 2 is the microphoto of 70 daniers of the constant compression thermoplastic polyurethane fibers of melt spinning of the invention.
Fig. 3 is the curve for showing the Y-axis of square (square micron) of the X-axis vs. fiber width as danier.This is sent out
Bright fiber is compared with commercially available dry-spinning fiber.
Summary of the invention
It is an object of the present invention to provide thin gauge, constant compression high strength fibres, at least 400% limit
Elongation and have load period and in the zero load period between 100% to 200% elongation opposing straight and/or constant
Modulus.This straight and/or constant modulus by load period stress under 100% elongation less than 0.023 gram-
The every danier of power, under 150% elongation less than the every danier of 0.023 fors, under 200% elongation less than 0.053 gram-
The every danier of power；With by the zero load period stress under 200% elongation less than the every danier of 0.027 fors, in
It is able to less than the every danier of 0.018 fors, under 100% elongation less than the every danier of 0.015 fors under 150% elongation
It confirms.
A kind of exemplary fiber is and by thermoplastic polyurethane polymer, the preferably spinning of polyester-polyurethane polymer melt
Manufacture.The fiber is by adding crosslinking agent (preferably 5-20 weight %) to the polymer melt during melt spinning process
And it is lightly crosslinked.
A kind of method preparing the fiber includes melt spinning process, from there through making polymer melt pass through spinneret
And form the fiber.The rate that fiber leaves the rate of the spinneret and fiber is wound into bobbin is relatively close to.?
That is the fiber should be to be greater than the rate volume that fiber leaves the rate at most 50%, preferably 20%, more preferable 10% of spinneret
Around enter bobbin.
It is a further object of this invention to manufacture fabric with the thin gauge, constant compression fiber.In illustrative embodiment party
In case, by the way that the elastomer (such as is passed through knitting in conjunction with the hard fibre of such as nylon and/or polyester fiber etc
(knit) or tatting (weave)) and manufacture the fabric.Also there is high bursting with the fabric of the novel fiber manufacture
Intensity (burst strength).
Clothing garment, such as underwear are manufactured by the elastomer.The clothes provide good comfort for wearer.
The invention further relates to scheme is implemented as follows:
1. the elastomer of a kind of thin gauge, constant compression, high bursting strength, at least 400% ultimate elongation
Rate and have load period and in the zero load period between 100% to 200% elongation opposing straight modulus.
2. the fiber of embodiment 1, wherein the monfil of 40 daniers has the width less than 100 microns.
3. the fiber of embodiment 1, wherein when the fiber of 70 danier is made into fabric and according to ASTM D751
Measuring the fabric when puncture strength of the fabric has the fracture load for being greater than 6 pounds.
4. the fiber of embodiment 1, wherein the fiber is thermoplastic polyurethane fibers.
5. the fiber of embodiment 4, wherein the fiber is polyester thermoplastic's polyurethane.
6. the fiber of embodiment 5, wherein the fiber is crosslinked with polyether crosslinking agent.
7. the fiber of embodiment 5, wherein the weight average molecular weight of polyester thermoplastic's polyurethane is 200,000-700,
000 dalton.
8. the fiber of embodiment 6, wherein the crosslinking agent is polyester thermoplastic's polyurethane and the crosslinking agent
The 5-20 weight % of total weight.
9. the fiber of embodiment 8, wherein the crosslinking agent is polyester thermoplastic's polyurethane and the crosslinking agent
The 8-12 weight % of total weight.
10. a kind of fabric comprising at least two different fibers, wherein at least one of described fiber is thermoplastic poly
At least one of urethane fiber and the fiber are hard fibres, and wherein thermoplastic polyurethane's fiber have in
The load-deformation curve of opposing straight between 100% to 200% elongation.
11. the fabric of embodiment 10, wherein the fabric is by the two beam thermoplastic poly ammonia relatively per a branch of hard fibre
Ester fiber is made.
12. the fabric of embodiment 10, wherein the thermoplastic polyurethane fibers have 20-600 danier.
13. the fabric of embodiment 12, wherein the thermoplastic polyurethane fibers have 70-360 danier.
14. the fabric of embodiment 10, wherein the hard fibre is selected from nylon and polyester.
15. the fabric of embodiment 14, wherein the hard fibre has about 70 daniers and the thermoplastic polyurethane
Fiber has about 140 daniers.
16. clothing item, it includes the fabrics of embodiment 10.
17. the clothing item of embodiment 16, wherein the product is underwear.
18. the clothing item of embodiment 17, wherein the product is brassiere.
19. a kind of method for preparing elastomer, the elastomer have load period and in the zero load period in
The modulus of opposing straight between 100% to 200% elongation, the described method includes:
(a) thermoplastic elastomer polymer melt spinning is passed through into spinneret；With
(b) elastomer is rolled up with the winding rate for leaving the rate 50% of the spinneret no more than polymer melt
Around enter bobbin.
20. the method for embodiment 19, wherein the winding rate leaves the spinneret no more than polymer melt
The 20% of rate.
21. the method for embodiment 20, wherein the winding rate leaves the spinneret no more than polymer melt
The 10% of rate.
22. the method for embodiment 19, wherein the thermoplastic elastomer polymer is thermoplastic polyurethane.
Detailed description of the invention
Fiber of the invention is prepared by thermoplastic elastomer (TPE).Preferred thermoplastic elastomer (TPE) is thermoplastic polyurethane polymer
(TPU).The present invention will be described using TPU, it should be appreciated that this is a kind of embodiment and those skilled in the art
Other thermoplastic elastomer (TPE)s can be used.
It can be any conventional TPU polymerization known in this area and the literature for TPU polymer type of the invention
Object, as long as the TPU polymer has enough molecular weight.The TPU polymer generally passes through polyisocyanates and intermediate example
Such as or mixtures thereof hydroxy-end capped polyester, hydroxy-end capped polyethers, hydroxy-end capped polycarbonate and one or more expansions
Chain agent is reacted and is prepared, and all these is well-known to those skilled in the art.
The hydroxy-end capped intermediate polyester is usually that number-average molecular weight (Mn) is about 500 to about 10,000, hopefully
About 700 to about 5,000, preferably about 700 to about 4,000 and acid value is generally less than the linear polyesters of 1.3, preferably smaller than 0.8.
Molecular weight is determined by analysis functional end-group and is related to number-average molecular weight.The polymer is prepared as follows:
(1) esterification or (2) of one or more glycol and one or more dicarboxylic acids or acid anhydrides pass through ester exchange reaction,
That is, one or more glycol are reacted with dicarboxylic ester.It is preferred that acid relatively is generally excess of greater than the molar ratio of a diol, with
Obtain the linear chain of terminal hydroxyl dominance.Suitable intermediate polyester further includes a variety of lactones, such as polycaprolactone, typical case
Ground is prepared by 6-caprolactone and bifunctional initiator such as diethylene glycol (DEG).The dicarboxylic acids of desired polyester can be aliphatic series, rouge
Ring race, aromatics or a combination thereof.There can be 4- in total individually or by the suitable dicarboxylic acids that mixture uses
15 carbon atoms and include: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid,
M-phthalic acid, terephthalic acid (TPA), cyclohexane dicarboxylic acid etc..The acid anhydrides of above-mentioned dicarboxylic acids, such as adjacent benzene two can also be used
Formic anhydride, tetrahydrophthalic anhydride etc..Hexanedioic acid is preferred acid.The two of desired intermediate polyester is formed for reacting
Alcohol can be aliphatic series, aromatics or combinations thereof, and have 2-12 carbon atom in total, including ethylene glycol, 1,2- the third two
Alcohol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 2,2- dimethyl -1,3- the third two
Alcohol, 1,4 cyclohexane dimethanol, 1,10- decanediol, 1,12- dodecanediol etc..1,4- butanediol is preferred glycol.
Hydroxy-end capped polyether intermediate is polyether polyol, be originated from glycol with 2-15 carbon atom in total or
Polyalcohol, optimizing alkyl glycol (diol or glycol), the alcohol with include have 2-6 carbon atom alkylene oxide (typical case
Or mixtures thereof ground ethylene oxide or propylene oxide) ether reaction.Such as it can be by making propylene glycol anti-with propylene oxide first
It should be followed by the polyethers for preparing hydroxyl-functional with reacting ethylene oxide.By ethylene oxide generate primary hydroxyl more than secondary hydroxyl
Have reactive and is therefore preferred.Available commercially available polyether polyol includes: comprising the epoxy second with glycol reaction
The poly(ethylene glycol) of alkane, includes anti-with tetrahydrofuran (PTMEG) at poly- (propylene glycol) comprising the propylene oxide reacted with propylene glycol
Poly- (the oxygen tetramethylene glycol) for the water answered.PEO macromonomer (PTMEG) is preferred polyether intermediate.Polyether polyol into
One step includes the polyamide adducts of alkylene oxide and may include, such as, the reaction product comprising ethylenediamine and propylene oxide
Ethylenediamine adduct, the diethylenetriamines adduct and class of the reaction product comprising diethylenetriamines and propylene oxide
As polyamide type polyether polyalcohol.Copolyether can also be used in the present invention.Typical copolyether includes THF and ring
The reaction product or THF of oxidative ethane and the reaction product of propylene oxide.These can be from BASF as Poly THF B (block copolymerization
Object) and Poly THF R (random copolymer) buy.Different polyether intermediates generally has by analyzing functional end-group
Determining number-average molecular weight (Mn), average molecular weight are greater than about 700, for example, about 700 to about 10,000, it is desirable to ground about 1000
To about 5,000, preferably about 1000 to about 2500.A kind of specific desired polyether intermediate is two or more differences
The blend of the PTMEG of the blend of the polyethers of molecular weight, such as 2000Mn and 1000Mn.
Most preferred embodiment of the invention is used and is blended by adipic acid with the 50/50 of 1,4- butanediol and 1,6-HD
The intermediate polyester of object reaction and preparation.
Polycarbonate of the invention-based polyurethanes resin passes through diisocyanate and hydroxy-end capped polycarbonate and chain extension
The blend of agent is reacted and is prepared.The hydroxy-end capped polycarbonate can be prepared by glycol and carbonate reaction.
Disclosure in United States Patent (USP) US 4,131,731 in relation to hydroxy-end capped polycarbonate and their preparation
It is incorporated herein by reference.Above-mentioned polycarbonate is line style and has terminal hydroxyl and substantially exclude other terminal groups
Group.Fundamental reaction object is two pure and mild carbonic esters.Suitable glycol is selected from comprising 4-40, preferably 4-12 carbon atom alicyclic two
Pure and mild aliphatic diol and include the polyoxy Asia that 2-20 alkoxy and each alkoxy include 2-4 carbon atom selected from per molecule
Alkyl diol.It include the aliphatic diol comprising 4-12 carbon atom, such as butanediol -1,4, penta suitable for glycol of the invention
Glycol -1,4, neopentyl glycol, hexylene glycol -1,6,2,2,4- trimethyl hexylene glycol-l, 6, decanediol -1,10, two flax bases of hydrogenation
Glycol (hydrogenated dilinoleylglycol), hydrogenation two oil base glycol (hydrogenated
dioleylglycol)；And alicyclic diol such as cyclohexanediol -1,3, hydroxymethyl-cyclohexane -1,4, cyclohexane diol -
1,4, hydroxymethyl-cyclohexane -1,3,1,4- endo-methylene group -2- hydroxyl -5- methylol hexamethylene, polyalkylene glycol.For this
The glycol of reaction can be single glycol or diol mixture, this depends on property desired by finished product.
Hydroxy-end capped intermediate polycarbonate be usually it is known in this area and the literature those.Suitable carbonic ester choosing
From the alkylene carbonates being made of 5 to 7 member rings with following general formula:
Wherein R is the saturation bivalent group comprising 2-6 carbons.Suitable carbonic ester used in this application includes
Carbonic acid ethylidene ester, carbonic acid 1,3- propylidene ester, carbonic acid 1,4- Aden base ester, carbonic acid 1,2- propylidene ester, carbonic acid 1,2- Aden
Base ester, carbonic acid 2,3- Aden base ester, carbonic acid 1,2- ethylidene ester, carbonic acid 1,3- pentylidene ester, carbonic acid 1,4- pentylidene ester, carbonic acid
2,3- pentylidene ester and carbonic acid 2,4- pentylidene ester.
In addition, being suitble to the application's to be dialkyl carbonate, carbonic acid alicyclic ester and diaryl carbonate.The carbonic acid
Dialkyl ester can include 2-5 carbon atom in each alkyl and its specific example is diethyl carbonate and carbonic acid dipropyl
Ester.Carbonic acid alicyclic ester, particularly two alicyclic ester of carbonic acid can include 4-7 carbon atom in each cyclic structure, and can
With there are one of described structure or two kinds.When a group is alicyclic, another can be alkyl or aryl.
On the other hand, if a group is aryl, another can be alkyl or alicyclic.It can include 6-20 in each aryl
The preferred embodiment of the diaryl carbonate of a carbon atom is dipheryl carbonate base ester, carboxylol base ester and carbonic acid dinaphthyl base ester.
By there is or be not present transesterification at 100 DEG C -300 DEG C of temperature and the pressure of 0.1-300mm Hg
In the case where catalyst, make glycol and carbonic ester, preferred as alkylene carbonates by 10:1-1:10 but mole of preferably 3:1-1:3
Range reacts and carries out the reaction, while low boiling point glycol is removed by distillation.
More particularly, it is seen that hydroxy-end capped polycarbonate is prepared with two stages.In the first phase, glycol and carbonic acid
Alkylene ester reaction is to form the polycarbonate that low-molecular-weight hydroxyl blocks.By at 100 DEG C -300 DEG C, preferably 150 DEG C -250
It is distilled under the reduced pressure of 10-30mm Hg, preferably 50-200mm Hg at DEG C and removes more low-boiling glycol.Using point
Tower is evaporated to separate the by-product glycol from reaction mixture.The by-product glycol is taken out simultaneously from the top of the tower
And reaction vessel is back to using unreacted alkylene carbonates and diol reactant as reflux.Inert gas flow can be used
Or atent solvent stream promotes the removing of by-product glycol when formed.When the amount of obtained by-product glycol shows that hydroxyl seals
When the degree of polymerization of the polycarbonate at end is 2-10, the pressure is gradually decrease to 0.1-10mm Hg and removes unreacted two
Pure and mild alkylene carbonates.This mark reaction second stage beginning, during which by when formed 100 DEG C -300 DEG C, it is excellent
Select the polycarbonate for distilling out glycol under 150 DEG C -250 DEG C and 0.1-10mm Hg of pressure and being condensed low-molecular-weight hydroxyl sealing end
Hope molecular weight until obtaining hydroxy-end capped polycarbonate.The molecular weight (Mn) of hydroxy-end capped polycarbonate can be about
500 to about 10,000, but in a preferred embodiment, it will be 500-2500.
The second neccessary composition for preparing TPU polymer of the invention is polyisocyanates.
Polyisocyanates of the invention generally has formula R (NCO)n, wherein n is generally 2-4, and since ingredient is thermoplastic
Property and very preferably 2.Therefore, due to they cause crosslinking and only with considerably less amount, such as based on all polyisocyanic acid
The polyisocyanates that the total weight of ester is less than 5 weight %, hopefully 3 or 4 using degree of functionality less than 2 weight %.R can be one
As there is the aromatics of about 20 carbon atoms of 2-, alicyclic and aliphatic or their combination in total.Suitable aromatics diisocyanate
The example of ester includes diphenyl methane -4,4 '-diisocyanate (MDI), H12MDI, meta-xylene diisocyanate (XDI),
M- tetramethylene xylene diisocyanate (TMXDI), phenylene -1,4- diisocyanate (PPDI), 1,5- naphthalene diisocyanate
(NDI) and diphenyl methane -3,3 '-dimethoxy-4 ', 4 '-diisocyanate (TODI).Suitable aliphatic vulcabond
Example includes isoflurane chalcone diisocyanate (IPDI), 1,4- cyclohexane diisocyanate (CHDI), two isocyanide of 1,6- hexamethylene
Acid esters (HDI), 1,6- diisocyanate base -2,2,4,4- tetramethyl hexane (TMDI), 1,10- decane diisocyanate and trans- -
Dicyclohexyl methyl hydride diisocyanate (HMDI).It is a kind of non-containing the o- MDI to (2,4) isomers less than about 3 weight %
Normal preferred diisocyanate.
The third neccessary composition for manufacturing TPU polymer of the invention is chain extender.Suitable chain extender be with about 2- about
The lower aliphatic or short-chain diol of 10 carbon atoms, and including such as ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol, 3 third
Glycol, triethylene glycol, the cis-trans-isomer of cyclohexyl dihydroxymethyl, neopentyl glycol, 1,4- butanediol, 1,6- hexylene glycol, 1,3- fourth
Two pure and mild 1,5- pentanediols.Furthermore aromatic diol can be used as chain extender, and (high heat is applied for high fever
Application aromatic diol) is preferentially selected.Benzenediol (HQEE) and Xylene glycol are TPU for manufacturing the present invention
Suitable chain extenders.Xylene glycol is the mixture of (methylol) benzene of 1,4- bis- and 1,2- bis- (methylol) benzene.Benzenediol is excellent
The aromatic chain extender of choosing and specifically include hydroquinone, that is, bis- (β-hydroxyl of also referred to as 1,4- bis- (2- hydroxyl-oxethyl) benzene
Base ethyl) ether；Resorcinol, that is, bis- (beta-hydroxy ethyl) ethers of also referred to 1,3- bis- (2- hydroxyethyl) benzene；Catechol,
That is, bis- (beta-hydroxy ethyl) ethers of also referred to 1,2- bis- (2- hydroxyl-oxethyl) benzene)；And a combination thereof.A kind of preferred chain extender
It is 1,4- butanediol.
Above-mentioned three kinds of neccessary compositions (hydroxy-end capped intermediate, polyisocyanates and chain extender) preferably depositing in catalyst
In lower reaction.
Generally, any conventional catalyst can be used so that diisocyanate and hydroxy-end capped intermediate or chain extension
Agent is reacted and the catalyst is usually well known in the art and literature.The example of suitable catalyst includes bismuth or tin
Various alkyl ethers or alkyl sulfide alcohol ether, wherein moieties have about 20 carbon atoms of 1-, and specific example include Bismuth Octoate,
Lauric acid bismuth etc..Preferred catalyst includes various tin catalysts, such as stannous octoate, two sad dibutyl tins, tin dilaurate
Dibutyl tin etc..The amount of the catalyst is generally a small amount of, such as forms the total weight about 20ppm- of monomer about based on polyurethane
200ppm。
TPU polymer of the invention can be manufactured by any typical polymerization methods of well known in the art and literature.
Thermoplastic polyurethane of the invention is prepared preferably via " step (one shot) " method, wherein together by all components
Simultaneously or substantially it is added to the extruder being heated simultaneously and its reaction is made to form the polyurethane.Diisocyanate and hydroxyl
The equivalent proportion of the total yield of the intermediate and diol chain-extension agent of base sealing end is typically about 0.95- about 1.10, it is desirable to which ground about 0.97- is about
1.03, preferably about 0.97- about 1.00.The Xiao A hardness for being formed by TPU should be for 65A-95A, preferably about 75A- about
85A, to obtain most desirable end product properties.Using the reaction temperature of urethane catalyst be generally about 175 DEG C-about
245 DEG C, preferably about 180 DEG C-about 220 DEG C.The molecular weight (Mw) of thermoplastic polyurethane is generally about 100,000- about 800,
000, hopefully about 400,000, preferably about 150,000- about 350,000 about 150,000-, by relative to polystyrene
The gpc measurement of reference substance.
The thermoplastic polyurethane can also be prepared using prepolymer process.It, will be hydroxy-end capped in prepolymer approach
Intermediate is reacted with the excessive one or more polyisocyanates of generally equivalent to be formed and wherein have free or unreacted
Polyisocyanates pre-polymer solution.Reaction is generally in the presence of suitable urethane catalyst in about 80 DEG C-about 220
DEG C, carry out at preferably from about 150 DEG C-about 200 DEG C.Then, the chain extender of selective type as noted above is by generally equivalent to isocyanide
The equivalent addition of acid esters end group and any free or unreacted diisocyanate cpd.Thus diisocyanate total amount
The total yield ratio of total yield relative to hydroxy-end capped intermediate and chain extender is about 0.95- about 1.10, it is desirable to ground about 0.98-
About 1.05, preferably about 0.99- about 1.03.Hydroxy-end capped intermediate is adjusted relative to the equivalent proportion of chain extender to generate 65A-
95A, preferably 75A-85A Shore hardness.Chain extending reaction temperature is typically about 180 DEG C-about 250 DEG C, and preferably about 200 DEG C-about 240
℃.Typically, prepolymer approach can carry out in any conventional equipment, and described device is preferably extruder.Therefore, hydroxyl seals
The intermediate at end in the first part of extruder with the excessive di-isocyanate reaction of equivalent with formed pre-polymer solution and
Then chain extender is added in downstream part and is reacted with the pre-polymer solution.Various conventional extruders, extruder can be used
It is the separating screw rod of at least 20, preferably at least 25 equipped with draw ratio.
Available additive can be used with suitable amount, the additive includes that opaque pigment, colorant, mineral are filled out
Material, stabilizer, lubricant, UV absorbent, processing aid and other desired additives.Available opaque pigment includes
Titanium dioxide, zinc oxide and titan yellow (titanate yellow), and available coloring pigment includes carbon black, oxide yellow object
(yellow oxides), brown oxide (brown oxides), natural and fumed loess or umber, chrome oxide green, cadmium face
Material, chromium pigment and other mixed metal oxides and organic pigment.Available filler includes diatomite (superfloss)
Clay, silica, talcum, mica, wollastonite (wallostonite), barium sulfate and calcium carbonate.If desired, it can be with
Using the useful stabilizer of such as antioxidant etc, including phenol antioxidant, and available light stabilizer includes organic
Phosphate and organo-tin mercaptide (mercaptides).Available lubricant includes metallic stearate, paraffin oil and amide waxe.It can use
UV absorbent include 2- (2'- hydroxyl phenol) benzotriazole and 2- Viosorb 110.
Plasticiser additive can also be advantageously used to reduce hardness without influencing property.
During melt spinning process, TPU polymer as described above can be lightly crosslinked with crosslinking agent.The crosslinking agent
Be reacted with polyisocyanates be or mixtures thereof polyethers, polyester, polycarbonate, polycaprolactone hydroxy-end capped centre
The prepolymer of body.Polyester or polyethers are the preferred hydroxy-end capped intermediates for manufacturing crosslinking agent, are combined when with polyester TPU
Polyethers is most preferred when use.The crosslinking agent prepolymer have greater than about 1.0, preferably about 1.0- about 3.0, more preferably
The isocyanate functionality of about 1.8- about 2.2.If the both ends of particularly preferably hydroxy-end capped intermediate are sealed with isocyanates
Therefore end then has 2.0 isocyanate functionality.
For manufacture the polyisocyanates of crosslinking agent with it is described above identical in manufacture TPU polymer.Such as MDI it
The diisocyanate of class is preferred diisocyanate.
The number-average molecular weight (Mn) of the crosslinking agent is about 10,000 dalton of about 1,000-, preferably from about 1,200- about 4,
000, more preferably from about 1,500- about 2,800.Crosslinking agent with greater than about 1500Mn generates preferable permanent deformation property (set
properties)。
The weight percent of crosslinking agent for TPU polymer is about 2.0%- about 20%, preferably from about 8.0%- about 15%,
More preferably from about 10%- about 13%.The percentage of crosslinking agent used is the weight hundred of the total weight based on TPU polymer and crosslinking agent
Divide ratio.
The preferred melt spinning process of TPU fiber for manufacturing the present invention includes supplying preformed TPU polymer
To extruder so that TPU polymer melting and the downstream that extruder position is left close to TPU melt or TPU melt from
Open extruder continuous addition crosslinking agent later.It can be incited somebody to action before melt leaves extruder or after melt leaves extruder
The crosslinking agent is added in extruder.If added after melt leaves extruder, then the crosslinking agent is needed using quiet
State or dynamic mixer make it with TPU melt mixed to ensure that crosslinking agent is suitably mixed into TPU polymer melt.From
After opening extruder, melting TPU polymer flows into spinning manifold together with crosslinking agent.Melt material flow is divided into difference by spinning manifold
Stream, wherein each stream is conducted to multiple spinnerets.Typically, the presence of each different streams for being flowed out from spinning manifold
Melt Pump, wherein each Melt Pump is fed to several spinnerets.The spinneret has aperture, and melt is forced through described small
Hole and the spinneret is left in the form of monfil.The size in the hole in spinneret will depend on desired fiber ruler
Very little (danier).
The TPU polymer melt can be made to pass through spinning pack (spin pack assembly) and leave the spinneret group
Part is used as fiber.Preferred spinning pack used is that for generating the plug-like stream of the TPU polymer by the component.Most preferably
Spinning pack be described in the PCT Patent Application WO 2007/076380 that, full text is incorporated into the application.
Once the fiber leaves spinneret, it is cooled before being wound up on bobbin.The fiber passes through the first godet,
Finish is applied, and the fiber advances to the second godet.One important side of the technique of fiber for manufacturing the present invention
Face is the relative speed that fiber is wound into bobbin.For relative speed, refer to for winding rate melt from
Open the rate (meltflow ability) of spinneret.In normal prior art TPU melt spinning process, fiber is with 4-6 times of meltflow ability
Rate be wound.Draw or stretch in this way the fiber.For unique fiber of the invention, it is not desired to this extension
It draws (extensive drawing).The fiber must be wound with the rate at least equal to meltflow ability to implement the work
Skill.For fiber of the invention, it is necessary to be more than meltflow ability no more than 50%, be preferably no greater than 20%, more preferably not
The fiber is wound greater than 10% rate, no more than 5% the case where generates fabulous result.It is believed that equal with meltflow ability
Winding rate can be ideal, but slightly faster winding rate must be taken to implement the technique.For example, fine
Dimension leaves spinneret with 300 meters of rate per minute, most preferably with 300-315 meters of rate per minute winding.
Fiber of the invention can be made with a variety of danier numeral systems.Danier is the art for showing fiber size in this field
Language.Danier is the weight in terms of the grams of 9000 meters of fibre lengths.Fiber of the invention is typically fabricated as 20-600 denier Buddhist nun
The size of that, preferably 40-400, more preferable 70-360 danier.
When manufacturing fiber by method of the invention, usually after cooling or period and it is being wound entrance just
The release additives (one example is silicone oil) of such as finish etc are added to the surface of fiber before bobbin.
One importance of melt spinning process is the mixing of TPU polymer melt and crosslinking agent.It is appropriate uniformly mixed
It closes to the consistent fibre property of acquisition and is important in the case where not generating fibrous fracture for the realization long running time.
The mixing of TPU melt and crosslinking agent should be the method for obtaining plug-like stream, i.e. first in first out.It can use dynamic mixer or quiet
State mixer realizes mixing appropriate.Static mixer is more difficult to clean；Therefore, dynamic mixer is preferred.With into
The dynamic mixer for expecting screw rod and mixing pin is preferred mixer.The United States Patent (USP) US 6 being incorporated herein by reference,
709,147 disclose this mixer and have rotatable mixing pin.Mixing pin is also in fixed position,
Such as the center line being connected on the cylinder of mixer and towards feed screw extends.Mixed feeding screw rod can be invested by screw thread
The end of extruder screw, and the shell of mixer can be bolt-connected on extruder.The charging of dynamic mixer
Screw rod should be designed as follows, almost without back-mixing, keep polymer melt mobile in a manner of being progressively advanced
To obtain the plug-like stream of melt.The L/D of mixing screw should be greater than 3 and less than 30, and preferably from about 7 to about 20, more preferably from about 10
To about 12.
Temperature in the mixed zone that wherein TPU polymer melt is mixed with crosslinking agent is about 200 DEG C-about 240 DEG C, preferably
About 210 DEG C-about 225 DEG C.These temperature are necessarily used for obtaining the reaction non-degradable polymer simultaneously.
TPU and crosslinking agent are formed by melt spinning process present invention to obtain the TPU's in final fibers form
Molecular weight (Mw) is about 200,000- about 800,000, and preferably from about 250,000- about 500,000, more preferably from about 300,000- is about
450,000。
The fusing point that spinning temperature (temperature of spinneret interpolymer melt) should be above polymer, preferably higher than polymerize
About 10 DEG C-about 20 DEG C of object fusing point.The spinning temperature that can be used is higher, and spinning effect is better.However, when spinning temperature is too
Height, polymer can degrade.Therefore, degrade for realization in non-polymer higher than about 10 DEG C-about 20 DEG C of the fusing point of TPU polymer
In the case of good spinning balance for be optimal.If spinning temperature is too low, polymer may solidify simultaneously in spinneret
Lead to fibrous fracture.
Unique fiber of the invention have load period and in the zero load period between 100% to 200% elongation
Opposing straight and/or constant modulus.The constant modulus by load period stress be less than under 100% elongation
The every danier of 0.023 fors is less than under 150% elongation less than the every danier of 0.036 fors, under 200% elongation
The every danier of 0.053 fors is confirmed；And by the zero load period stress under 200% elongation less than 0.027
The every danier of fors, under 150% elongation less than the every danier of 0.018 fors, under 100% elongation less than 0.015
The every danier of fors is confirmed, wherein all this data are collected by 360 denier fibers.
In addition, the constant modulus by load period stress under 100% elongation less than the every denier of 0.158 fors
Neil, under 150% elongation less than the every danier of 0.207 fors, under 200% elongation less than the every denier of 0.265 fors
Neil is confirmed；And by the zero load period stress under 200% elongation less than the every danier of 0.021 fors,
It is obtained less than the every danier of 0.012 fors, under 100% elongation less than the every danier of 0.008 fors under 150% elongation
To confirm, wherein all this data are collected by 360 denier fibers.
Code test regulation for obtaining the above modulus values is to be directed to one kind that elastomeric yarn is developed by DuPont.
The test makes fiber be subjected to a series of 5 circulations.In each circulation, fiber is stretched to 300% elongation, and using constant
Rate of extension makes its loose (between original measuring length and 300% elongation).Measurement % permanently becomes after the 5th circulation
Shape.Then, make the fiber samples by the 6th circulation and be stretched to fracture.Load of the instrument record under each elongation, disconnected
Maximum load before splitting, and unit are the fracture load (breaking load) of the every danier of fors and bear in maximum
Elongation at break and elongation under lotus.The test usually carries out (23 DEG C ± 2 DEG C at room temperature；With 50% ± 5% humidity).
Fiber of the invention has at least 400%, preferably from about 450 to 500% elongation at break.The fiber is round single
Silk.Referring to Fig. 2, it is seen that 70 Denier monofilament fibers are substantially circular in transverse shape.Fig. 1 shows 70 danier lists
Silk dry-spinning fiber, with biggish cross-sectional width.
Fig. 3 shows the curve for being compared dry-spinning fiber with melt spun fibre of the invention.The curve describes danier (X
Axis) vs. fiber width square (square micron) relationship.The curve shows that melt spun fibre of the invention has on the curve
Constant-slope, and the dry-spinning fiber has the slope that exponentially increases.The result is that prepared with fiber of the invention
Fabric is thinner and thus enables wearer more comfortable.
Another important feature of fiber of the invention is the bursting that it shows improvement in the fabric compared with dry-spinning fiber
Intensity.
It can be by implementing Ball Burst Puncture Strength using 1 inch diameter ball according to ASTM D751
Test shows this feature.This test simulation finger passes through the fabric until forming hole.Very surprisingly fiber of the invention
Opposite dry-spinning polyurethane fiber shows the improvement of about 50-75% in terms of bursting strength.Even if the tensile strength of fiber is almost
Identical, there is also the improvement of the bursting strength.
Furthermore fiber of the invention thermal capacitance with higher.Straight modulus curve, higher thermal capacitance and thinner specification
Combination cause with fiber of the present invention prepare fabric enable garment wearer be comfortable on.
The fabric prepared with fiber of the present invention can be manufactured by knitting or tatting.Often preferably with other fibers and this
TPU fiber manufactures fabric together.Particularly preferably using hard fibre together with elastomer of the invention.It is preferred that hard fibre,
Such as nylon and/or polyester.The hard fibre improves the anti-snagging of the fabric for 100% elastic fiber fabric.
A kind of preferred fabric is that being knitted with alternating strands, for example a branch of 140 danier TPU/70 Denier nylon of alternating strands
Replace followed by the 2 of (referred to as 1-1 fabric) or a branch of 140 danier TPU/70 Denier nylon with a branch of 140 danier TPU
140 danier TPU of beam (referred to as 1-2 fabric).
Clothes can be manufactured with fabric of the invention.Due to the comfort that the fiber provides, the optimal selection of the fabric
Way is manufacture underwear or fitted garment.The underwear and T-shirt of such as brassiere etc and such as run for campaign item, cunning
Snow, bicycle or the sportswear of other movements can benefit from the property of these fibers.The clothes worn next to the skin are benefited from
The straight modulus of these fibers, because once the fiber reaches body temperature, then the modulus is even lower.Feel that close-fitting clothes will
Become more comfortable in about 30 seconds to 5 minutes after the fiber reaches body temperature.It will be appreciated by those skilled in the art that can be sent out with this
Bright fiber and fabric manufacture any clothes.Illustrative embodiment can be by woven fabric manufacture Shoulder belt of brassiere and by
The cup cover of the brassiere of knitted fabric manufacture, wherein the woven fabric and knitted fabric both include melt-spun TPU of the invention fine
Dimension.The bra belt does not need adjustable button, because the fabric is elastic.
The present invention is better understood with by reference to following embodiment.
Embodiment
The intermediate (polyalcohol) and 1,4- chain expansion of succinic acid that TPU polymer for embodiment is blocked by polyester hydroxyl
Agent and MDI are reacted and are made.The polyester polyol passes through 50/50 mixture of adipic acid and 1,4- butanediol and 1,6-HD
It reacts and is made.The polyalcohol has 2500 Mn.The TPU is made by a step process.TPU is added to during spinning technique
In crosslinking agent be to be reacted with MDI as 1000Mn PTMEG to generate polyethers pre-polymerization prepared by isocyanate-terminated polyethers
Object.The dosage of the crosslinking agent is 10 weight % of total weight that TPU adds crosslinking agent.Melt spinning fibers are used for reality to manufacture
Apply 40,70,140 and 360 denier fibers of example.
Embodiment 1
This embodiment is provided to illustrate and the melt spinning TPU fibers of the prior art (40 danier) and commercially available dry-spinning fiber (70
Danier) it compares, the modulus curve of the opposing straight of fiber (70 danier) of the present invention.
Used testing regulations is as above with regard to described in testing elastic property.Using with Merlin software
5564 tensometer of Instron model.The experimental condition is 23 DEG C ± 2 DEG C and 50% ± 5% humidity.The fiber of test specimen is long
Degree is 50.0mm.Four samples are tested simultaneously and the result is that the average value of 4 test specimens.As the result is shown in Table I.
Table I
Above-mentioned all data are the average value of 4 test specimens.
From above data, it is seen that melt spun fibre of the invention is during the 5th test cycle with the modulus of opposing straight
Curve.Circulation is typically ignored because this is the stress mitigated in fiber for the first time.
Embodiment 2
This embodiment is provided to illustrate the width of melt spun fibre of the invention compared with commercially available dry-spinning fiber.It is surveyed by SEM
The fixed width.As the result is shown in table ii.
Table II
As can be seen, there is dry-spinning fiber much bigger width and the difference to increase with danier number and become
It obtains bigger.
Embodiment 3
This embodiment is provided to illustrate the improvement of melt spinning TPU fibers of the invention compared with commercially available dry-spinning urethane fibers
Bursting strength.Single jersey (signel Jersey) knitted fabric is prepared by each types of fibers using 70 denier fibers.According to
The bursting puncture strength of ASTM D751 measurement fabric.As the result is shown in Table III.This result is that 5 test specimens average value.
Table III
| Test | Dry-spinning | Melt-spun |
| Fracture load (load at failure, lbs) | 5.78 | 9.03 |
| Fault displacement (displacement at failure, in.) | 8.7 | 10.6 |
| Fracture load/thickness (lbf/in.) | 705 | 1250 |
| Energy to fracture (lbf-in) | 23.0 | 40.8 |
It is surprising to be that while that melt spun fibre of the invention does not have higher tensile strength compared with dry-spinning fiber, but
Be the melt spun fibre bursting strength it is higher.
Although having elaborated best mode and preferred embodiment, the scope of the present invention is not according to patent statute
It is limited to this, but is limited by the scope of the appended claims.
Claims (11)
1. a kind of melt spun elastic fibers prepared by polyester thermoplastic's polyurethane, polyester thermoplastic's polyurethane is from including polyisocyanate
The reaction mixture preparation of cyanate, linear hydroxy-end capped intermediate polyester, one or more chain extenders and crosslinking agent；
Wherein the polyisocyanates includes diphenyl methane -4,4 '-diisocyanate；
Wherein the linear hydroxy-end capped intermediate polyester includes the 50/50 of adipic acid and 1,4- butanediol and 1,6-HD
The reaction product of blend；Wherein the number-average molecular weight (Mn) of the intermediate is 500 to 10,000 and acid value is less than 1.3；
Wherein one or more chain extenders include 1,4- butanediol；With
Wherein the crosslinking agent includes polyether crosslinking agent.
2. the melt spun elastic fibers of claim 1, wherein the weight average molecular weight of polyester thermoplastic's polyurethane is 200,000-
700,000 dalton.
3. the melt spun elastic fibers of claim 1, wherein the crosslinking agent is polyester thermoplastic's polyurethane and the crosslinking
The 5-20 weight % of total weight of agent.
4. the melt spun elastic fibers of claim 1, wherein the crosslinking agent is polyester thermoplastic's polyurethane and the crosslinking
The 8-12 weight % of total weight of agent.
5. a kind of fabric comprising at least two different fibers, wherein at least one of described fiber is the molten of claim 1
Spinning at least one of elastomer and the fiber is hard fibre.
6. the fabric of claim 5, wherein melt-spun bullet of the fabric by the two beam claims 1 relatively per a branch of hard fibre
Property fiber is made.
7. the fabric of claim 5, wherein the melt spun elastic fibers of the claim 1 have 20-600 danier.
8. the fabric of claim 5, wherein the hard fibre is selected from nylon and polyester.
9. the fabric of claim 8, wherein the hard fibre has 140 denier with 70 daniers and the melt spun elastic fibers
Neil.
10. clothing item, it includes the fabrics of claim 5.
11. the clothing item of claim 10, wherein the product is underwear or fitted garment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22035709P | 2009-06-25 | 2009-06-25 | |
| US61/220,357 | 2009-06-25 | ||
| CN201080027998.4A CN102803586B (en) | 2009-06-25 | 2010-06-24 | The high strength fabric be made up of Thin Specs constant compression elastomer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080027998.4A Division CN102803586B (en) | 2009-06-25 | 2010-06-24 | The high strength fabric be made up of Thin Specs constant compression elastomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105696101A CN105696101A (en) | 2016-06-22 |
| CN105696101B true CN105696101B (en) | 2019-07-16 |
Family
ID=42470526
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510244031.6A Pending CN104831377A (en) | 2009-06-25 | 2010-06-24 | High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers |
| CN201080027998.4A Active CN102803586B (en) | 2009-06-25 | 2010-06-24 | The high strength fabric be made up of Thin Specs constant compression elastomer |
| CN201610074529.7A Active CN105696101B (en) | 2009-06-25 | 2010-06-24 | The high strength fabric being made of thin gauge constant compression elastomer |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510244031.6A Pending CN104831377A (en) | 2009-06-25 | 2010-06-24 | High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers |
| CN201080027998.4A Active CN102803586B (en) | 2009-06-25 | 2010-06-24 | The high strength fabric be made up of Thin Specs constant compression elastomer |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US20100325782A1 (en) |
| EP (3) | EP2883983A1 (en) |
| JP (4) | JP5717733B2 (en) |
| KR (2) | KR101733649B1 (en) |
| CN (3) | CN104831377A (en) |
| AU (2) | AU2010264444B2 (en) |
| BR (1) | BRPI1015425B1 (en) |
| CA (1) | CA2765405C (en) |
| MX (1) | MX2011014050A (en) |
| MY (2) | MY154572A (en) |
| SG (2) | SG10201402444YA (en) |
| TW (2) | TWI591221B (en) |
| WO (1) | WO2010151633A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2801568C (en) * | 2010-06-15 | 2018-12-18 | Lubrizol Advanced Materials, Inc. | Melt spun elastic fibers having flat modulus |
| US20120028542A1 (en) * | 2010-07-30 | 2012-02-02 | Krishan Weerawansa | Self-Adjusting Bra Strap |
| SG191064A1 (en) | 2010-12-21 | 2013-07-31 | Lubrizol Advanced Mat Inc | Elastomer resins, fibers and fabrics thereof, and uses thereof |
| US20130255103A1 (en) | 2012-04-03 | 2013-10-03 | Nike, Inc. | Apparel And Other Products Incorporating A Thermoplastic Polymer Material |
| CN109222294A (en) * | 2012-12-28 | 2019-01-18 | 英威达技术有限公司 | Clothes comprising Stretchable composite fabric |
| US9565877B2 (en) | 2013-10-18 | 2017-02-14 | Mast Industries (Far East) Limited | Garment that clings to a wearer's skin and method of manufacture thereof |
| US20180291526A1 (en) * | 2014-12-04 | 2018-10-11 | Zhengzhou Zhongyuan Spandex Engineering Technology Co., Ltd. | Spandex fiber dry spinning component and spinning part |
| US9883702B2 (en) | 2015-10-07 | 2018-02-06 | Mast Industries (Far East) Limited | Portion of bra and bra having zones of varying elastic moduli |
| EP3793390B1 (en) | 2019-08-02 | 2021-07-21 | Nike Innovate C.V. | An upper for an article of footwear |
| CN112725927B (en) * | 2020-12-31 | 2022-04-15 | 江苏恒科新材料有限公司 | Super-soft and thick dyed nylon-like polyester fiber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816652A (en) * | 2003-06-30 | 2006-08-09 | 诺沃恩Ip控股公司 | Melt spun monofilament or elastic tape and process |
| CN1846018A (en) * | 2003-09-01 | 2006-10-11 | 株式会社晓星 | Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2435863C3 (en) * | 1974-07-25 | 1983-02-24 | Dynamit Nobel Ag, 5210 Troisdorf | Linear, saturated, semi-crystalline copolyesters |
| US3981310A (en) * | 1975-01-22 | 1976-09-21 | International Playtex, Inc. | Molded brassiere cups |
| GB1562711A (en) * | 1976-06-16 | 1980-03-12 | Fisher M | Brassiere |
| US4131731A (en) * | 1976-11-08 | 1978-12-26 | Beatrice Foods Company | Process for preparing polycarbonates |
| US4393186A (en) * | 1979-06-19 | 1983-07-12 | Lord Corporation | Thermoplastic polyurethanes prepared by reacting polyisocyanate, polyester polyol, cycloaliphatic diol and a monofunctional chain-terminating compound |
| US4727094A (en) * | 1983-09-27 | 1988-02-23 | Union Carbide Corporation | Method for producing polyurethanes |
| JPS61185520A (en) * | 1985-02-12 | 1986-08-19 | Kuraray Co Ltd | Production of polyester polyurethane |
| US4877856A (en) * | 1987-08-31 | 1989-10-31 | The Bf Goodrich Company | Soft thermoplastic polyurethane for blown film application |
| JPH0465521A (en) * | 1990-07-05 | 1992-03-02 | Toray Ind Inc | Production of polyphenylene sulfide monofilament |
| DE4319953A1 (en) * | 1993-06-16 | 1994-12-22 | Basf Ag | Non-tacky, highly elastic mono- and multifilament polyester-polyurethane elastomer threads, processes for their production by melt spinning and their use |
| JP3422857B2 (en) * | 1994-04-04 | 2003-06-30 | 保土谷化学工業株式会社 | Thermoplastic polyurethane resin having a wide rubber region and method for producing the same |
| DE4414327A1 (en) * | 1994-04-25 | 1995-10-26 | Bayer Ag | Process for the production of elastane threads |
| KR100212616B1 (en) * | 1996-12-26 | 1999-08-02 | 전원중 | Polyurethane elastic yarn full support stocking |
| JP4132244B2 (en) * | 1998-07-06 | 2008-08-13 | 株式会社クラレ | Polyurethane elastic fiber comprising thermoplastic polyurethane and method for producing the same |
| JP2000109534A (en) * | 1998-10-05 | 2000-04-18 | Toyobo Co Ltd | Polyurethane and elastic fiber |
| KR100307214B1 (en) * | 1998-11-06 | 2001-11-30 | 조민호 | Melt-spinnable thermoplastic linear polyurethan-urea resin |
| JP3255615B2 (en) * | 1999-02-24 | 2002-02-12 | カネボウ株式会社 | Polyurethane elastic fiber nonwoven fabric, method for producing the same, and synthetic leather using the polyurethane elastic fiber nonwoven fabric |
| GB0030310D0 (en) * | 2000-12-13 | 2001-01-24 | Medical Res Council | Apparatus and method for imaging a histological sample |
| US6911502B2 (en) * | 2001-02-23 | 2005-06-28 | Noveon Ip Holdings Corp. | Polyurethane elastomeric fiber and process for making the fiber |
| CN1170017C (en) * | 2001-10-09 | 2004-10-06 | 江苏南黄海实业股份有限公司 | Preparation method of melt spinning polyurethane fiber thin denier filament |
| US6995231B2 (en) * | 2001-12-21 | 2006-02-07 | Noveon Ip Holdings, Corp. | Extrudable highly crystalline thermoplastic polyurethanes |
| US7202322B2 (en) * | 2002-11-08 | 2007-04-10 | Noveon, Inc. | Heat resistant high moisture vapor transmission thermoplastic polyurethane |
| US6709147B1 (en) | 2002-12-05 | 2004-03-23 | Rauwendaal Extrusion Engineering, Inc. | Intermeshing element mixer |
| US7357889B2 (en) * | 2003-04-09 | 2008-04-15 | Lubrizol Advanced Materials, Inc. | Melt spun TPU fibers and process |
| US8148475B2 (en) * | 2003-06-30 | 2012-04-03 | Lubrizol Advanced Materials, Inc. | Melt spun polyether TPU fibers having mixed polyols and process |
| DE102005028056A1 (en) * | 2005-06-16 | 2006-12-21 | Basf Ag | Thermoplastic polyurethane containing isocyanate |
| US7300331B2 (en) * | 2005-10-11 | 2007-11-27 | Invista North America S.Ar.L. | Brassiere construction using multiple layers of fabric |
| ATE441740T1 (en) | 2005-12-22 | 2009-09-15 | Lubrizol Advanced Mat Inc | WINDING MACHINE ARRANGEMENT |
| US20100248575A1 (en) * | 2006-11-10 | 2010-09-30 | Basf Se | Fibers, particularly nonwoven fabric based on thermoplastic polyurethane |
| CN101970518B (en) * | 2007-10-22 | 2013-03-13 | 路博润高级材料公司 | Soft, elastic, plasticizer-free thermoplastic polyurethane and process to synthesize the same |
| CN101457018A (en) * | 2007-12-14 | 2009-06-17 | 烟台万华新材料科技有限公司 | Thermoplastic polyurethane elastomer with hydrolytic stability and preparation method thereof |
-
2010
- 2010-06-24 CN CN201510244031.6A patent/CN104831377A/en active Pending
- 2010-06-24 BR BRPI1015425-6A patent/BRPI1015425B1/en active IP Right Grant
- 2010-06-24 JP JP2012517718A patent/JP5717733B2/en active Active
- 2010-06-24 CN CN201080027998.4A patent/CN102803586B/en active Active
- 2010-06-24 CA CA2765405A patent/CA2765405C/en active Active
- 2010-06-24 MX MX2011014050A patent/MX2011014050A/en active IP Right Grant
- 2010-06-24 WO PCT/US2010/039773 patent/WO2010151633A1/en active Application Filing
- 2010-06-24 MY MYPI2011006097A patent/MY154572A/en unknown
- 2010-06-24 TW TW105103262A patent/TWI591221B/en active
- 2010-06-24 KR KR1020127001956A patent/KR101733649B1/en active Application Filing
- 2010-06-24 AU AU2010264444A patent/AU2010264444B2/en active Active
- 2010-06-24 EP EP15150781.1A patent/EP2883983A1/en not_active Withdrawn
- 2010-06-24 SG SG10201402444YA patent/SG10201402444YA/en unknown
- 2010-06-24 SG SG2011092004A patent/SG176815A1/en unknown
- 2010-06-24 EP EP10729020.7A patent/EP2446073B1/en active Active
- 2010-06-24 CN CN201610074529.7A patent/CN105696101B/en active Active
- 2010-06-24 TW TW099120581A patent/TWI523980B/en active
- 2010-06-24 KR KR1020167024936A patent/KR101799924B1/en active IP Right Grant
- 2010-06-24 US US12/822,441 patent/US20100325782A1/en not_active Abandoned
- 2010-06-24 EP EP20130155264 patent/EP2594667B1/en active Active
-
2011
- 2011-12-15 MY MYPI2014001890A patent/MY179095A/en unknown
-
2014
- 2014-10-23 JP JP2014216132A patent/JP2015025235A/en active Pending
-
2016
- 2016-01-27 JP JP2016013412A patent/JP2016113741A/en not_active Withdrawn
- 2016-09-02 US US15/255,258 patent/US20170029982A1/en not_active Abandoned
-
2017
- 2017-03-08 AU AU2017201591A patent/AU2017201591B2/en not_active Ceased
- 2017-11-02 JP JP2017212827A patent/JP2018024973A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816652A (en) * | 2003-06-30 | 2006-08-09 | 诺沃恩Ip控股公司 | Melt spun monofilament or elastic tape and process |
| CN1846018A (en) * | 2003-09-01 | 2006-10-11 | 株式会社晓星 | Process for preparing elastic fiber having high modulus, alkali-resistance and heat-resistance |
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105696101B (en) | The high strength fabric being made of thin gauge constant compression elastomer | |
| US20160053408A1 (en) | High strength constant compression elastic fibers and fabrics thereof | |
| JP7030525B2 (en) | Polyurethane fiber containing copolymer polyol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |