CN101003681A - Porous fiber - Google Patents

Porous fiber Download PDF

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Publication number
CN101003681A
CN101003681A CN 200710084713 CN200710084713A CN101003681A CN 101003681 A CN101003681 A CN 101003681A CN 200710084713 CN200710084713 CN 200710084713 CN 200710084713 A CN200710084713 A CN 200710084713A CN 101003681 A CN101003681 A CN 101003681A
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Prior art keywords
fiber
polymer
diameter
pore
polymkeric substance
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越智隆志
木代明
野中修一
三原崇晃
铃木则雄
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Toray Industries Inc
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Toray Industries Inc
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Abstract

The present invention provides a nanoporous fiber being substantially free from coarse pores and having homogeneously dispersed nanopores, unlike conventional porous fibers. A porous fiber has pores each having a diameter of 100 nm or less, in which the area ratio of pores each having a diameter of 200 nm or more to the total cross section of the fiber is 1.5% or less, and the pores are unconnected pores, or a porous fiber has pores each having a diameter of 100 nm or less, in which the area ratio of pores each having a diameter of 200 nm or more to the total cross section of the fiber is 1.5% or less, the pores are connected pores, and the fiber has a strength of 1.0 cN/dtex or more.

Description

Multiporous fiber
The application be that July 28, application number in 2003 are 03818838.4 the applying date, denomination of invention divides an application for the application of " multiporous fiber ".
Technical field
The present invention relates to contain hardly the thick pore of diffuse-reflectance visible light, have the multiporous fiber of trickle and uniform a plurality of nanometer pores, and relate to when making this multiporous fiber polymer-alloy fibre and manufacture method thereof as its precursor.
In the following explanation that the present invention relates to, so-called " nanometer pore " is meant the fine holes that diameter 100nm is following.
In the present invention, so-called " nanoporous fiber " is meant at 1/μ of the pore m that contains on the axial fiber cross sections perpendicular to fiber below the diameter 100nm 2Above fiber.
This fiber that the present invention relates to a plurality of pores is to realize liquid-absorbent or the very fast fiber that increases of gas adsorbability.
And except realizing above-mentioned those good performances, the more important is not have the very fine such thick hole of can not saying so, or many and even, neat being present on the fiber cross sections of pore.
The present invention relates to and the diverse high-caliber multiporous fiber of the multiporous fiber of existing level, as mentioned above, this fiber not only can obtain making liquid-absorbent or the very fast effect that increases of gas adsorbability, and, utilize this nanometer pore structure can have various performances.
That is, this fiber not only all can use in the fiber industry but also in various industrial communitys, is epoch-making and very useful material.
Background technology
With nylon 6 (following usefulness ' N6 ' expression) or nylon 66 (following usefulness ' N66 ' expression) is the tynex of representative; Or, with polyethylene terephthalate (following usefulness ' PET ' expression) or polybutylene terephthalate (following usefulness ' PBT ' expression) is the trevira of representative, because mechanical characteristic and excellent size stability, not only can be used as dress material, and on upholstery and upholstery, industry, also be used widely.
In addition, be the polyolein fiber of representative with polyethylene (following usefulness ' PE ' expression) or polypropylene (following usefulness ' PP ' expression) etc., extensively be used industrial owing to light weight.
Yet any fiber all is to constitute fiber by single polymkeric substance, and its performance is restricted, so, begin inquiring into the polymer modification of copolymerization or polymeric blends in the past always, or passed through compoundization of function of conjugate spinning or blend spinning.
Wherein, polymeric blends needn't design new polymkeric substance, and, even adopt single composition spinning-drawing machine also can make, so, inquire into especially actively.
But,, before this, hollow fiber or multiporous fiber are also being inquired in order to give sense of fiber lightweight or water-absorbent.
About hollow fiber, develop at high hollow rate, but in false twisting processing etc., have the hollow problem that is damaged.Therefore, recently, utilization is also being developed with the multi-island type hollow fiber (most island components become hollow part) of the conjugated fibre of water-soluble polymers, general because hollow part diameter is more than 1 μ m, so interface at the polymkeric substance and the air of hollow part, the diffuse-reflectance of visible light increases, and has the remarkable problem that descends of color emissivity of fiber.
On the other hand, the multiporous fiber with the horizontal pore of a plurality of submicron (sub μ m) is also inquired into, still, main still the discussion utilized the polymeric blends spinning, rather than utilizes conjugate spinning.。
For example, sneak into hydrophilic polymerized PET fibrosis in addition in nylon, the technology by stripping copolymerization PET thus obtains the porous nylon fiber has been documented in the spy and has opened in the flat 2-175965 communique.Because this invention forms the concave-convex surface or the pore of pattern of sub-micron level thus, so, can obtain pearl shape gloss, but being color emissivity, the problem that exists significantly descends on the contrary.This is because pore size is the wavelength of visible light level, and pore is a lot, compares with above-mentioned multi-island type hollow fiber, due to the diffuse-reflectance of visible light increases.
In addition, as example with pore size pore littler than visible light, the spy opens clear 56-107069 communique (the 1st～3 page) and has done record, but the thick aggregated particle that in fact in blend fiber, has PET, make this aggregated particle stripping and form the thick pore of submicron～1 μ m level, so it is low that the problem of existence remains color emissivity.In fact, the page 2 of opening clear 56-107069 communique this spy is past down to the 7th row from upper left hurdle, put down in writing " polyester composition major part exists with the bar of 0.01～0.1 μ m thickness in the polymeric amide, forms almost onesize cavity after the stripping ", the existence of hint PET aggregated particle.
In addition, utilize the example of the multiporous fiber of nylon/PET blend fiber, opening flat 8-158251 communique and spy the spy opens flat 8-296123 communique and has done record, but because the dispersion size deviation of PET is big in nylon, keep the distribution about 0.1～1 μ m, still can not solve the problem of the color emissivity reduction that causes because of thick hole.In addition, as above-mentioned example in the past, when the distribution of sizes of pore is big, the shared influence of thick pore in the whole pore is sharply strengthened, influence to trickle nanometer pore does not almost have on the contrary, so the problem of existence is to give full play to the effect that porous produces.
Therefore, seek to realize not containing the multiporous fiber of thick pore.
On the other hand, the polymer-alloy fibre to the precursor that becomes multiporous fiber or super extra fine filament has also carried out all discussions.
For example, can enumerate, can calculate 9.4 * 10 by utilizing the silent oscillation mixing roll -5The PET superfine fiber of DENIER with polystyrene (following usefulness " PS " expression) as sea component, with the example (United States Patent (USP) 4th, 686, No. 074 specification sheets (28th page)) of PET as the polymer alloy island type structure fiber of island component.
But actual situation is, in this embodiment, put down in writing when surveying the fiber number of this PET superfine fiber, and filamentary fiber number has 1 * 10 -4DENIER～1 * 10 -2The amplitude of DENIER, the dispersion diameter of island component PET is 100～1000nm in the resulting polymer-alloy fibre, has only obtained containing the alloy fiber on a plurality of thick islands.
In addition, there is example to enumerate, by in the copolyester of the polyethylene terephthalate composition of 0 mole of % of PET copolymer-1, admixtured polyether imide (following usefulness " PEI " expression) 30 weight % make the granular dispersive utmost point specific polymers alloy fiber (spy open flat 8-113829 communique (1st～12 page)) of PEI with 2～80nm level.Yet in this embodiment, because PEI is dispersed into granularly, the spinning instability only obtains the big fiber of strand spot, poor practicability.
In addition, open disclosed fiber in the invention of flat 8-113829 communique the spy, consistent with the fusing point of PEI, because at 320 ℃ with for the too high temperature spinning of copolyester, pyrolysis is remarkable, the result of supplementary test shows that the intensity of resulting polymer-alloy fibre is lower than 1.5cN/dtex, finally can not actually use.In addition, open in the invention of flat 8-113829 communique this spy, by it being used 6%NaOH solution, in 90 ℃ of alkaline purifications 2 hours, obtain the interconnected spongy fiber of pore thus, but because PEI and copolyester hydrolysis, so silk intensity is lower than 1.5cN/dtex, even consider from this point of this intensity, can not be made for practicality fully.
Summary of the invention
The 1st purpose of the present invention is in view of the premises, provides a kind of and original multiporous fiber level of inquiring into different, and the nanometer pore that contains thick pore hardly is rich in homogeneity ground dispersive and has a plurality of nanoporous fibers that constitute.
The multiporous fiber of the present invention that reaches above-mentioned the 1st purpose is the multiporous fiber with the following pore of diameter 100nm, and wherein, the area ratio of the pore in whole fiber cross sections more than the diameter 200nm accounts for below 1.5%, and pore exists as separate wells.
Reach above-mentioned the 1st purpose another multiporous fiber of the present invention, be the multiporous fiber with the following pore of diameter 100nm, wherein, the pore area ratio in whole fiber cross sections more than the diameter 200nm accounts for below 1.5%, and pore exists as communicating aperture, and intensity is more than 1.0cN/dtex.
In addition, the 2nd purpose of the present invention, as mentioned above, it is different with the original multiporous fiber level of inquiring into to provide a kind of employing, the nanometer pore that contains thick pore hardly, the nanoporous fiber that homogeneity disperses to constitute is admirably made silk, cotton, felt, packing timber (パ ッ ケ one ジ), fabric, knitted fabrics or non-woven fabrics, or further use the clothing product that they obtain, the dress material material product, the upholstery goods, the vehicle interior decorated articles, life material product, produce material product, various articles for use such as medical articles (below it all being called " fibre product ").
Reach the fibre product of the present invention of the 2nd purpose, it is multiporous fiber with the following pore of above-mentioned diameter 100nm, the area ratio of the pore in whole fiber cross sections more than the shared diameter 200nm is below 1.5%, and, pore exists for the 1st multiporous fiber of the present invention of feature as separate wells, or itself and other blending in of fibers and constituting.
Perhaps, reach the of the present invention another fibre product of described the 2nd purpose, it is multiporous fiber with the following pore of diameter 100nm, wherein, the area ratio of the pore in whole fiber cross sections more than the shared diameter 200nm is below 1.5%, and pore exists as communicating aperture, and intensity is the 2nd multiporous fiber of the present invention of feature more than 1.0cN/dtex, or itself and other blending in of fibers and constituting.
According to the present invention, can be contained the multiporous fiber that how all to have thick pore in the original multiporous fiber hardly, pass through nanometer pore dispersive nanoporous fiber very equably specifically, the color emissivity that obtains the original multiporous fiber of a kind of ratio significantly improves, and has the fibre product of the high added value of good moisture absorption, characterization of adsorption.
The 3rd purpose of the present invention provides a kind of new polymers alloy fiber, as the raw fibre that can make the invention described above multiporous fiber.
Reach the polymer-alloy fibre of the present invention of this 3rd purpose of the present invention, with difficult solvability polymkeric substance as sea component, with easy solvability polymkeric substance as island component, and, constituted list structure and formed island type structure by the island, the above island shared area ratio in whole islands of diameter 200nm is below 3%.
In addition, the 4th purpose of the present invention provides a kind of particulate object lesson of making the new polymers alloy fiber that is applicable to, described polymer-alloy fibre is as the raw fibre that is applicable to the multiporous fiber of making the invention described above.
Reaching the particle of the present invention of the present invention's the 4th purpose, is the polymer alloy particle that is made of polymeric amide and polyester, and wherein, the average mark shot of dispersed polymeres directly is 1～50nm.
Perhaps, reaching another particle of the present invention of the present invention's the 4th purpose, is the polymer alloy particle that is made of polymeric amide and polyester, wherein, the ratio of mixture of the polyester of copolymerization sulfonate copolymer-1 .5～15 moles of % is 30～90 weight %, and 1 particulate weight in average is 2～15mg.
Perhaps, reaching another particle of the present invention of the present invention's the 4th purpose, is by being selected from polymeric amide, polyester, polyolefin polymers, and has the polymer alloy particle that hot water solubility's polyether ester constitutes, the ratio of mixture of polyether ester is 10～30 weight %, the b of chromogenic indicator as particle *Value is below 10.
In addition, the 5th purpose of the present invention provides the melt spinning method of new polymers alloy fiber that a kind of conduct is used to make the raw fibre of the invention described above fiber.
Reach the melt spinning method of the polymer-alloy fibre of the present invention of the 5th purpose of the present invention, difficult solvability polymkeric substance and easy solvability polymkeric substance are independently measured respectively, supply with, extrude that mixing roll carries out melting mixing and the polymer alloy that obtains when carrying out melt-spinning with twin shaft, the mode of the condition of following to satisfy (1)～(3) is carried out spinning:
(1) ratio of mixture=5～60 weight % of easy solvability polymkeric substance;
(2) difficult solvability polymkeric substance and easily the melt viscosity ratio=0.1～2 of solvability polymkeric substance;
(3) to extrude the kneading part length of mixing roll be 20～40% of screw rod useful length to twin shaft.
Perhaps, reach the another melt spinning method of the polymer-alloy fibre of the present invention of the 5th purpose of the present invention, difficult solvability polymkeric substance and easy solvability polymkeric substance are independently measured respectively, supply with, carry out melting mixing and the polymer alloy that obtains when carrying out melt-spinning with the silent oscillation mixing roll of number of partitions more than 1,000,000, the mode of the condition of following to satisfy (4)～(5) is carried out spinning:
(4) ratio of mixture=5～60 weight % of easy solvability polymkeric substance;
(5) difficult solvability polymkeric substance and easily the melt viscosity ratio=0.1～2 of solvability polymkeric substance;
Perhaps, reach the another melt spinning method of the polymer-alloy fibre of the present invention of the 5th purpose of the present invention, tempering tank is set before particle fusion, in a single day in this groove, preserve particle more than 2 kinds, after dried the mixing, mix the pellet supply fusing department doing, when difficult solvability polymkeric substance carried out the melting mixing spinning with easy solvability polymkeric substance, the mode of the condition of following to satisfy (6)～(8) was carried out spinning:
(6) ratio of mixture of the easy solvability polymkeric substance in the fiber=5～60 weight %;
(7) difficult solvability polymkeric substance and easily the melt viscosity ratio=0.1～2 of solvability polymkeric substance;
(8) capacity of particle tempering tank=5～20kg particle.
Description of drawings
Fig. 1 is the TEM photo in transverse section of the nanoporous fiber of the following embodiment of the invention 1 of expression.
Fig. 2 is the TEM photo of longitudinal section of the nanoporous fiber of the following embodiment of the invention 1 of expression.
Fig. 3 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 1 of expression.
Fig. 4 is the TEM photo of one of longitudinal section example of the polymer-alloy fibre of the following embodiment of the invention 1 of expression.
Fig. 5 is the TEM photo of one of the polymer alloy particulate transverse section of the following embodiment of the invention 1 of expression example.
Fig. 6 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 4 of expression.
Fig. 7 is the TEM photo of one of transverse section example of the nanoporous fiber of the following embodiment of the invention 4 of expression.
Fig. 8 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 8 of expression.
Fig. 9 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 8 of expression.
Figure 10 is the TEM photo of one of longitudinal section example of the polymer-alloy fibre of the following embodiment of the invention 8 of expression.
Figure 11 is the TEM photo of one of transverse section example of the nanoporous fiber of the following embodiment of the invention 8 of expression.
Figure 12 is the TEM photo of one of longitudinal section example of the nanoporous fiber of the following embodiment of the invention 8 of expression.
Figure 13 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 9 of expression.
Figure 14 is the TEM photo of one of transverse section example of the nanoporous fiber of the following embodiment of the invention 9 of expression.
Figure 15 is the TEM photo of one of longitudinal section example of the nanoporous fiber of the following embodiment of the invention 9 of expression.
Figure 16 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 10 of expression.
Figure 17 is the TEM photo of one of the vertical section of the polymer-alloy fibre of the following embodiment of the invention 10 of expression example.
Figure 18 is the TEM photo of one of transverse section example of the nanoporous fiber of the following embodiment of the invention 10 of expression.
Figure 19 is the TEM photo of one of longitudinal section example of the nanoporous fiber of the following embodiment of the invention 10 of expression.
Figure 20 is the TEM photo of one of the polymer alloy particulate transverse section of the following comparative example 2 of the present invention of expression example.
Figure 21 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 15 of expression.
Figure 22 is the TEM photo of one of transverse section example of the nanoporous fiber of the following embodiment of the invention 15 of expression.
Figure 23 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 16 of expression.
Figure 24 is the TEM photo of one of transverse section example of the nanoporous fiber of the following embodiment of the invention 16 of expression.
Figure 25 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 19 of expression.
Figure 26 is the TEM photo of one of transverse section example of the nanoporous fiber of the following embodiment of the invention 19 of expression.
Figure 27 is the TEM photo of one of transverse section example of the polymer-alloy fibre of the following embodiment of the invention 35 of expression.
Figure 28 is one of an expression device for spinning illustration.
Figure 29 is one of an expression false-twisting device illustration.
Figure 30 is one of an expression nozzle illustration.
Figure 31 is one of an expression device for spinning illustration.
Figure 32 is one of an expression stretching device illustration.
Figure 33 is one of an expression device for spinning illustration.
Figure 34 is one of an expression draw false twisting device illustration.
Embodiment
Below nanoporous fiber of the present invention is illustrated.
As the polymkeric substance that constitutes nanoporous fiber of the present invention, known polyester or polymeric amide are arranged or be the thermosetting polymer such as thermoplastic polymer, resol, polyvinyl alcohol of representative with polyolefine etc., be the bad polymkeric substance of the thermoplasticity of representative or biological polymer etc. with the polyacrylonitrile, from the formability viewpoint, thermoplastic polymer is most preferred.
Wherein, polyester or polymeric amide are owing to its most fusing point height, so be preferred.When the fusing point of polymkeric substance more than 165 ℃ the time, thermotolerance is good, is preferred.For example, generally speaking, fusing point is at 170 ℃ for poly(lactic acid) (following usefulness " PLA " expression), and PET is 255 ℃, and N6 is about 220 ℃, so be preferred.
In addition, in these polymkeric substance, also can contain additives such as particle, fire retardant, antistatic agent.In addition, in the scope of not damaging polymer property, with other composition copolymerization also can, but in order to keep original thermotolerance of polymkeric substance or mechanical characteristic, the copolymerization rate is preferred at 5 moles of % or below the 5 weight %.
Particularly the time as dress material, upholstery, vehicle interior decoration etc., from points such as fusing point, mechanical characteristic, liquor styles, polyester or polymeric amide are preferred, the copolymerization rate at 5 moles of % or below the 5 weight %, relative viscosity is nylon 6, nylon 66 more than 2, perhaps limiting viscosity is PET, Poly(Trimethylene Terephthalate), the polybutylene terephthalate below 0.50, and weight-average molecular weight is that PLA more than 70,000 etc. is particularly preferred.What in addition, 80 weight % of these polymkeric substance formation multiporous fibers were above is preferred.
In the present invention, the multiporous fiber with the following pore of diameter 100nm is important.
As mentioned above, so-called multiporous fiber of the present invention is meant and contains 1/μ m in fiber cross sections 2The fiber of the pore that above diameter 100nm is following in the present invention, is called the nanoporous fiber with it.By this nanometer poreization of the present invention, liquid-absorbent or gas adsorbability are rapidly increased.
In addition, the above pore shared area ratio in whole fiber cross sections of diameter 200nm is being important below 1.5%.Because wavelength of visible light is about 400～800nm, so, because the above thick pore of diameter 200nm exists hardly, so, the reduction that can significantly lower the color emissivity when making the nanoporous fiber.Here, the diameter of pore or area can be by being cut into ultrathin section(ing) to the nanoporous fiber, with infiltration type electron microscope (TEM) it observed and estimating, measure in this way in the present invention.
In addition, the pore form has the ellipse of becoming or other erose situations, and being not limited to must proper circle, and in the present invention, diameter is to be converted into proper circle and to obtain from this pore area.
In addition, so-called whole fiber cross sections is meant filamentary fiber cross sections area,, is meant the polymkeric substance part area suitable with pore part here.These areas can better simplyly be obtained when image processing softwares such as employing WINROOF.In multiporous fiber of the present invention, more preferably the above pore of diameter 50nm account for whole fiber cross sections area than below 1.5%, especially preferred below 0.1%.
In addition, as the mean diameter of pore Time Xia 0.1～50nm Yi, causing the diffuse-reflectance of visible light hardly, is transparent to visible light, but because near deleterious ultraviolet wavelength, thereby presents the new function of so-called UV cutting.In addition, because fiber surface area increases very fast, thereby has the advantage of unimaginable good water absorbability of original multiporous fiber or adsorptivity.
In addition, when this pore the more, increase the more the receptivity of various liquid such as organic solvent is very fast beyond dewatering.But as the mean diameter Guo of pore Xiao Time, because thermal treatment and easily causing is broken, according to the inventor's discovery, the mean diameter of pore is 5～30nm more preferably.
One of nanoporous fiber of the present invention is illustrated in Fig. 1 (the TEM photo of N6 nanoporous fiber cross sections), can observe because of metallochromy cause trickle deep or light.Here, dense part is the N6 high-density region, and light part is the N6 density regions.Can think that light part is equivalent to pore here.In addition, these pores both can interlink into communicating aperture, and separate wells hardly also can link.
In the present invention, so-called communicating aperture is meant that pore interlinks, the state that links to each other continuously from the fiber top layer to internal layer in fact, on the other hand, so-called separate wells, be meant that pore links hardly, the pore on fiber top layer becomes disjunct state with the internal layer pore in fact.
These pores as described belowly can embed various molecules in pore, but consider its washing resistance and Huan Shi Time, because of the molecule that embeds by to a certain degree capture or encapsulated, so separate wells is preferred.
When being communicating aperture, descend owing to form the polymkeric substance continuity of fiber, so intensity easily reduces.Therefore, under the situation for multiporous fiber with communicating aperture, fibre strength is important more than 1.0cN/dtex among the present invention.
In the present invention, the nanometer pore forms as separate wells on earth, still forms as communicating aperture, and the admixture of island polymkeric substance that can be by selected polymer-alloy fibre as precursor or the leaching condition of island polymkeric substance are distinguished making.
In addition, under for the situation of multiporous fiber with communicating aperture, the mean diameter by making pore can make the intensity of fiber reach more than the 1.0cN/dtex more than 50cN.
As mentioned above, nanoporous fiber of the present invention has countless nanometer pores and constitutes, and therefore, specific surface area increases, and has the advantage that shows good moisture absorption adsorptivity etc.
According to the inventor's discovery, the rate of moisture absorption of nanoporous fiber (Δ MR) is being preferred more than 4%.For this rate of moisture absorption (Δ MR) more than 4%, is not particularly limited, according to the inventor's various discoveries, employing has the formed nanoporous fiber of the present invention of hygroscopic to a certain degree hydrophilic polymer and can reach.As one of hydrophilic polymer example, can enumerate polymeric amide such as N6 and N66 here.In addition, even can't help the nanoporous fiber that hydrophilic polymer such as polyester constitutes,, also can make this rate of moisture absorption (Δ MR) more than 4% by contain hygroscopic matter at the nanometer pore.As one of hygroscopic matter example, can enumerate polyalkylene oxide or its modifier etc. here.
In addition, this nanoporous fiber also can be used as offensive odor eliminating fibre and uses not only to water vapor but also good to the adsorptivity of various materials.For example, it is preferred that the smelly rate of disappearing of ammonia is reached more than 50%, but multiporous fiber of the present invention can purify it.In the nanoporous fiber of the present invention, for the smelly rate of disappearing of ammonia is reached more than 50%, be not particularly limited,, can reach by adopting the polymkeric substance that shows the smelly property that disappears to a certain degree to make nanoporous fiber of the present invention according to the inventor's various discoveries.Certainly, in the nanometer pore, also can contain various sorbent materials.
Also have, the smelly rate that disappears of ammonia can be measured by following method.That is, in 5 liters of cubic cartons, put into nanometer pore fiber 100% cloth and silk 1g, import 3 liters of ammoniated gases, starting point concentration (C 0) transfer to 40ppm.Behind the 2 Xiao Time, get the gas sample, measure ammonia concentration (C from cubic carton 1).In addition, do not put into the cloth and silk sample, carry out blank test, still measure ammonia concentration (C behind the 2 Xiao Time B).Calculate the smelly rate that disappears of ammonia according to following formula:
Smelly rate (the %)=[(C that disappears of ammonia B-C 1)/C B] * 100 (%)
Multiporous fiber of the present invention, not only the absorptivity of gas but also liquid is good, and can bring into play the water-retentivity of general cotton, and majority can be realized the water retention more than 60%.In nanoporous fiber of the present invention,, be not particularly limited, but according to the inventor's various discoveries, can have the nanoporous fiber of the present invention that the polymkeric substance of water-retentivity to a certain degree makes by employing and reach for water retention is reached more than 60%.As one of the polymkeric substance with water-retentivity to a certain degree example, can enumerate polymeric amide such as N6 and N66, certainly, in the nanometer pore, also can contain water-absorbing materials such as polyalkylene oxide.
Here, so-called water retention can be measured by following method.At first, nanometer pore fiber 100% cloth and silk flooded 1 Xiao Time and make abundant suction in water after, hanging is 1 minute on suspension bracket, uses family expenses washing machine (manufacturers: SANYO again, model: SW 150P (A)) dehydration is 3 minutes, makes that the residual moisture in the space removes between fiber surface or fiber.
Weight (W from this moment 1) and in 1 hour dry weight (W of 60 ℃ of dryings 0), calculate water retention according to following formula: in addition, the water retention of nylon is about 20～30% usually.
Water retention=[(W 1-W 0)/W 0] * 100 (%)
Multiporous fiber woolliness of the present invention is such, the situation that shows the swelling of reversible liquid at the length direction of silk is arranged, though be the function that synthon have natural fiber.Here, so-called " showing the swelling of reversible liquid ", mean the nanoporous fiber impregnation in liquid the time, nanoporous fiber absorbs liquid, in the length direction generation swelling (elongation) of silk, if remove liquid by drying etc. from the nanoporous fiber, then the length direction at silk shrinks, be back to the behavior of original length, this operation can reversibly be carried out repeatedly.Here, to reach more than 6% be preferred to the reversible liquid swelling rate of Si length direction.
Like this, be not particularly limited the nanoporous fiber of reversible liquid swelling,, nanometer pore homodisperse on whole fiber cross sections can be reached according to the inventor's various discoveries for the length direction that is manufactured on silk shows.In addition, reach more than 6%, can reach 30nm by the mean diameter that makes the nanometer pore with the realization of getting off for making reversible liquid swelling rate at the length direction of silk.
The above is the very big feature and advantage of nanoporous fiber of the present invention.
In addition, because various functional mass enter the nanometer pore easily, so, compare with original fiber, be the fiber that carries out function processing easily.
For example, in order to give the cloth and silk that constitutes by common trevira water absorbability, also almost can not exhaust even give polyoxyethylene glycol (following usefulness " PEG " expression) the class moisture adsorbent of molecular weight more than 1000.Yet,, can exhaust in a large number when giving same Xi Shi Ji Time to the formed cloth and silk of nanoporous fiber of the present invention that constitutes by PET.
In addition, recently as the material that has the skin care function because of preserving moisture, noticeable from the oily oil component fish Shark alkane in sky that Shark fish liver takes out, but this also is almost to be difficult to exhaust with the cloth and silk that common trevira constitutes, and the cloth and silk made from nanoporous fiber of the present invention can exhaust in a large number, and washing resistance also significantly improves.This is shocking action for the people who is familiar with common trevira.
In addition, the functional medicine that is exhausted is not only moisture adsorbent or wetting Agent for Printing Inks, and for example fire retardant, water-resisting agent, cold-retaining agent, heat preserving agent or smooth agent etc. also use as object.Its proterties is not limited to particulate, and polyphenol or amino acid, protein, capsaicine, VITAMIN etc. are used to promote the medicament of health cosmetic, or tetter medicament such as pompholyx etc. also can use as object.Even also can use pharmaceuticals such as sterilizing agent, antiphlogistic, analgesic agent.Perhaps, the medicament that also can further use the such absorption that is used for objectionable impurities of polyamine or photocatalyst nanoparticle to decompose.Perhaps, as required, exhaustion makes its polymerization can be made into hybrid materials after having the monomer that forms organic or inorganic polymer ability.Effectively utilize big specific surface area, make the activation of pore wall by chemical process, also can be so that have the absorption of selection and catalytic capability.Can make above-mentioned various function structure keep autonomous effect as required, also be wonderful.
If the intensity of nanoporous fiber of the present invention more than 1.5cN/dtex, then can improve the tear strength and the weather resistance of fibre product, so preferred.Intensity is more preferably more than the 2cN/dtex, more than the especially preferred 2.5cN/dtex.
In addition, when degree of stretching reaches 20% Yi Shang Time, the weather resistance of fibre product is improved, so preferred.
In order to make intensity more than 1.5cN/dtex, and degree of stretching reaches more than 20%, still can obtain the polyester of above-mentioned mechanical characteristic even adopt at Zhi Si Time separately, and it is preferred making the nanoporous fiber.In addition,, can obtain polymkeric substance such as high-intensity polymeric amide or polyester when adopting independent throwing, or the area that suppresses thick pore is important than the granular of, pore mean diameter etc. in order further to improve intensity.In addition, it is important being selected in the easy solvability polymkeric substance that uses in the polymer-alloy fibre as precursor, and selected not containing hinders that false what be cross-linked into material that the fibrous texture that grades forms is preferred.
Nanoporous fiber of the present invention also can adopt various fiber section forms such as three leaf sections, cross section, hollow section.At this moment, can adopt the different in nature cross-section fiber that adopts before this to realize with the spinning nozzle.
In addition, also can be fiber cross sections become nanoporous comprehensively, perhaps also can partly be located at fiber top layer side or internal layer to nanoporous, or the local part that is located at off-centre etc.
The so-called nanoporous portion here is meant the zone of containing the following pore of the above diameter 100nm of 1/μ m.
Portion becomes nanoporous portion when the fiber internal layer, and the fiber skin section becomes under the situation of common polymkeric substance, can improve antifriction consumption or dimensional stability, intensity.
Perhaps, the fiber skin section becomes nanoporous portion, and fiber internal layer portion becomes under the situation of common polymkeric substance, and dimensional stability, intensity can be improved.
Perhaps, nanoporous portion suction in the length direction swelling of silk, makes its off-centre occupy Pian heart Wei Zhi Time again, can reinforcing fiber curl.
When nanoporous portion occupied the curling outside, swelling further made to curl and strengthens owing to absorb water, and extensibility and bulkiness improve.
On the other hand, when nanoporous portion occupies curlingly when inboard, because suction, curling quilt extends, so thread present the effect of elongation as wool, the constraint of cloth and silk tissue obtains mitigation, presents the raising of air permeability because of coil or the expansion of knitting the hole.
Shown in these examples,, can provide the cloth and silk of breathing by suction when nanoporous portion when off-centre exists in fiber cross sections.But, when above-mentioned nanoporous portion part exists, all exist in order to make effect that the nanometer pore produces and the effect beyond the nanoporous portion, the nanoporous part reaches 5～95% to the area ratio of whole fiber cross sections, and is preferred, more preferably 30～80%, especially preferred 40～60%.The local nanoporous fiber that exists of such nanoporous portion can pass through, from the easy solvability composition of polymer-alloy fibre stripping the time, end dissolution process halfway, easily the solvability composition remains in the fiber, and perhaps the easy solvability of stripping becomes to assign to obtain in the conjugated fibre of the conjugate spinning of polymer alloy and common polymkeric substance.
In addition, nanoporous fiber of the present invention bores the fluffing handling ease of processing (the ウ オ one one パ Application チ) physics of etc.ing and carries out fibrillation by polishing processing or water, also as the so-called fibrillated fibre or the fibre product use of making thus.
The protofibril diameter of this moment, the form of combination that can be by the polymkeric substance in becoming the polymer-alloy fibre of precursor, the rerum natura of polymer-alloy fibre, the pore in the nanoporous fiber or fluffing processing conditions etc. are controlled in the scope of 0.001～5 μ m.Particularly, the form of pore is important, and the about decimal of pore the more has fibrillation more to be easy to tendency.This is to also having big influence in assorted size or ratio of mixture as the easy solvability polymkeric substance in the polymer-alloy fibre of precursor.Also have, the fiber good excessively to antifriction consumptions such as polymeric amide, owing to do not have fibrillated fibre before this, so be very useful.
Nanoporous fiber of the present invention both can use separately, also can knit by mixing, blending, mixed cotton, interweave, hands over volume, mixed use with common synthon or regenerated fibre or natural fiber etc.When using with, can improve the morphological stability of cloth and silk or weather resistance, chemical proofing with the good synthon of dimensional stability or weather resistance.When mixing use with regenerated fibre or natural fiber etc., can seek the further raising of moisture absorption, absorbent function or liquor style.
In addition, when nanoporous fiber of the present invention is yarn, both can be not have curling flat yarn, also can be crimped filament, can also be other forms in addition, when being crimped filament, in cloth and silk, have bulkiness and extensibility, of many uses so preferred.In addition, can adopt various fibre product forms such as macrofiber, staple fibre, fabric, knitted fabrics, non-woven fabrics, felt, leatheroid, thermoformed articles.During in particular as general dress material or upholstery goods, fabric, volume thing are preferred.On the other hand, during as functional products such as leatheroid or filter cloth, sorbing material, cloth for wiping or dusting, abrasive cloths, non-woven fabrics is preferred.
The nanoporous fiber of the invention described above is compared with original porous fiber, can provide that color emissivity does not reduce, water absorbability or the also good high quality stains cloth and silk of adsorptivity.
Therefore, in dress material purposes such as stocking, tights, underwear, shirt, spencer, pants, overcoat, can realize the goods that snugness of fit is good, not only be suitable for these purposes, but also be applicable to dress material material applications such as oversleeve or liner, maybe can control vehicle interior finish purposes such as Industrial materials purposes, vehicle seat or ceiling material such as life material applications such as upholstery purposes, cloths for wiping or dusting such as the curtain of indoor environment or carpet, cushion, furniture even filter cloth, abrasive cloth etc.
By the absorption of functional molecular, can be as the such most advanced material of environment, medicine, IT industry of the electrode of healthy, beauty treatment relative article or pharmaceuticals base cloth, fuel cell etc.
Nanoporous fibre manufacture of the present invention is not particularly limited, and for example, can obtain by removing the processable polymkeric substance from the polymer-alloy fibre of following insoluble polymkeric substance and processable polymkeric substance formation, below this method is illustrated.
For example, constitute sea component by the insoluble polymkeric substance, constitute by the processable polymkeric substance under the situation of polymer-alloy fibre of the formed island type structure of island component utilizing, the island that diameter 200nm is above, the area ratio that whole islands are compared in the existence of promptly thick cohesion polymer particle is to be preferred below 3%.The reduction of the color emissivity in the time of thus, can significantly reducing the nanoporous fibrosis.,, be not defined as proper circle here, so diameter is converted into circle from the island area and obtains because the island is the sub-elliptical shape of Dou slightly sometimes.In addition, to the area on whole islands the total areas on all islands of existing in the fiber section, can observe or the polymkeric substance mixing ratio estimate from the fiber section.The area on the island that diameter 200nm is above is than preferred below 1%.More preferably the area on the island more than diameter 100nm ratio is below 3%, and the area ratio on the island that especially preferred diameter 100nm is above is below 1%.
In addition, the mean diameter when the island is 1～100nm Time, can obtain the nanoporous fiber littler than original multiporous fiber aperture by removing the island, so preferred.When pore size reaches Na rice Shui Ping Time, owing to the diffuse-reflectance that causes visible light hardly, so not only color emissivity significantly improves, and to deleterious ultraviolet diffuse-reflectance increasing, so present the new function of UV cutting.In addition, because surface-area increases very fast, so present original multiporous fiber unexpected good water absorbability or adsorptivity, this is very big advantage.
Therefore, from the viewpoint of color emissivity or adsorptivity, little person is favourable for the mean diameter on island, but as too small Time, it is excessive that polymer interface becomes, and it is excessive to interact, and the refinement behavior of spinning is unstable easily.Therefore, more preferably 10～50nm of the mean diameter on island.
In addition, formation list structure in island is preferred.Therefore, because the refinement of island polymkeric substance support polymer alloy as reinforcing bar, so make spinning refinement behavior stable.The so-called list structure here, the fibre axis that is meant the island to L/D ratio in the structure more than 4, but usually fibre axis to L/D ratio more than 10, majority exceeds outside the TEM visual field.
In order to be contained thick island as described above hardly, and the island polymkeric substance is with the homodisperse polymer-alloy fibre of nano-scale, as described below, it is important having considered the combination of the affinity between the polymkeric substance or having become the selected of highly mixing compounding process.
In addition, as other manufacture method, the polymer alloy of available island type structure not only can also utilize the alloy fiber of following special layers structure.
The so-called special layers structure here is to adopt tem observation fiber Heng Duan Mian Time to show the structure of following state.
That is, through blended similar polymers form layers each other not, intermingling is made up the state (Fig. 8, fiber cross sections TEM photo) of existence.Therefore, similar polymers does not form with island structure (Fig. 3, Figure 16, fiber cross sections TEM photo) and compares in the interface each other, become quite big, compare intermiscibility with island structure and be improved, but when comparing the extremely special structure that consistency is low with so-called uniform texture such as PET/PBT.But, owing to do not find the clear and definite periodicity of layer, so, decompose the modulated structure that causes with so-called Yin Sipinuoda and have any different.Here, the TEM sample is by metallochromy, the awkward solvability polymkeric substance of dense part and light part is easy solvability polymkeric substance.In addition, from cambial viewpoint, island component is indefinite what is called ' an extra large structure ', structurally also can clearly be distinguished.The extra large structure in this sea is in polymeric blends, in the sea/extremely unsettled structure that the ratio of mixture nearby that reverses on the island presents, certainly, extremely difficulty is stablized spinning in this zone.At 1 layer of mean thickness of the layer of fiber cross sections direction easy-soluble component as at 1～100nm, then not full and uniform the disperseing of similar polymers with nano-scale, even mixed with little amount, the blended polymer performance also can be given full play to.1 layer of preferred 1～50nm of mean thickness of the layer of easy-soluble component.In addition, be in the structure (Figure 10, fiber cross sections TEM photo) of staple length direction at observable this layer of fiber cross sections with the strip elongation.
Polymer-alloy fibre with the special layers structure shown in the above-listed figure, can obtain by combination with certain particular polymers and spinning condition, for example, can be by copolymerization PET (15～30 weight %) and the polymeric amide (70～85 weight %) that copolymerization is had 4～6 moles of sulfonate compositions, carry out spinning after adopting the static mixing roll (number of partitions is more than 1,000,000) that is located in the spinning tank mixing and obtain.
As mentioned above, difficult solvability polymkeric substance, remove easy solvability polymkeric substance in the homodisperse polymer-alloy fibre, can obtain nanoporous fiber of the present invention thus with nano-scale from easy solvability polymkeric substance.In the prior art, as the Ju He Wu Time that in easy solvability polymkeric substance, adopts low melting point or low softening point, because it disperses particle diameter big, so the operation trafficability characteristic in silks such as the curling processing of carrying out pyroprocessing or twisted filament processing or cloth and silk processing significantly worsens, can not obtain in fact curling or the processing silk or the cloth and silk of twisted filament etc.
Yet, in polymer-alloy fibre of the present invention, because easily the solvability polymkeric substance is with the nano-scale homodisperse, the silk of pyroprocessing is processed or cloth and silk processing so employing low melting point or low softening point polymkeric substance carry out, still can improve its operation perviousness, can also improve resulting quality of item.
Also have, the type of polymer in the polymer-alloy fibre so long as different get final product more than 2 kinds of solvability, can increase as required that indissoluble is separated, easy solvability type of polymer, certainly, can also also use the phase solvation.
In above-mentioned polymer-alloy fibre,,, can utilize common alkaline purification operation, so be preferred as fiber post-treatment operation owing to remove the porous operation on island when easy solvability polymkeric substance is the easy solvability Ju He of alkali Wu Time.For example, as easy solvability Ju He Wu Time,, then be very big characteristics at organic solvent dissolution polymkeric substance such as employing polystyrene if consider to need antiknock device.
When easy solvability polymkeric substance is hot water resolvability Ju He Wu Time, owing to removing the island, so be preferred at the refining procedure of fiber.As the easy solvability polymkeric substance of alkali, for example, can enumerate polyester or polycarbonate etc., as hot water resolvability polymkeric substance, can enumerate polyester, alkylene oxide or polyvinyl alcohol that copolymerization has a plurality of hydrophilic groups and their modifier etc.
In addition, carry out decrement Jia Gong Time removing easy solvability polymkeric substance,, can be suppressed at the pore that produces by decrement in the high temperature and destroy, or production efficiency is also high, is preferred when carrying out decrement Jia Gong Time with the speed more than the 20 weight %/Xiao Time.Also have, here the decrement speed to decrement processing is illustrated, and discontented 1 Xiao Time is also harmless between the Jia worker Chu Li Time of decrement processing.
For keeping the mechanical characteristic limit of nanoporous fiber of the present invention, the limit draws the function of nanometer pore, it is preferred reaching 5～60 weight % as the mixed with polymers ratio on easy solvability polymkeric substance island, more preferably 10～30 weight %, especially preferred 15～25 weight %.
Above-mentioned polymer-alloy fibre is not owing to contain thick cohesion polymer particle, and it is more stable than prior art to have a spinning process, and the little features such as fiber of silk spot are easy to get.The silk spot can be estimated by Wu Site spot (U%), the polymer-alloy fibre that uses among the present invention if making U% is 0.1～5%, then is being used for Xian dimension Zhi Pin Time such as dress material or upholstery, vehicle interior decoration, it is little and goods that quality is high are preferred to obtain stain.U% more preferably 0.1～2%, especially preferred 0.1～1.5%.In addition, particularly as dress material with and present Za Se Time, also can be with 3～10% crin.Therefore, reach 0.1～5%, can disperse equably to reach with nano-scale by making the island polymkeric substance in order to make U%.In order further to suppress U%, can independently measure respectively by the combination optimizing of polymkeric substance, at polymkeric substance Hun Lian Time and supply with polymkeric substance, spinning condition optimizings such as nozzle diameter or cooling conditions are reached.In addition, reach 3～10%, form the Cu Si Time that particularly produces variegated accent, can reach by known known technologies such as PET in order to make U%.
Intensity as above-mentioned polymer-alloy fibre is more than the 2cN/dtex, then can improve the operation perviousness at twisted filament or weaving, knitting process etc., so preferred.Intensity is more preferably more than the 2.5cN/dtex, more than the especially preferred 3cN/dtex.
For the intensity that makes polymer-alloy fibre more than 2cN/dtex, can reach by adopting the condition that suppresses polymer unwinds carry out spinning.
Reach more than the 2.5cN/dtex for making, can reach by making the compounding process optimizing.In order to reach high strength, can reach by the optimizing of the ratio of mixture of easy solvability polymkeric substance, the viscosity terminal group concentration of polymkeric substance, the optimizing that is copolymerized into the polymkeric substance that grades and spin-drawing condition, the processing conditions that curls.
In addition, if the degree of stretching of polymer-alloy fibre 15～70%, then still can improve the operation trafficability characteristic of twisted filament or weaving, knitting process etc., so preferred.As draw false twisting processing Yuan Si Time, consider that from this point of operation trafficability characteristic of false twisting processing degree of stretching reaches 70～200%, preferred.Concerning stretching with precursor, degree of stretching reaches about 70～500%, consider from this point of tensile operation trafficability characteristic, and be preferred.The degree of stretching of polymer-alloy fibre is generally suitably adjusted by spinning speed or stretching ratio etc.
Also have, when as tynex by the fiber of hygroscopicity generation swelling, be difficult to obtain the so-called high directed undrawn yarn of degree of stretching about 70～200%.This is because fiber generation swelling in spinning winding, and the packing timber shape of coiling is destroyed and can not reel.Therefore, under the situation of this polymkeric substance,, can obtain high directed undrawn yarn by mixing more than the 5 weight % polyester etc. that swelling does not take place because of moisture absorption, suction as the polymer-alloy fibre of principal constituent.
In addition, the viewpoint that the cloth and silk bulkiness that constitutes from the nanoporous fiber increases considers that it is preferred giving curling to above-mentioned polymer-alloy fibre.If false twist yarn, it is preferred reaching more than 20% as the CrimpRigidity value (CR value) of crimp tendency index.More preferably more than 30%, especially preferred be more than 40% to the CR value.In addition, adopt machine crimp silk or air-flow to spray processing silk etc., as the number of crimp of crimp tendency index reach 5/be preferred more than the 25mm.In addition, also can give curling by making arranged side by side or eccentric core shell composite filament.At this moment, number of crimp reach 10/be preferred more than the 25mm.The CR value generally can be adjusted by false twisting processing conditionss such as coiling method device, twisting frame revolution, heater temperatures.For the CR value is reached more than 20%, by heater temperature is transferred to (melting point polymer-70) ℃ with on reach.In order to improve this CR value more, it is effective suppressing the high temperatureization of heater temperature or the blend level of easy solvability polymkeric substance.
Machine crimp silk or air-flow are sprayed the processing silk waits, make number of crimp reach 5/more than the 25mm, the conditions such as selecting of applicator or input rate of can curling by suitable change easily reach.
When adopting arranged side by side or eccentric core shell to close a Time again, the melt viscosity difference of polymkeric substance that can be by making stickup is more than 2 times, or makes the thermal contraction rate variance that spins a Time separately 5% with first-class, reaches 10 of number of crimp/more than the 25mm.
The manufacture method of above-mentioned polymer-alloy fibre is not particularly limited, and for example, can adopt following method.
That is, difficult solvability polymkeric substance and easily the solvability polymkeric substance carry out melting mixing, can obtain difficult solvability polymkeric substance and/or the easy finely divided polymer alloy that constitutes by the solvability polymkeric substance of difficult solvability polymkeric substance/easily of solvability polymkeric substance.Then, it is carried out melt-spinning, can obtain polymer-alloy fibre of the present invention.
Here, melt spinning method is important, extrudes mixing roll or static mixing roll etc. by employing and forces mixingly, can significantly suppress the generation of thick cohesion polymer particle.
In prior art (spy opens clear 56-107069 communique), owing to adopted section to mix (dry blending), mixed stain is big, can not prevent the cohesion of island polymkeric substance.
In the present invention, from forcing mixing viewpoint, adopt biaxial extruder as extruding mixing roll, adopting the mixing roll of number of partitions more than 1,000,000 is preferred as the silent oscillation mixing roll.In addition, mixing polymkeric substance supply method by mixing polymkeric substance is measured respectively, supplies with, can suppress the ratio of mixture change of mixed stain Huo Jing Time, is preferred.At this moment, both can supply with respectively, also can supply with respectively in molten state as particle.In addition, can also supply with the main body (at all) of extruding mixing roll to the polymkeric substance more than 2 kinds, perhaps, a kind of composition also can from the supply midway of extruding mixing roll as the side charging.
Using twin shaft to extrude mixing roll, the inhibition between the Zhi Liu Time of highly mixing and polymkeric substance is coordinated as mixing Zhuan Zhi Time.Screw rod is made of feed portion and kneading part, is more than 20% of screw rod useful length by making kneading part length, and it is preferred carrying out height mixing.In addition, be below 40% of screw rod useful length by making kneading part length, can avoid over-drastic to cut off stress, and shorten between Zhi Liu Time, can suppress the thermal ageing of polymkeric substance or the gelation of polymeric amide composition.In addition, be in the exit side of biaxial extruder as far as possible, can shorten the residence time after mixing, suppress the cohesion again of island polymkeric substance by making kneading part.In addition, strengthening when mixing, also can in extruding mixing roll, be provided with and have the screw rod of polymkeric substance being delivered to reverse backflow functionality.
In addition, the decomposition gas by aspirating as ventilation opening (vent) formula when mixing, or reduce moisture in the polymkeric substance suppresses the hydrolysis of polymkeric substance, can also suppress amine end groups in the polymeric amide or the carboxylic end group amount in the polyester.
Adopt this twin shaft to extrude mixing roll and can obtain the polymer alloy particle, but consider,, can enumerate as the example of the combination of preferred polymers from this point of versatility:
Combination 1: polymeric amide and polyester;
Combination 2: the polymkeric substance of from polymeric amide, polyester, polyolefine, selecting and hot water solubility's polymkeric substance.
In the polymeric amide and polyester of preferred combination 1, it is preferred that dispersive polymkeric substance average mark shot directly reaches 1-50nm.In addition, by in this particulate transverse section, be converted into circular diameter and reach the area ratio of the above thick dispersive polymkeric substance of 100nm, the ratio of the whole dispersive polymkeric substance in the particulate transverse section reaches below 3% relatively, can be when polymer-alloy fibre, be difficult to generate thick island, so preferred.In addition, the amine end groups amount in the polymer alloy is that benchmark is 6 * 10 with the weight of polymeric amide -5When mol equivalent/g is following, from improving spinnability or reducing this point of silk spot and consider it is preferred.
On the other hand, in the polymkeric substance of from polymeric amide, polyester, polyolefine, selecting and hot water solubility's polymkeric substance of preferred combination 2, ratio of mixture as hot water solubility's polymkeric substance of easy-soluble component reaches 10～30 weight %, whereby, spinnability, cutting and fibrosis, the performance of the function after the nanoporousization of extracting silkworm gut out reach balance, so preferred.In addition, make the b that chromogenic indicator as the polymer alloy particle *Value is below 10, and so the tone in the time of can adjusting fibrosis is preferred.General hot water solubility's polymkeric substance, painted easily because of its molecular structure poor heat resistance, but the operation by the above-mentioned residence time is shortened can suppress painted.In addition, as hot water solubility's polymkeric substance, can enumerate polyester, polyalkylene oxide, polyvinyl alcohol and these modifier etc. that copolymerization has a large amount of hydrophilic groups, but consider from this point of dissolution rate, thermotolerance, be preferred as a kind of polyether ester of polyalkylene oxide modifier.
These kneading devices both can independently be provided with spinning-drawing machine, in case after the polymer alloy particle is made, it is supplied with spinning-drawing machine, also can be connected on the spinning-drawing machine mixing molten polymer is directly carried out spinning.In addition, when adopting static mixing roll, insert in the filament spinning component and also can.
In order to reduce the cost of spinning process, when cutting into slices mixing (dry blending), also can adopt following method.
That is, the blended polymer beads is carried out in independent metering, supply, once is stored in the tempering tank mixing of cutting into slices here.At this moment, reach 5-20kg, both can suppress mixed stain as far as possible, can improve mixing efficiency again by capacity tempering tank.Then, blended pellet supply is extruded mixing roll, make molten polymer from this tempering tank.Both can adopt twin shaft to extrude mixing roll here and carry out mixingly, and perhaps, molten polymer fed the static mixing roll be inserted in pipe arrangement and the assembly carry out mixing.At this moment, also can adopt the many precursor granules of combined amount of easy solvability polymkeric substance.
As precursor granules, when for the polymer alloy particle that constitutes by polymeric amide and polyester, adopt the polyester of copolymerization sulfonate 1.5～15mol% as polyester, can make affinity raising with polymeric amide, viewpoint from the extension rate that improves precursor granules, ratio of mixture fixes on 30～90 weight %, and from making the consistent viewpoint that suppresses mixed stain with weight of initial polymeric amide, the particle that 1 particulate weight in average reaches 2～15mg is preferred.
Making 1 particulate weight in average or shape identical with the polymer beads of dilution as far as possible, can suppress mixed stain, is preferred.Concrete is, the weight in average difference of 1 polymer beads of 1 polymer alloy particulate weight in average and dilution is preferred in-20～+ 20% scopes.
In addition, the cohesion again of island polymkeric substance from suppress spinning, suppressing the generation viewpoint of the polymer particle of thick cohesion sees, from polymer alloy formation, fusion, to the residence time from spinning nozzle ejection also be important, the time from polymer alloy fusing department front end to the spinning nozzle before the ejection was preferred in 30 minutes.Particularly during the alloy of nylon and hydrophilic group copolymerization PET, because hydrophilic group copolymerization PET cohesion more easily must be noted that.
In addition, disperse with nano-scale in order to make the island polymkeric substance, the combination of polymkeric substance also is important, and by improving the affinity of difficult solvability polymkeric substance and easy solvability polymkeric substance, the easy solvability polymkeric substance that constitutes the island easily disperses with nano-scale.For example, adopting nylon as difficult solvability polymkeric substance, when adopting polyethylene terephthalate (PET) as easy solvability polymkeric substance, if use copolymerization on PET has the sulfonate as hydrophilic composition, particularly the hydrophilic group copolymerization PET of 5-sodium sulphur m-phthalic acid (SSIA) then can improve the affinity with nylon.Especially preferably adopting SSIA copolymerization rate is the above hydrophilization PET of 4mol%.
In addition, the melt viscosity of extra large polymkeric substance and island polymkeric substance is important than also, and the viscosity ratio of extra large polymkeric substance/island polymkeric substance is bigger, and the shear strength that is applied to the island polymkeric substance is bigger, and the island disperses to become easy with nano-scale.But, when viscosity ratio is excessive, worsen owing to cause mixing spot and spinnability, so it is preferred that viscosity ratio reaches about 1/10～2.Also have, under the situation that is above-mentioned polyester or polyester and hot water solubility's combination of polymers, polymkeric substance also presents affinity each other, so viscosity ratio is important, viscosity ratio preferably reaches 0.5～1.5.
By above analysis as can be known, the melt spinning method of preferred polymer-alloy fibre of the present invention gathers as follows.
Promptly, the melt spinning method of polymer-alloy fibre is, independent metering, the difficult solvability polymkeric substance of supply and easy solvability polymkeric substance, extruding with twin shaft that mixing roll carries out melting mixing and the polymer-alloy fibre that obtains when carrying out melt-spinning carries out melt-spinning in the mode that satisfies following condition (1)～(3):
(1) ratio of mixture=5～60 weight % of easy solvability polymkeric substance;
(2) difficult solvability polymkeric substance and easily the melt viscosity ratio=0.1～2 of solvability polymkeric substance;
(3) to extrude the kneading part length of mixing roll be 20～40% of screw rod useful length to twin shaft.
Perhaps, silk method is prevented in the fusion of polymer-alloy fibre, difficult solvability polymkeric substance and easy solvability polymkeric substance are independently measured respectively, supply with, when the polymer alloy that obtains carrying out melting mixing with the silent oscillation mixing roll of number of partitions more than 1,000,000 carries out melt-spinning, make the condition that satisfies following (4)～(5):
(4) ratio of mixture=5～60 weight % of easy solvability polymkeric substance;
(5) difficult solvability polymkeric substance and easily the melt viscosity ratio=0.1～2 of solvability polymkeric substance;
The perhaps melt spinning method of polymer-alloy fibre, tempering tank is set before particle fusion, in a single day in this groove, preserve particle more than 2 kinds, after dried the mixing, mix the pellet supply fusing department doing, when difficult solvability polymkeric substance carries out the melting mixing spinning with easy solvability polymkeric substance, make the condition that satisfies following (6)～(8):
(6) ratio of mixture of the easy solvability polymkeric substance in the fiber=5～60 weight %;
(7) difficult solvability polymkeric substance and easily the melt viscosity ratio=0.1～2 of solvability polymkeric substance;
(8) particle capacity=particle 5～20kg of tempering tank.
Promptly, easily the ratio of mixture of solvability polymkeric substance reaches 5～60 weight %, the melt viscosity of difficult solvability polymkeric substance and easy solvability polymkeric substance is important than the scope 0.1～2 simultaneously, in addition, extrude mixing roll with twin shaft and carry out melting mixing, in addition during melt-spinning, the kneading part length that twin shaft is extruded mixing roll is that 20～40% of screw rod useful length is carried out melt-spinning, perhaps, when adopting static milling device to carry out after the melting mixing in addition melt-spinning, adopt the silent oscillation milling device of number of partitions more than 1,000,000, perhaps, when adopting dry blending to carry out melt-spinning, particulate tempering tank capacity reaches particle 5～20kg, and to carry out melt-spinning be important.Also have, dry mix is compared with the melting mixing method, the blended lack of homogeneity, but engineering is simple, has cost advantage.In addition, doing when mixing, when adopting above-mentioned precursor granules, can suppress mixed stain to a certain degree.
From the feature of above-mentioned manufacture method, owing to can suppress thick aggregated particle, compared with prior art, the visco-elasticity balance of polymer alloy is difficult to destroy, and the spinning ejection is stable, significantly improves spinnability and silk spot.
In order to improve stability of spinning process more, preferably use the low material of end group concentration in the polymkeric substance, particularly when adopting polymeric amide, the end group amount of amine is preferably in 5.5 * 10 -5Below mol equivalent/g.The thermotolerance of known polymeric amide presents the tendency of gelation than polyester difference because of thermal ageing.In addition, as polymeric amide and polyester generation Ju compound He Jin Time, because the polyester molecule chain end has katalysis, so, compare with polymeric amide independence Cun Zai Time, the tendency of easy gelation is arranged, this verifies in research of the present invention.As polyamide gels Time, not only produce fracture of wire or silk spot, and, the filter pressure of polymkeric substance or the engineering pressures such as backside pressure of nozzle rise, the upper limit of spray volume descends, and assembly life-span shortens, and not only the production efficiency between Mei Dan Wei Time declines to a great extent, and, cause significant problems such as the frequent generation of silk fracture.Therefore, the gelation of inhibition polyamide/polyester alloy is important.Therefore, the amine end of the polymeric amide that uses in the polymer alloy reaches 5.5 * 10 with end-blockings such as acetic acid, the terminal base unit weight of amine -5Be preferred below mol equivalent/g.Thus, in case a grain Time is a benchmark with polymer alloy particulate polymeric amide weight, the terminal base unit weight of amine reaches 6 * 10 when polyamide/polyester alloy -5Be preferred below mol equivalent/g.
In addition, from the thermolysis inhibition of polymkeric substance, the viewpoint that gelation suppresses, spinning temperature is being preferred below 300 ℃.
Therefore,, when using, the stress of cutting off of the polymer alloy in nozzle hole is reduced, can keep viscoelastic balance, so stability of spinning process improves than common big straight footpath Time as nozzle diameter.Concrete is that it is preferred adopting the nozzle of ejection linear velocity below 15m/ divides of the nozzle of polymer alloy.In addition, the cooling of strand also is important, and the distance from nozzle to the position that actively begins to cool down reaches 1～15cm Time, and elongation is flowed and is easy to instability, solidifies rapidly by polymer alloy, can make spinning stable.
In addition, from making the viewpoint of island polymkeric substance granular, spinning is ventilated and reached more than 100 is preferred.In addition, in order to suppress the silk spot of undrawn yarn in spinning process, it is preferred that spinning speed reaches more than the 800m/ branch.In addition, for size or the rerum natura De Jing Time that suppresses silk changes, spinning speed is reached more than the 2500m/ branch, it is preferred making the fibrous texture prosperity.
In addition, in case after the polymer-alloy fibre that obtains like this reeled, can implement the thermal treatment that stretches, or implement draw false twisting processing, or in case Juan Rao Time not, after spinning, directly stretch or directly implement air-flow and spray processing etc.
The thermal treatment temp that making implement to curl adds worker Time is lower than (difficult solvability melting point polymer-50 ℃), can prevent the molten sticking of manufacturing procedure of curling, and improves the quality of curling.In addition, also can after carrying out staple fibre, make non-woven fabrics or spun yarn.
In addition, the silk that obtains like this, itself and other silk is carried out air-flow mix and knit or mixed knitting such as composit false twisting, or close sth. made by twisting, or carry out mixed cotton or blending.In addition, polymer-alloy fibre can use separately, or uses with other silk, makes knitted fabrics or non-woven fabrics.Certainly, also can adopt spunbond property fabric or melt flow etc. to make non-woven fabrics.
From containing the easy solvability polymkeric substance of cloth and silk stripping of a part of polymer-alloy fibre that obtains so at least, can be contained the cloth and silk of a part of nanoporous fiber whereby at least.
Certainly, the easy solvability polymkeric substance of not stripping also can as the cloth and silk use that contains a part of polymer-alloy fibre at least.Particularly, when being Ju Xian An Time, owing to obtaining above-mentioned original impossible high directed undrawn yarn, with the cloth and silk of silk union formations such as its crimped filament used flexibly or composit false twisting silk, have than more bulk softish high-quality feel originally, only this just can obtain higher value.In addition, even mix the cloth and silk knit the polymer-alloy fibre 100% beyond the silk, because of the polymer alloy of nano-scale improves thermotolerance and mechanical characteristic, only this still can obtain high value.
For the cloth and silk of nanoporous fiber 100%,, can deal with problems by using ， You Time with other silk at dimensional stability and antifriction consumption Bu Man Zu Time.At Hun Time, carry out stripping Jia Gong Time at easy solvability polymkeric substance, be benchmark with weight as the polymer-alloy fibre of nanoporous fiber precursor, polymer-alloy fibre with 20 weight %/hour more than speed to carry out decrement processing be preferred.
As mentioned above, by adopting by the fiber that obtains with original different manufacture method, can obtain nanoporous fiber of the present invention, its pore size is littler than original, contain thick pore hardly, not only can be used as dress material usefulness, and be to realize the premium properties De Hua Time raw material in generation in various fields.
Embodiment
Adopt embodiment to describe the present invention in detail below.Various physics value measuring methods among the embodiment adopt following method.
A. the melt viscosity of polymkeric substance
The キ ヤ ピ ロ ゲ ラ Off 1B that adopts the smart machine of Japan to make measures the melt viscosity of polymkeric substance.Also have, putting into between the polymkeric substance Ting Liu Time that begins to measure from sample is 10 minutes.
B. the relative viscosity of nylon
The nylon particle is dissolved in 98% sulphuric acid soln, be made into 0.01mg/ml concentration after, measure in 25 ℃.
C. the limiting viscosity of polyester [η]
In 25 ℃, in ortho chloro phenol, measure.
D. fusing point
With Perkin Elmaer DSC-7, use 2nd run, the fusing point of the peak temperature that shows the polymkeric substance fusion as polymkeric substance.The heat-up rate of this moment is 16 ℃/minute, and sample size is 10mg.
E. mechanical characteristic
At room temperature (25 ℃), draw speed=100%/minute, under the condition shown in the JIS L1013, obtain loading-extension curve.Then, loading value when removing fracture with initial titre, as its intensity, elongation is obtained the strength and elongation curve as elongation at break when removing fracture with initial specimen length.
F. the Wu Site spot (U%) of polymer-alloy fibre
The USTER TESTER 4 that adopts the manufacturing of Star エ Le ベ ガ one ウ ス one Co., Ltd. measures with normal mode to give silk speed 200m/ a branch.
G. percent thermal shrinkage
Percent thermal shrinkage (%)=[(L0-L1)/L0] * 100 (%)
L0: drawn yarn is made reeled yarn, measure the former length of reeled yarn at initial loading 0.09cN/dtex;
L1: the reeled yarn of measuring L0 substantially do not had under the load state handled 15 minutes in boiling water, the reeled yarn that air-dry back is measured under the initial loading 0.09cN/dtex is long
H. use the tem observation fiber cross sections
Cross-sectional direction or longitudinal section direction along fiber are cut into ultrathin section(ing), observe the transverse section of fiber with infiltration type electron microscope (TEM).In addition, implement metallochromy as required:
The TEM device: Hitachi society makes, the H-7100FA type
I: pore diameter or island polymkeric substance diameter
Pore diameter is obtained by laxative remedy.That is, the fiber cross sections photo that records with TEM with image processing software (WINROOF), is obtained diameter by the circle conversion on island.In addition, meticulous and complex-shaped, when being difficult to resolve, with the naked eye resolve with handwork with WINROOF.Mean diameter is obtained their simple several mean values.
At this moment, as average pore, in same transverse section, extract the pore more than 300 arbitrarily out.But,, break or hole so sample easily produces because the sample that tem observation is used is made ultra-thin shred.Thus, limit and sample situation carefully contrast the limit and carry out cautiously when diameter is resolved.In addition, inorganic particles or the space around it are not contained in the pore at this.Island polymkeric substance diameter is resolved according to pore diameter and is carried out.
J. color emissivity evaluation
The sample that obtains is dyeed by well-established law, compare with the color emissivity of painted comparative sample under the same terms.What comparative sample adopted is the sample that the polymkeric substance that constitutes the nanoporous fiber is made by the well-established law spinning.Specifically used following method.
When being nylon, " the NylosanBlue N-GFL " that dyestuff adopts Network ラ リ ア Application ト ジ ヤ パ Application Co., Ltd. to make transfers to 0.8 weight %, the pH of fibre product this dyestuff in 5 the staining fluid, with 100 times of bath raioes, 90 ℃ of processing 40 minutes.
When being polyester, " the ForonNavy S-2GL " that dyestuff adopts Network ラ リ ア Application ト ジ ヤ パ Application Co., Ltd. to make, this dyestuff in 0.8 weight %, the pH of fibre product transfer to 5 staining fluid, was handled 40 minutes with 1: 100 times of bath raio, 130 ℃ (poly(lactic acid) is 110 ℃).
Judge that by naked eyes obtain above or being of equal color emissivity " outstanding " almost of comparison, with " ◎ " expression, the poorer dress material that can be used as is represented with " zero " with being " well " fully.More than two be evaluated as qualified.Than the two the difference be defective, in detail, " poor slightly " represented with △, that is on duty mutually represents with x, all estimates with these 4 grades.
K. rate of moisture absorption (Δ MR)
Take by weighing about sample 1～2g and put into weighing bottle, kept dry 2 hours in 110 ℃, measure weight (Wo), secondly, object is measured weight (W65) in 20 ℃, relative humidity 65% after keeping 24 hours.Then, after keeping 24 hours, 30 ℃, relative humidity 90% measure weight (W90).And, calculate with following formula:
MR65＝[(W65-Wo)/Wo]×100％ (1)
MR90＝[(W90-Wo)/Wo]×100％ (2)
ΔMR＝MR90-MR65 (3)
L. the swelling rate of reversible water-swellable and filament length degree direction
Fiber is measured former length (L in 60 ℃ of dryings after 4 hours 0').Then, this fiber flooded 10 minutes in 25 ℃ water after, from water, take out and handle back measured length (L rapidly 1').Again this fiber after 4 hours, is measured dry back length (L in 60 ℃ of dryings 2').
And, carry out drying/water retting repeatedly 3 times, if the swelling rate of the filament length degree direction of the swelling rate of the 3rd time filament length degree direction with respect to the 1st time reaches more than 50%, then expression has the reversible water-swellable.The swelling rate of filament length degree direction can be calculated as follows.The length of fiber is that the silk painted fiber 2 places connected, and measures distance therebetween.This distance reaches 100mm.
Swelling rate (the %)=((L of filament length degree direction 1'-L 0')/L 0') * 100 (%)
M. water retention
Sample was flooded 1 hour in 25 ℃ of water, it is fully absorbed water after, hanging is 1 minute on suspension bracket, with family expenses washing machines dehydration 3 minutes, the residual moisture in space between fiber surface and fiber is deviate from then.The weight of this moment is (W 1).In 60 ℃ of dryings 1 hour, obtain dry weight (W 0).
Water retention (%)=[(W 1-W 0)/W 0] * 100 (%)
N. the ammonia smelly rate that disappears
In 5 liters of cubic cartons, put into the cloth and silk 1g of nanoporous fiber 100%, import 3 liters of ammoniated gases, starting point concentration (C 0) transfer to 400ppm.In cubic carton, gas is taken a sample after 2 hours, measure ammonia concentration (C 1).In addition, different therewith, do not put into the cloth and silk sample and carry out blank test, still after 2 hours, measure ammonia concentration (C B).Calculate the smelly rate that disappears with following formula:
The smelly rate that disappears (%)={ (C B-C 1)/C B} * 100 (%)
O. the curl characteristics of false twist yarn, CR value
False twist yarn is made reeled yarn, under the state that does not have loading in fact, in boiling water, handled 15 minutes air-dry 24 hours.This sample is applied the loading that is equivalent to 0.088cN/dtex (0.1gf/d) and is immersed in the water, measure the long L of reeled yarn after 2 minutes 0".Then, Yu Shuizhong removes the loading that is equivalent to 0.088cN/dtex, is replaced by the little loading that is equivalent to 0.0018cN/dtex (2mgf/d), measures the long L1 of reeled yarn after 2 minutes ".Calculate the CR value by following formula:
CR(％)＝[(L 0”-L 1”)/L 0”]×100(％)
P. number of crimp
Get fiber sample 50mm, the joint number that counting curls is obtained the joint number of every 25mm, this on duty 1/2 as number of crimp.
Q. tone (b *Value)
Measure b with MINOLTA SPECTROPHOTOMETER CM-3700d *Value.At this moment, adopt D as light source 65(colour temperature 6504K) is with 10 0The open country is looked and is measured.
Embodiment 1
Relative viscosity 2.15, melt viscosity 274 pools (280 ℃ were cut off speed 2432 seconds -1), 220 ℃ of fusing points, amine are terminal uses the acetic acid end-blocking, the terminal base unit weight of amine is 5.0 * 10 -5The N6 of mol equivalent/g (80 weight %), and relative viscosity 0.60, melt viscosity 1400 pools (280 ℃ were cut off speed 2432 seconds -1), 250 ℃ of fusing points, copolymerization 5-sodium sulphur m-phthalic acid 5mol%, contain the copolymerization PET (20 weight %) of the titanium oxide of 0.05 weight %, extrude mixing roll with twin shaft and carry out melting mixing in 260 ℃, obtain the polymer alloy particle.
This polymer alloy particulate section TEM photo is shown in Fig. 5, round conversion diameter as the copolymerization PET on island is that 20-30nm (average dispersion diameter 26nm), circle conversion diameter are that the above thick island of 100nm does not all have, copolymerization PET in N6 with the nano-scale homodisperse.
In addition, 1 particulate weight in average is 3mg, and the terminal base unit weight of amine is a benchmark with N6 weight, reaches 3.3 * 10 -8Mol equivalent/g, the mixing condition of this moment is as follows:
2 screws of the equidirectional complete occlusal pattern of screw rod model
Screw diameter 37mm, useful length 1670mm, L/D=45.1
Kneading part length is 28% of screw rod useful length
Kneading part is positioned at the discharge side of screw rod useful length 1/3
There is backflow portion at 3 places midway
Polymkeric substance is supplied with and will be measured respectively with the PET of N6 copolymerization, supplies with mixing roll respectively
260 ℃ of temperature
Ventilation opening 2 places
At this polymer alloy of 270 ℃ fusing departments, 2 fusions, import in the turning unit of 275 ℃ of spinning temperatures.Then, behind the metal non-woven fabrics filtration polymer alloy molten mass with ultrafiltration diameter 15 μ m, carry out melt-spinning (Figure 28).At this moment, the residence time from fusing department 2 to ejection is 10 minutes.Adopt ejection aperture 0.3mm, squit hole length to be the nozzle of 0.65mm, the spray volume of each single hole is the 2.1g/ branch, and the nozzle ejection linear velocity of polymer alloy is the 28m/ branch.In addition, the distance to cooling starting point (upper end of air flue (チ ニ system) 5) is 9cm below nozzle.Through 1m curings that is cooled, after oil supply guide rod 7 oil supply that are arranged on below the 1.8m of nozzle 4, the 1st draw roll 8 and the 2nd draw roll 9 by non-heating batch with the speed of 3800m/ branch the strand of ejection with 20 ℃ cold wind.
The spinnability of this moment is good, below nozzle, and the ballast phenomenon that the swelling polymer of ejection causes or because of disconnected carefully can not taking place that the spinnability deficiency causes, the fracture of wire during 24 hours continuous spinnings is zero.In addition, also not having becomes destroying by batching the packing timber that packing timber De Jing Time swelling causes of problem concerning nylon, have good operability.
In addition, this polymer alloy undrawn yarn shows that intensity is that 2.6cN/dtex, degree of stretching are 138%, U% is 0.9% good rerum natura.Adopt the device of Figure 29 to implement draw false twisting processing to it, obtain the polymer alloy false twist yarn of false twisting direction S and Z.At this moment, stretching ratio is that 1.5 times, the temperature of well heater 13 are 165 ℃, what adopt as false twist spindle 15 is 3 external mounted friction false twist devices of urethane dish, and the surface velocity of dish/processing silk velocity ratio (D/Y compares) is 1.65.Processibility is good, does not find fracture of wire or to the coiling of roller, false twist spindle.
The false twist yarn of resulting 87dtex, 24 threads, demonstration intensity are that 2.7cN/dtex, degree of stretching are 21%, percent thermal shrinkage is 8%, U% is 1.0%, CR is 38% good rerum natura (table 2), do not have not backtwisting part, and curling quality is also good.
The result that the filamentary transverse section of resulting polymer alloy false twist yarn is observed with TEM, show that N6 is the island structure (Fig. 3) on island (thin part) for sea (dense part), copolymerization PET, the mean diameter on island is 25nm, obtains copolymerization PET with the homodisperse polymer-alloy fibre of nano-scale.
Compare below 0.1% the area on whole islands on island more than the diameter 200nm, and compare below 0.9% the area on whole islands on the island more than the diameter 100nm.Here, so-called area to whole islands becomes the standard of thick cohesion polymer than the ratio that is meant the summation of island component area.In addition, the island from fiber longitudinal section tem observation is list structure (Fig. 4).Also have, the molten section TEM photo that touches mixing polymer alloy thin slice shows dried Fig. 5, and the island polymkeric substance is lower than 20～30nm with particle diameter and carries out ultra-fine dispersion, and is equal with the island polymkeric substance particle diameter (Fig. 3) in the fiber cross sections.Can stretch about about 200 times to the polymkeric substance of nozzle ejection by draw false twisting, the particle diameter of the island polymkeric substance of original fiber cross sections, polymer alloy is compared, should be reduced to below 1/14, as the island polymkeric substance particle diameter of the chip of raw material and fiber cross sections much at one, from melting between the nozzle ejection of polymer alloy, show that the island polymkeric substance condenses again, for cohesion is with the nano-scale homodisperse again while suppressing, it is important suitably selecting the such spinning condition of present embodiment.
Yet, stretch the polymer alloy false twist yarn of false twisting direction S and Z neat, carry out knitting with the 20G circular knitter it, aqueous sodium hydroxide solution (95 ℃; bath raio 1: 50) with 3 weight % was handled 1 hour; whereby, dissolved the copolymerization PET that removes more than 99% from the polymer alloy false twist yarn, obtained the bulking intensity 63cm that is made by N6 nanoporous fiber 3The fibre product of/g.
The circular knitting tricot that constitute from this N6 nanoporous fiber are implemented dyeing, carry out the color emissivity evaluation, as a result good, the no color spot of color emissivity.The result who surveys its rate of moisture absorption (Δ MR) is, shows 5.6% and surpass cotton good water absorbability.
This N6 nanoporous fiber being taken out from circular knitter, observe the lateral result of fiber with SEM and be, about 2000 times of enlargement ratios, do not see concavo-convexly at fiber surface, is beautiful configuration of surface.In addition, the fiber cross sections of this N6 nanoporous fiber is to confirm to exist the pore about diameter 20～30nm with the result (Fig. 1) of tem observation.The mean value of this pore is 25nm, and diameter is that the above big pore of 50nm does not all have.
In addition, as shown in Figure 1, it is the fiber with separate wells.The measurement result of its mechanical characteristic is that intensity is that 2.0cN/dtex, degree of stretching are 25%, shows sufficient mechanical characteristic as fibre product.In addition, it shows reversible water-swellable, and after 1 minute, the swelling rate of the filament length degree direction of the silk of extraction is 7.3% to the tubular knitted goods that is made of this N6 nanoporous fiber in 180 ℃ of setting.The rerum natura of N6 nanoporous fiber is shown in table 1.
Embodiment 2
The ratio of mixture of N6 and copolymerization PET is transferred to 95 weight %/5 weight %, carry out mixing similarly to Example 1.Then, change spray volume, the nozzle hole count of each single hole, carry out melt-spinning, draw false twisting processing similarly to Example 1, obtain the polymer alloy crimped filament of 90dtex, 34 threads.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.
The high directed undrawn yarn that obtains is that intensity is that 2.7cN/dtex, U% are 0.8% high-quality silk.In addition, do not have fracture of wire in the draw false twisting manufacturing procedure, processibility is also good.In addition, not only show the CR value greatly to 45% bulkiness, and backtwisting and curling quality are ungood yet.The fiber cross sections of resulting polymer alloy crimped filament shows island structure with the result of tem observation, and the mean diameter on island is 20nm, obtains copolymerization PET with the homodisperse polymer-alloy fibre of nano-scale.Compare below 0.1% the area on whole islands on island more than the diameter 200nm, and compare below 1% the area on whole islands on the island more than the diameter 100nm.Observe as can be known from fiber cross sections, the island polymkeric substance is a list structure.The rerum natura of false twist yarn is shown in table 2.
To the weak twist of this polymer alloy crimped filament enforcement 300T/m, make flat fabric with organizine and tram, similarly to Example 1 by alkaline purification, remove the copolymerization PET more than 99%, obtain the fabric that constitutes by N6 nanoporous fiber.
The fabric that is made of N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, good, the no color spot of color emissivity.Extract N6 nanoporous fiber out from this fabric, the tem observation result of fiber cross sections is, the vestige of extracting the island polymkeric substance out becomes the separate wells of mean diameter 25nm, and the above big pore of diameter 50nm does not all have.N6 nanoporous fiber has good rerum natura as shown in table 1.
Embodiment 3
The ratio of mixture of N6 and copolymerization PET is transferred to 90 weight %/10 weight %, carry out mixing similarly to Example 1.Then, change spray volume, the nozzle hole count of every single hole, carry out melt-spinning, draw false twisting processing similarly to Example 1, obtain the polymer alloy crimped filament of 90dtex, 34 threads.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.The directed undrawn yarn of resulting height is that intensity is that 2.7cN/dtex, U% are 0.8% high-quality silk.In addition, at draw false twisting manufacturing procedure non-cracking silk, processibility is also good.In addition, not only show the CR value, and it is also good not have not backtwisting part and curling quality greatly to 40% bulkiness.
The fiber cross sections of resulting polymer alloy crimped filament shows island structure with the result of tem observation, and the mean diameter on island is 25nm, obtains copolymerization PET with the homodisperse polymer-alloy fibre of nano-scale.Compare below 0.1% the area on whole islands on island more than the diameter 200nm, and compare below 1% the area on whole islands on the island more than the diameter 100nm.In addition, observe as can be known from fiber cross sections, the island polymkeric substance is a list structure.The rerum natura of false twist yarn is shown in table 2.
To the weak twist of this polymer alloy crimped filament enforcement 300T/m, make flat fabric with organizine and tram, by using alkaline purification similarly to Example 1, remove the copolymerization PET more than 99%, obtain the fabric that constitutes by N6 nanoporous fiber.The fabric that is made of N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, good, the no color spot of color emissivity.Extract N6 nanoporous fiber out from this fabric, the tem observation result of fiber cross sections is, the vestige of extracting the island polymkeric substance out becomes the following separate wells of mean diameter 20nm, and the above big pore of diameter 50nm does not all have.Good rerum natura shown in the N6 nanoporous fiber indicator gauge 1.
Embodiment 4
The ratio of mixture of N6 and copolymerization PET is transferred to 50 weight %/50 weight %, carry out mixing similarly to Example 1.Then, change spray volume, the nozzle hole count of every single hole, carry out melt-spinning, draw false twisting processing similarly to Example 1, obtain the polymer alloy crimped filament of 150dtex, 34 threads.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.
The directed undrawn yarn of resulting height is that intensity is that 2.5cN/dtex, U% are 1.0% high-quality silk.In addition, non-cracking silk in the draw false twisting manufacturing procedure, processibility is also good.Do not have not backtwisting part, the quality of the product that curl is also good.The fiber cross sections of resulting polymer alloy crimped filament is with the Fig. 6 that the results are shown in of tem observation, copolymerization PET, the island of diameter 10～20nm is linked to be a plurality of pearls and exists, do not contain thick cohesion polymer particle, compare below 0.1% the area on whole islands on island more than the diameter 200nm, and compare below 1% the area on whole islands on the island more than the diameter 100nm.In addition, observe as can be known island polymkeric substance strip structure from fiber cross sections.The rerum natura of false twist yarn is shown in table 2.
To the weak twist of this polymer alloy crimped filament enforcement 300T/m, make flat fabric with organizine and tram, by using alkaline purification similarly to Example 1, remove the copolymerization PET more than 99%, obtain the fabric that constitutes by N6 nanoporous fiber.The fabric that is made of N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good, also do not have color spot.Extract N6 nanoporous fiber out from this fabric, the tem observation result of fiber cross sections is, the vestige of extracting the island polymkeric substance out becomes the separate wells of mean diameter 20nm, and the above big pore of diameter 50nm does not all have.Good rerum natura shown in the N6 nanoporous fiber indicator gauge 1.
Embodiment 5
The melt viscosity of N6 and copolymerization PET than transfer to 0.9, the terminal base unit weight of the amine of N6 is as 6.5 * 10 -3Mol equivalent/g carries out melting mixing, melt-spinning, draw false twisting processing similarly to Example 1.At this moment, owing to the terminal base unit weight many (6.2 * 10 of the amine of N6 in the polymer alloy -3Mol equivalent/g), so the fracture of wire during 24 hours continuous spinnings is 2, no problem almost, but compare with embodiment 1, spinnability worsens slightly, and the U% of the directed undrawn yarn of resulting height is 2%, and the silk spot is big slightly.Also have, the intensity of high directed undrawn yarn is 2.5cN/dtex.In addition, in the draw false twisting manufacturing procedure, it is unstable that backtwisting becomes slightly, compares with embodiment 1, and the not part of backtwisting sporadically appears slightly.
Resulting polymer alloy crimped filament is any not to contain thick cohesion polymer particle, compare below 0.1% the area on whole islands on island more than the diameter 200nm, compare below 1% the area on whole islands on island more than the diameter 20nm, and the island polymkeric substance is the rib strip shaped structure.In addition, the CR value is 32%, compares with embodiment 1, and the silk spot of Fang Si Time is big slightly, and when U% is 2.2% Time, the silk spot of crimped filament also strengthens.The rerum natura of false twist yarn is shown in table 2.
This polymer alloy crimped filament, carry out similarly to Example 1 circle knitting after, by using alkaline purification, remove the copolymerization PET more than 99%, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber with the separate wells below the diameter 100nm.The fabric that is made of this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good, see color spot slightly.N6 nanoporous fiber has rerum natura good shown in the table 2.
Embodiment 6
The polymer alloy of making among the embodiment 1, carry out melt-spinning similarly to Example 1.At this moment, as shown in figure 30, adopt squit hole top to have the metering portion 18 of diameter 0.2mm, ejection aperture 20 be 0.5mm, and squit hole length 19 is the nozzle of 1.25mm, and making the single hole spray volume is that to spray linear velocity be the 10m/ branch for the nozzle of 2.1g/ branch, polymer alloy.The spinnability of this moment is good, and the fracture of wire during 24 hours continuous spinnings is zero.Can not take place concerning nylon, to become problem (the volume I is got breaking of packing timber that り パ Star ケ one ジ) De Jing Time swelling caused, has good operability by batching packing timber.And, its stretching ratio is decided to be 1.3 times, implement draw false twisting processing similarly to Example 1.
The false twist yarn of resulting 50dtex, 12 threads shows that intensity is that 3.5cN/dtex, degree of stretching are 29%, percent thermal shrinkage is 8%, CR is 38% good rerum natura (table 2).In addition, resulting polymer alloy crimped filament transverse section shows with the result of tem observation, obtain showing that N6 is that sea (dense part), copolymerization PET are the island structure of island (thin part), the mean diameter on island is 25nm, and copolymerization PET is with the homodisperse polymer-alloy fibre of nano-scale.Compare below 1% the area on whole islands on island more than the diameter 200nm.In addition, show that from fiber longitudinal section tem observation the island is list structure.The rerum natura of false twist yarn is shown in table 2.
Make that tubular knitted goods is twisted with the fingers as this polymer alloy crimped filament S and Z twists with the fingers mariages, with 3 weight % aqueous sodium hydroxide solutions (95 ℃, bath raio 1: 100) dip treating 1 hour, whereby, the copolymerization PET more than 99% was removed in hydrolysis from polymer-alloy fibre with it.Then, wash, drying.Obtain the round pin fabric products made by N6 nanoporous fiber from it.
The fiber cross sections of this N6 nanoporous fiber shows that with the result of tem observation the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is 25nm.Here, dense part is the N6 polymkeric substance, and thin part is equivalent to pore, but pore is a separate wells.
The round pin fabric that constitutes from this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good as a result.The result who surveys its rate of moisture absorption (Δ MR) is 5.6%, shows to surpass cotton good water absorbability.In addition, survey result's demonstration of its mechanical characteristic, intensity is that 2.6cN/dtex, degree of stretching are 30%, shows sufficient mechanical characteristic as fibre product.In addition, it shows reversible water-swellable, and after 1 minute, the swelling rate of the filament length degree direction of the silk of extraction is 7% to the tubular knitted goods that is made of this N6 nanoporous fiber in 180 ℃ of setting.The rerum natura of N6 nanoporous fiber is shown in table 1.
Embodiment 7
N6 adopt melt viscosity be 1260 pools (280 ℃ were cut off speed 2432 seconds -1), the terminal base unit weight of amine reaches 5.0 * 10 -5The N6 of mol equivalent/g, the melt viscosity ratio is 0.9, carries out melting mixing, melt-spinning, draw false twisting similarly to Example 6.At this moment, change single hole spray volume, nozzle hole count, obtain the polymer alloy crimped filament (table 2) of 105dtex, 96 threads, intensity 3.8cN/dtex, degree of stretching 29%, percent thermal shrinkage 8%, CR35%.The fiber cross sections of resulting polymer alloy crimped filament with the result of tem observation is, do not contain the polymer particle of thick cohesion, and the island in whole islands more than the diameter 200nm accounts for below 0.1%, and the above shared area of diameter 100nm is than below 1%.In addition, fiber cross sections is that the island forms list structure with the result of tem observation.
Twist with the fingers mariages as this polymer alloy crimped filament S sth. made by twisting/Z, operation similarly to Example 1 behind the making tubular knitted goods, by alkaline purification, is removed the copolymerization PET more than 99%.Obtain the round pin fabric products made by N6 nanoporous fiber.
The fiber cross sections of this N6 nanoporous fiber shows that with the result of tem observation the pore mean diameter of extracting the vestige of island polymkeric substance out is 20nm, and the above big pore of diameter 50nm does not all have, and these pores are separate wells.
The round pin fabric that constitutes from this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.N6 nanoporous fiber has the good rerum natura shown in the table 1.
Table 1
Average pore diameter (nm) Area is than 1 (%) Area is than 2 (%) Intensity (cN/dt ex) ΔMR (％) Color emissivity The smelly rate that disappears (%) Water retention (%)
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 25 25 25 25 20 25 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2.0 3.8 3.0 2.0 1.8 2.6 3.0 5.6 3.6 4.2 6.0 5.0 5.6 5.5 ◎ ◎ ◎ ◎ ○ ◎ ◎ 60 45 52 62 55 60 60 85 67 76 90 80 82 82
Average pore diameter: by the average pore diameter of tem observation estimation
Area is than 1: the pore more than the diameter 200nm is to the area ratio of whole fibers
Area is than 2: the pore more than the diameter 500nm is to the area ratio of whole fibers
Smelly rate disappears: the ammonia smelly rate that disappears
Table 2
The N6 polymkeric substance Area is than (%) Island mean diameter (nm) Spinnability Intensity (cN/dt ex) CR( ％) U％ (％) Percent thermal shrinkage (%)
NH 2Concentration (mol/g) wt％
Embodiment
1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 5.0×10 -55.0×10 -55.0×10 -55.0×10 -56.5×10 -55.0×10 -55.0×10 -5 80 95 90 50 80 80 80 0.1 following below 0.1 below 0.1 below 0.1 below 0.1 below 0.1 below 0.1 25 20 25 18 20 25 20 ○ ○ ○ ○ △ ○ ○ 2.7 4.0 3.5 2.5 2.5 3.5 3.8 38 45 40 35 32 38 35 1.0 0.8 0.9 1.2 2.2 1.5 1.5 8 12 11 8 9 8 8
The area ratio: the thick cohesion polymer particle more than the diameter 200nm is to the area ratio on whole islands.
Embodiment 8
With the N6 of use among the embodiment 1 and the device of copolymerization PET employing Figure 31, after carrying out fusion with 270 ℃, 290 ℃ respectively, cut apart 1,040,000 and mixed by being arranged on silent oscillation mixing roll 21 in the assembly 3 (eastern レ エ Application ジ ニ ア リ Application グ society make " Ha イ ミ キ サ one " 10 sections).Then, after its metal nonwoven fabric filter filtration, from the nozzle hole ejection of aperture 0.35mm with absolute filtration bore 20 μ m.At this moment, 280 ℃ of spinning temperatures, the distance of 5 upper ends reaches 7cm from nozzle 4 to air flue.Divide its traction with spinning speed 900m/, reel by the 2nd take off roll 9.Carry out spinning in 24 hours, fracture of wire does not take place when spinning, show good spinnability.The device that adopts Figure 32 with its stretching, heat-treat.At this moment, setting stretching ratio and be 3.2 times, the 1st hot-rolling 24 temperature and be 70 ℃, the 2nd hot-rolling 25 temperature is 130 ℃, and in stretching thermal treatment, fracture of wire does not all have, and shows good stretchiness.
Obtain the polymer-alloy fibre of 56dtex, 12 threads thus, but U% is 1.5%, in addition, this fiber cross sections figure with the result of tem observation is, become dense part N6 and light PET partly to form special layer structure by metallochromy, the thickness of pet layer part is about (Fig. 8) about 20nm.In addition, this fiber from the fiber top layer to 150nm about, special layer structure is damaged, form island structure, but estimate the result of the area of special layer structure division, relatively all fiber cross sections reaches 98%, and almost all the fiber section forms special layer structure (Fig. 9).In addition, the vertical section of this polymer-alloy fibre result of tem observation, layer becomes strip (Figure 10).Also have, the rerum natura of polymer-alloy fibre is shown in table 4.
Adopt polymer-alloy fibre to make tubular knitted goods, but the knitting process trouble free show good operation trafficability characteristic.In addition, 3% aqueous sodium hydroxide solution of this tubular knitted goods with 95 ℃ flooded 1 hour, remove PET fully, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber from polymer-alloy fibre.
This tubular knitted goods shows the good water absorbability that is better than Δ MR=5.7% and cotton.
The fiber cross sections of this polymer-alloy fibre result (Figure 11) of tem observation, the deep or light spot that is made of metallochromy is thinner than original polymer-alloy fibre.Here, dense part is a N6 high-density part, and light part is a N6 low density part.Yet light part can be thought and is equivalent to pore.The mid diameter that can judge pore thus is between 10～20nm.Hence one can see that, and the above big pore of diameter 50nm does not all have.In addition, be difficult to judge that from Figure 11 pore is separate wells or communicating aperture, but low density partly is configured to strip in longitudinal section observation (Figure 12), so be judged as separate wells.
In addition, the round pin fabric that is made of this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.Good rerum natura shown in the N6 nanoporous fiber indicator gauge 3.
Embodiment 9
The ratio of mixture of N6 and copolymerization PET is transferred to 50 weight %/50 weight %, carry out melt-spinning similarly to Example 8.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.With its stretch similarly to Example 8, thermal treatment, fracture of wire does not all have, and shows good stretchiness.
The fiber cross sections of resulting polymer-alloy fibre is with the Figure 13 that the results are shown in of tem observation, the pearl island that the trickle island of copolymerization PET about as diameter 10～20nm is linked to be exists, do not contain thick cohesion polymer particle, compare below 0.1% the area on whole islands on island more than the diameter 200nm, and the above area of diameter 100nm compares below 1%.In addition, from fiber longitudinal section tem observation as can be known, the island is a list structure.In addition, the silk rerum natura is as shown in table 4 is good rerum natura.
To this polymer-alloy fibre carry out similarly to Example 8 circle knitting after, use alkaline purification, remove the copolymerization PET more than 99%, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber.
The tem observation of the fiber cross sections that this N6 nanoporous fiber constitutes the results are shown in Figure 14, shows the trickle gradation pattern about 10～20nm, observes the following pore of diameter 20nm.The mean diameter that can judge pore thus is between 10～20nm.In addition, observe (Figure 15) from the longitudinal section of fiber, it is indeterminate that bar becomes, so, can judge that these pores are interconnection, form communicating aperture.Therefore, only adopt combination, compounding process, the blend level of particular polymers, then can obtain having the nanoporous fiber of communicating aperture.
The round pin fabric that is made of N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.The good rerum natura of N6 nanoporous fiber is shown in table 3.
Embodiment 10
Adopting the polymer alloy thin slice that obtains among the embodiment 1, change spray volume, nozzle hole count, is the 900m/ branch with the spinning speed, carries out melt-spinning similarly to Example 1.At this moment, the residence time from fusing department 2 to ejection is 12 minutes.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.Can not take place concerning nylon, to become problem by batch packing timber through the time swelling packing timber that causes destroy then, have good operability.In addition, it is operated similarly to Example 8, with 3.2 times of stretching ratios, the 1st hot-rolling 24 temperature are that 70 ℃, the 2nd hot-rolling 25 temperature are 130 ℃, stretch, thermal treatment (Figure 32).
The polymer-alloy fibre that obtains thus demonstrates 70dtex, 34 threads, intensity and is 3.7cN/dtex, degree of stretching and be 4.7%, U%=1.2%, percent thermal shrinkage are 11% good characteristic.
In addition, the transverse section of the resulting polymer-alloy fibre result of tem observation, show that N6 is the island type structure (Figure 16) on island (light part) for sea (dense part), copolymerization PET, the mean diameter on island is 38nm, can obtain the ultra-fine dispersive polymer-alloy fibre of copolymerization PET, the area ratio on whole relatively islands, island that diameter 200nm is above is 1.2%.In addition, from the tem observation of fiber longitudinal section as can be known, the island is list structure (Figure 17).The rerum natura of polymer-alloy fibre is shown in table 4.
Adopt the polymer-alloy fibre that obtains to make tubular knitted goods here, this tubular knitted goods was flooded 1 hour with 3% aqueous sodium hydroxide solution (90 ℃, bath raio 1: 100), the PET more than 99% is removed in hydrolysis from polymer-alloy fibre.Then the washing, drying.
With opticmicroscope this N6 nanoporous fiber is carried out the result that the fiber side is observed, compare with the fiber before the alkaline purification, Fibre diameter reduces, and by removing the island polymkeric substance, causes contraction at the radial direction of fiber.
The result that this fiber side is observed with SEM, when enlargement ratio was 2000 times of left and right sides, fiber surface was not seen concavo-convex, was the condition of surface of beauty.In addition, the fiber cross sections of this N6 nanoporous fiber result (Figure 18) of tem observation, the deep or light spot that causes because of metallochromy is thinner than original copolymer alloy fiber (Figure 16).Here, dense part is a N6 high-density part, and light part is a N6 low density part.And, can think that light part is equivalent to pore.That is, by removing the island polymkeric substance, the size of pore is trickleer than former island polymkeric substance, and the mean diameter of pore is in 10～20nm scope, and the above thick pore of diameter 50nm does not all have.Can judge that from the gradation pattern of Figure 18 (fiber cross sections) and Figure 19 (fiber longitudinal section) pore is a separate wells.
In addition, the round pin fabric that is made of this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.In addition, be 6% to the measurement result of its rate of moisture absorption (Δ MR), show to be better than cotton good water absorbability.The mechanical characteristic measurement result of this N6 nanoporous fiber is that intensity is that 2.0cN/dtex, degree of stretching are 70%, shows sufficient mechanical characteristic as fibre product.The rerum natura of N6 nanoporous fiber is shown in table 3.
Embodiment 11
The ratio of mixture of N6 and copolymerization PET is located at 40 weight %/60 weight %, carries out melt-spinning similarly to Example 1, make precursor granules.This 1 particulate weight in average is 3mg, and the terminal base unit weight of amine is that the basis reaches 3.5 * 10 with N6 weight -5Mol equivalent/g.
The new particle of the N6 that uses in this precursor granules and the melting mixing (バ one ジ Application ペ レ Star ト) (1 particulate weight in average is 3mg) is put into independently funnel 1,, supply with tempering tank 29 (capacity 7kg) (Figure 33) with the 28 independent meterings of metering portion.At this moment, the new particulate ratio of mixture of precursor granules and N6 is 1/3 by weight, in order to prevent attaching particles on the tempering tank wall, contains static inhibitor (Sanyo changes into industry (strain) society and makes, ェ マ Le ミ Application 40) 20ppm.Then, supply with twin shaft after stirring particles makes and mixes in this tempering tank and extrude mixing roll 30, the copolymerization PET ratio of mixture of making melting mixing reaches the polymer alloy of 15 weight %.At this moment, kneading part length is 33% of screw rod useful length, and melting temperature is 260 ℃.Then, melt-spinning is carried out in operation similarly to Example 1, obtains high directed undrawn yarn.Carry out that fracture of wire is zero during 24 hours continuous spinnings.In addition, can not take place concerning nylon, to become problem by batch packing timber because of through the time swelling destruction of causing packing timber.Present good operability.In addition, this polymer alloy undrawn yarn, demonstration intensity is that 2.5cN/dtex, degree of stretching are 130%, U% is 1.4% good rerum natura.It is operated similarly to Example 8, with 130 ℃ of the temperature of 90 ℃ of the temperature of 1.5 times of stretching ratios, the 1st hot-rolling 24, the 2nd hot-rolling 25 stretch, thermal treatment.This polymer-alloy fibre shows the good rerum natura (table 4) of 87dtex, 24 threads, intensity 3.2cN/dtex, degree of stretching 33%, percent thermal shrinkage 8%, U%1.6%.The transverse section of resulting polymers alloy fiber with the tem observation result is, shows that N6 is the island structure of island (thin part) for sea (dense part), copolymerization PET, and the mean diameter that obtains the island is the polymer-alloy fibre of 45nm, copolymerization PET superfineization.The area ratio on whole relatively islands, island that diameter 200nm is above is 1.6%.The longitudinal section tem observation result of fiber, the island forms list structure.
Then, be made into the tubular knitted goods of 20G, handled 1 hour, dissolve the copolymerization PET that removes more than 99% from polymer-alloy fibre thus with the aqueous sodium hydroxide solution (95 ℃, bath raio 1: 50) of 3 weight %.
The round pin fabric that is made of this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good, but sees stain slightly.In addition, be 5.0% to the measurement result of its rate of moisture absorption (Δ MR), show to be better than cotton good water absorbability.
To the fiber plane of structure section of this N6 nanoporous fiber result, can confirm that the separate wells about diameter 20～50nm exists with tem observation.The mean diameter of this pore is 30nm, and the area ratio of the big pore that diameter 50nm is above is 1.0%.The measurement result of its mechanical characteristic, intensity are that 2.0cN/dtex, degree of stretching are 25%, as fibre product, show sufficient mechanical characteristic.The rerum natura of N6 nanoporous fiber is shown in table 3.
Embodiment 12
N6 that is used for melting mixing among the embodiment 1 and copolymerization PET are put into independently funnel 1,, supply with tempering tank 29 (capacity 7kg) (Figure 33) with the 28 independent meterings of metering portion.At this moment, the ratio of mixture of N6 and copolymerization PET is 85 weight %/15 weight %, in order to prevent attaching particles on the tempering tank wall, contains static inhibitor (Sanyo changes into industry (strain) manufacturing, エ マ Le ミ Application 40) 20ppm.Then, supply with twin shaft after stirring particles is mixed in this tempering tank and extrude mixing roll 30, make polymer alloy.At this moment, kneading part length is 33% of screw rod useful length, and melting temperature is 260 ℃.Then, melt-spinning is carried out in operation similarly to Example 1, obtains high directed undrawn yarn.Carry out during the continuous spinning fracture of wire taking place in 24 hours.In addition, do not take place concerning nylon, to become yet problem by batch packing timber because of through the time swelling destruction of causing packing timber, present good operability.In addition, this polymer alloy undrawn yarn, the good rerum natura of demonstration intensity 2.4cN/dtex, degree of stretching 125%, U%1.6.It is carried out draw false twisting similarly to Example 1, compare with embodiment 1, it is unstable slightly that backtwisting becomes.The false twist yarn of the 87dtex that obtains, 24 threads, intensity 2.4cN/dtex, degree of stretching 21%, percent thermal shrinkage 9%, U%2.2, CR30% though do not constitute problem, compare with embodiment 1, and not backtwisting (table 4) sporadically appears.The transverse section tem observation result of resulting polymers alloy crimped filament, show that N6 is the island structure (Fig. 3) on island (thin part) for sea (dense part), copolymerization PET, the mean diameter on island is 52nm, obtains the decentralized polymer-alloy fibre of copolymerization PET superfine.The area ratio on whole relatively islands, island that diameter 200nm is above is below 2.0%.The longitudinal section of fiber is that the island forms list structure by the tem observation result.
Be made into the tubular knitted goods of 20G, this tubular knitted goods was handled 1 hour with 3% aqueous sodium hydroxide solution (95 ℃, bath raio 1: 50), the PET more than 99% is removed in dissolving from the polymer alloy false twist yarn.
In addition, the round pin fabric that is made of this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good, but sees color spot slightly.In addition, be 5.0% to the measurement result of its rate of moisture absorption (Δ MR), show to be better than cotton good water absorbability.
To the fiber plane of structure section of this N6 nanoporous fiber result, can confirm that the separate wells about diameter 20～50nm exists with tem observation.The mean value of this pore is 35nm, and the area ratio of the big pore that diameter 50nm is above is 1.6%.The measurement result of its mechanical characteristic is that intensity is 1.8cN/dtex, degree of stretching 25%, as fibre product, shows sufficient mechanical characteristic.The rerum natura of N6 nanoporous fiber is shown in table 3.
Embodiment 13
Carry out melt-spinning similarly to Example 10, the device spinning of employing Figure 34 also directly stretches.At this moment, change spray volume, the nozzle hole count of single hole, 40 ℃ of the circumferential speed 2000m/ branch of the 1st hot-rolling 31, temperature, 150 ℃ of the 2nd hot-rolling 32 circumferential speed 4500m/ branches, temperature obtain the polymer-alloy fibre of 55dtex, 12 threads, intensity 4.4cN/dtex, degree of stretching 37%, U%1.2, percent thermal shrinkage 12%.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.Resulting polymer-alloy fibre, anyly do not contain thick cohesion polymer particle yet, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, and the area on the island more than diameter 100nm ratio is below 1%, in addition, from the tem observation of fiber longitudinal section as can be known, the island is a list structure.Good silk rerum natura is shown in table 4.
The polymer-alloy fibre that obtains here, it is knitting to carry out circle similarly to Example 10, to this tubular knitted goods alkaline purification, removes the copolymerization PET more than 99%, obtains the tubular knitted goods that is made of N6 nanoporous fiber.
Fiber plane of structure section to this N6 nanoporous fiber with the tem observation result is, can confirm the deep or light spot that causes because of metallochromy, trickleer than original polymer-alloy fibre, by removing the island polymkeric substance, the size of pore is trickleer than original polymkeric substance, the mean diameter of pore is in the scope of 10～20nm, and the above big pore of diameter 50nm does not all have.Can judge that from tem observation these pores are separate wells.In addition, the tubular knitted goods that this N6 nanoporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.The rerum natura of N6 nanoporous fiber is shown in table 3.
Comparative example 1
Compounding process does not adopt twin shaft to extrude mixing roll and adopts conduct to mix the device of Figure 28 of simple thin slice (dry blending), carries out melt-spinning similarly to Example 1.Polymkeric substance ejection in the spinning is unstable, and spinnability is poor, and the fracture of wire in the spinning frequently takes place, and can not stably batch silk.Therefore, spinning speed is decided to be the 900m/ branch, but still can not stablizes and batch.Yet, adopt not at all easy undrawn yarn that obtains, be that 70 ℃, the 1st hot-rolling 25 temperature are 130 ℃ of thermal treatments that stretch, and obtain polymer-alloy fibre with 3.2 times of stretching ratios, the 1st hot-rolling 24 temperature.The transverse section of resulting polymer-alloy fibre, the result is with tem observation, mixed stain is big, the polymer particle of the thick cohesion that sporadically appears, the area ratio on whole relatively islands, island that diameter 200nm is above is 10% (table 4).Adopt it to make tubular knitted goods, implement alkaline purification similarly to Example 6, obtain the N6 multiporous fiber, the thick pore area ratio more than the diameter 200nm is greatly to 2.0%, and the coloured light that therefore looses is many, whiting, color emissivity poor (table 3).
Adopting the polymer-alloy fibre that obtains here, is 165 ℃ of temperature, 1.01 times of the stretching ratios of false twisting lesser trochanter lateral pin, well heater 13 with rotor 15, implements false twisting processing, the backtwisting instability, and the fracture of silk frequently takes place.Not at all easy false twist yarn that obtains, backtwisting is extremely not many, and is of poor quality.
Comparative example 2
Kneading part length is 10% of screw rod useful length, carries out melting mixing similarly to Example 1.Obtain the polymer alloy thin slice, with the result of the dispersion state of tem observation copolymerization PET be, dispersion diameter also is about 30nm, but the above existence of dispersion diameter 100nm is a lot, forms inhomogeneous dispersion (Figure 20).The above thick dispersed polymeres area ratio of circle conversion diameter 100nm, in the particle transverse section, relatively all dispersed polymeres reaches more than 50%.
Adopt this polymer alloy particle, melt-spinning is carried out in operation similarly to Example 1, but spinnability is poor, and the fracture of wire in the spinning frequently takes place, and can not stably batch silk.Therefore, still can not stablize and batch when spinning speed reaches the 900m/ timesharing.Yet, adopt not at all easy undrawn yarn that obtains, with comparative example 1 thermal treatment of advancing to stretch equally, obtain polymer-alloy fibre.The transverse section of polymers obtained alloy fiber with the tem observation result is, mixed stain is big, the cohesion polymer particle that sporadically appears thick, but the above island of diameter 200nm relatively all the area ratio on islands be 8% (table 4).Adopt its to make tubular knitted goods, implement alkaline purification with comparative example 1 is same, obtain the N6 multiporous fiber, but the above thick pore area of diameter 200nm is than greatly to 1.9%, the coloured light that therefore looses is many, whiting, color emissivity poor (table 3).
Adopt the polymer-alloy fibre that obtains here, with comparative example 1 same enforcement false twisting processing, but the backtwisting instability, the fracture of silk frequently takes place.Not at all easy false twist yarn that obtains not backtwisting is extremely many, of poor quality.
Table 3
Average pore diameter (nm) Area is than 1 (%) Area is than 2 (%) Intensity (cN/dt ex) ΔMR (％) Color emissivity The smelly rate that disappears (%) Water retention (%)
Embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 Below 20 below 20 below 20 below 30 35 20 0 0 0 0 0 0 0 0 0 1.0 1.6 0 2.1 2.0 2.0 2.0 1.8 3.4 5.7 3.6 6.0 5.0 5.0 5.8 ◎ ◎ ◎ ○ ○ ◎ 60 62 60 58 55 60 83 84 83 80 80 80
Comparative example 1 comparative example 2 - - 2.0 1.9 - - 1.3 1.3 4.3 4.2 × × - - - -
Average pore diameter: by the average pore diameter of tem observation estimation
Area is than 1: the pore more than the diameter 200nm is to the area ratio of whole fibers
Area is than 2: the pore more than the diameter 500nm is to the area ratio of whole fibers
Smelly rate disappears: the ammonia smelly rate that disappears
Table 4
The method of mixing Area is than (%) Island mean diameter (nm) Spinnability Intensity (cN/dte x) U％ (％) Percent thermal shrinkage (%)
Embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 Static EXT tempering tank → EXT tempering tank → EXT EXT 0.1 it is following below 0.1 below 1.2 1.6 2.0 0.1 20 (thick) 15 38 45 52 26 ○ ○ ○ ○ △ ○ 3.5 3.2 3.7 3.2 2.4 4.4 1.5 1.5 1.2 1.6 2.2 1.2 12 12 11 8 9 12
Comparative example 1 comparative example 2 Thin slice mixing EXT 10 8 130 120 × × 2.8 2.8 8.2 8.0 11 11
The area ratio: the thick cohesion polymer particle more than the diameter 200nm is to the area ratio on whole islands
Static: the static device that mixes (1,040,000 divide)
EXT: twin shaft extruding muller
Tempering tank → EXT: the thin slice mixing is thick on a small quantity in tempering tank, twin shaft extruding muller
Thin slice mixes: with the dry blending of graininess
Embodiment 14
N6 adopt melt viscosity be 1540 pools (280 ℃ were cut off speed 2432 seconds -1), the terminal base unit weight of amine reaches 5.0 * 10 -5The full-bodied N6 of mol equivalent/g makes N6 and copolymerization PET melt viscosity ratio reach 1.1, carries out melting mixing, melt-spinning, stretching thermal treatment similarly to Example 10.At this moment, change single hole spray volume, nozzle hole count, obtain the polymerization au-alloy fiber of 105dtex, 96 long filaments.Any spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.Any polymer particle that does not all contain thick cohesion of resulting polymer-alloy fibre, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, the area ratio on whole relatively islands, island that diameter 100nm is above is below 1%.The good rerum natura of silk is shown in table 6.In addition, learn that from the tem observation of fiber longitudinal section the island is a list structure.
The polymer-alloy fibre that obtains here, it is knitting to carry out circle similarly to Example 10, uses alkaline purification, removes the copolymerization PET more than 99%, obtains the tubular knitted goods that is made of N6 nanoporous fiber.
Fiber to this N6 nanoporous fiber with opticmicroscope, SEM observations is, by removing the island polymkeric substance, cause contraction similarly to Example 10, adopt about 2000 times of multiplying powers in the fiber radius direction, it is concavo-convex to confirm that fiber surface does not occur, and is clean configuration of surface.In addition, the fiber cross sections of this N6 nanoporous fiber can be judged with the result of tem observation, the deep or light spot that is made of metallochromy is thinner than original polymer-alloy fibre, by removing the island polymkeric substance, pore diameter is trickleer than original island polymkeric substance, the mean diameter of pore is the scope of 10～20nm, and the above big pore of diameter 50nm does not all have.In addition, pore is a separate wells.
In addition, the tubular knitted goods that this N6 nanoporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.The good rerum natura of N6 nanoporous fiber is shown in table 5.
Embodiment 15
The PET (50 weight %) that the N6 (50 weight %) that adopts among the embodiment 10 and copolymerization are had 12mol%5-sodium sulphur m-phthalic acid, 26mol% m-phthalic acid extrudes mixing roll with twin shaft and carries out mixingly in 245 ℃, obtains the polymer alloy thin slice.This polymer alloy is carried out fusion for 250 ℃ in spinning temperature, and nozzle diameter is decided to be 0.6mm, changes the single hole spray volume, carries out melt-spinning similarly to Example 3, divides with spinning speed 800m/ and batches undrawn yarn.With its stretching ratio is 3.4 times, 90 ℃ of the 1st hot-rolling 24 temperature, 130 ℃ of thermal treatments that stretch of the 2nd hot-rolling 25 temperature.Obtain the polymer alloy silk of 85dtex, 36 long filaments thus.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.The result of the fiber cross sections usefulness tem observation of this polymer-alloy fibre as shown in figure 21, the stratiform island of copolymerization PET about as minor axis 10～20nm, major axis 50～100nm exists, do not contain thick cohesion polymer particle, the above area ratio of island in whole islands of diameter 200nm accounts for below 0.1%, and the area more than the diameter 100nm is than also accounting for below 1%.In addition, the fiber longitudinal section shows that with the result of tem observation the island is a list structure.In addition, Si good rerum natura is shown in table 6.
The polymer-alloy fibre that obtains here, make tubular knitted goods similarly to Example 10 after, handled 1 hour with 3% aqueous sodium hydroxide solution (90 ℃; bath raio 1: 50); whereby, the copolymerization PET more than 99% is removed in dissolving, obtains the tubular knitted goods that is made of N6 nanoporous fiber.At this moment, can observe remarkable contraction in the fiber radius direction (radius shrinking percentage about 22%, area of section shrinking percentage about 40%).(2000 times) are observed with SEM in the fiber side that nylon after this dissolving removed is 6, but do not observe the vestige of extracting copolymerization PET out, promptly do not observe so-called strip ditch or space.
Fiber cross sections to this N6 nanoporous fiber the results are shown in Figure 22 with tem observation, but can judge the scope of the mean diameter of pore at 10～20nm, and the above big pore of diameter 50nm does not all have.In addition, can judge the pore formation communicating aperture that interlinks.
In addition, the tubular knitted goods that this N6 nanoporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.The water-swellable measurement result of N6 nanoporous fiber shows that the swelling rate of filament length degree direction is 11.1% big value.In addition, even the 3rd time is measured, the swelling rate of filament length degree direction does not almost descend, and reversibility, weather resistance are also abundant.This tubular knitted goods after 10 minutes, is measured the water-swellable of N6 nanoporous fiber in 160 ℃ of thermal treatments once more, and the swelling rate of filament length degree direction is 7.3%, and compares before the thermal treatment, and the swelling rate descends, and is very large value but compare with 3% of common N6 fiber.This shows that through hole thermal treatment can control the swelling rate of filament length degree direction, becomes the cloth and silk design and is easy to advantage.The good rerum natura of this N6 nanoporous fiber is shown in table 5.
Embodiment 16
Copolymerization PET adopts copolymerization that copolymerization PET (225 ℃ of the fusing points of 7mol% m-phthalic acid, 4mol% bisphenol-A epoxy ethane affixture are arranged, the titanium oxide that contains 0.05 weight %), the weight ratio of N6 and copolymerization PET is 50 weight %/50 weight %, nozzle diameter 0.7mm carries out melt-spinning, stretching thermal treatment similarly to Example 10.Though be out of question, compare with embodiment 10, the spinning instability, fracture of wire is 2 times during 24 hours continuous spinnings.Fiber cross sections to this N6 nanoporous fiber the results are shown in Figure 23 with tem observation, but the polymer particle of thick cohesion is few, and the mean diameter on island is 143nm, and the area ratio on whole relatively islands, island that diameter 200nm is above is 5%.In addition, learn that from the tem observation of fiber longitudinal section the island is a list structure.The rerum natura of silk is shown in table 6.
Polymer-alloy fibre, make tubular knitted goods similarly to Example 10 after, by alkaline purification, remove the copolymerization PET more than 99%, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber.
To this N6 nanoporous fiber is by removing the island polymkeric substance, to see contraction in the fiber radius direction similarly to Example 10 with the fractographic result of optics.In addition, the fiber cross sections of this N6 nanoporous fiber with the result of tem observation as shown in figure 24, but the vestige of extracting the island polymkeric substance out breaks, forming wide is 10～30nm, the pore about long 100nm, the big pore of the diameter 50～100nm that sporadically appears.In addition, the area ratio of the thick pore more than the diameter 200nm is 0.5%.It is carried out the color emissivity evaluation, but compare with embodiment 10, color emissivity is poor, but reaches the level that can use as dress material.In addition, this pore is a separate wells.
Embodiment 17
Be used as " the パ イ ゲ Application PP-15 " that the 1st industrial Pharmaceutical Co., Ltd of hot water solubility's polymkeric substance of polyalkylene oxide derivative makes and replace copolymerization PET, carry out melting mixing similarly to Example 1 in 240 ℃.The b of resulting polymer alloy thin slice *Value is 4.5.In addition, changing spray volume, the nozzle hole count of each single hole, is 1.2 times of 4000m/ branch, stretching ratios with the spinning speed, carries out melt-spinning, stretching thermal treatment similarly to Example 10, obtain 55dtex, 68 threads polymer-alloy fibre.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.The transverse section of resulting polymer-alloy fibre with the result of tem observation is, do not contain the polymer particle of thick cohesion, the above island of diameter 200nm to the area on whole islands than 1.3%.In addition, the island polymkeric substance disperses with strip.Good silk rerum natura is shown in table 6.
Adopt this polymer-alloy fibre, make tubular knitted goods similarly to Example 10 after, with 100 ℃ of hot-water cure 1 hour, remove the hot water solubility's polymkeric substance more than 99%, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber.
The fiber cross sections of this N6 nanoporous fiber with the result of tem observation is, pore is a separate wells, and its mean diameter is 30nm, and the above big pore of diameter 50nm does not all have.This pore is a separate wells.
In addition, the round pin fabric that is made of this N6 nanoporous fiber is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.The good rerum natura of N6 nanoporous fiber is shown in table 5.
Embodiment 18
With weight-average molecular weight 150,000, melt viscosity 857 pools (240 ℃, 2432 seconds -1), the poly-L-lactic acid (optical purity is more than 99.5%) of 170 ℃ of fusing points replaces copolymerization PET, in 220 ℃ of melting temperatures, carries out melting mixing similarly to Example 1.Also have, the weight-average molecular weight of poly(lactic acid) is obtained by laxative remedy.That is, in the chloroformic solution of sample, sneak into THF (tetrahydrofuran (THF)), as measuring liquid.With its gel permeation chromatography (GPC) Waters 2000 that makes with Waters society, measure in 25 ℃, use polystyrene conversion, obtain weight-average molecular weight.The N6 that uses among the embodiment 1 is at 240 ℃, 2432 seconds -1Melt viscosity be 570 the pool.In addition, change every single hole spray volume and nozzle hole count, spinning speed is the 3500m/ branch, carries out melt-spinning similarly to Example 1, obtains the high directed undrawn yarn of 105dtex, 36 threads, intensity 3.1cN/dtex, degree of stretching 107%, U%1.2%.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.Its stretching ratio is decided to be 1.4 times, carries out draw false twisting processing similarly to Example 1, obtain the false twist yarn of 76dtex, 36 threads, intensity 4.0cN/dtex, degree of stretching 29%, U%1.3%, CR35%.At this moment, consider the fusing point of poly-L-lactic acid, the temperature of well heater is fixed on 160 ℃, so almost there is not the not also good false twist yarn of backtwisting, quality, the operation trafficability characteristic of draw false twisting is also good.The fiber cross sections of resulting polymer alloy crimped filament with the result that TEM observes is, the polymer particle that does not contain thick cohesion, the area ratio of the whole relatively island components in island that diameter 200nm is above is below 0.1%, and the mean diameter of island polymkeric substance is 80nm.In addition, good silk rerum natura is shown in table 6.
Adopt this polymer alloy crimped filament, make tubular knitted goods similarly to Example 1 after, advance to handle with alkali, remove the poly-L-lactic acid more than 99%, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber.In addition, the tubular knitted goods that this N6 nanoporous fiber is constituted dyes, and carries out the color emissivity evaluation, and color emissivity is good.
Extract N6 nanoporous fiber from this tubular knitted goods out, fiber cross sections with the result of tem observation is, the vestige of extracting the island polymkeric substance out becomes the pore about diameter 30nm, and the big pore more than the diameter 50nm does not all have.In addition, the height of the strength ratio embodiment 1 of resulting nanoporous fiber.This is owing to contained sulfonic group among the copolymerization PET used among the embodiment 1 generates false crosslinking structure, have and hinder the tendency that the N6 fibrous texture forms, and this detrimentally affect of PLA is little.
Comparative example 3
Simple thin slice mix 50 weight % relative viscosity 2.8, melt viscosity 1260 pools (280 ℃ were cut off speed 2432 seconds -1) N6 and after the copolymerization of 50 weight % has the polyethylene terephthalate of 2.5mol%5-sodium sulphur m-phthalic acid, 3.5mol% bisphenol-A epoxy ethane affixture, carry out fusion in 290 ℃, spray from aperture 0.6mm circular hole nozzle, adopt the device of Figure 28, divide with spinning speed 1200m/ and carry out melt-spinning.Yet the polymkeric substance ejection in the spinning is unstable, and spinnability is bad, and fracture of wire frequently takes place in the spinning, can not stablize and batch silk.Adopt not at all easy undrawn yarn that obtains,, stretch for 2.7 times with stretching ratio with 120 ℃ of thermometal plates.Whereby, obtain the polymer-alloy fibre of 85dtex, 24 threads.This fiber cross sections with the result of tem observation is, mixed stain is big, the polymer particle of the thick cohesion that sporadically appears, and the area ratio of the above island of diameter 200nm in whole islands accounts for 10%.
Then, use alkaline purification, remove copolymerization PET more than 99% from its dissolving.At this moment, Fibre diameter does not almost change.It is carried out the color development evaluation, and the area of the thick pore that diameter 200nm is above, whitens so scattered light is many than greatly to 5.0%, and color emissivity is poor.
Comparative example 4
Simple thin slice mixes the N6 that uses in the comparative example 3 of 70 weight %, and the copolymerization of 30 weight % has the polyethylene terephthalate of polyoxyethylene glycol 8.5 weight % of 5-sodium sulphur m-phthalic acid 4.5mol%, the molecular weight 4000 of limiting viscosity 0.60, carry out fusion in 280 ℃, spray from aperture 0.6mm circular hole nozzle, adopt the device of Figure 28, divide with spinning speed 1000m/ and carry out melt-spinning.Yet the polymkeric substance ejection in the spinning is unstable, and spinnability is bad, and fracture of wire frequently takes place in the spinning, can not stablize and batch silk.Adopt not at all easy undrawn yarn that obtains, with 3.35 times of stretching ratios, the 1st hot-rolling 24 temperature be 90 ℃, the 2nd hot-rolling 25 temperature be 130 ℃ stretch, thermal treatment.Whereby, obtain the polymer-alloy fibre of 85dtex, 24 threads.This fiber cross sections with the result of tem observation is, mixed stain is big, the polymer particle of the thick cohesion that sporadically appears, and the area ratio of the above island of diameter 200nm in whole islands accounts for 8%.
Then, use alkaline purification, the copolymerization PET more than 90% is removed in dissolving.At this moment, Fibre diameter does not almost change.It is carried out the color development evaluation, and the area of the thick pore that diameter 200nm is above, whitens so scattered light is many than greatly to 2.4%, and color emissivity is poor.
Comparative example 5
Simple thin slice mixes the block polyether polymeric amide (polyalkylene glycol moiety 45 weight %+ poly-epsilon-caprolactone parts 55 weight %) of conduct phase solvation of homogeneous PET, the 3 weight % of the N6, the 20 weight % that use in the comparative example 3 of 77 weight %, with the device of Figure 28, carry out melt-spinning similarly to Example 1.Yet the polymkeric substance ejection in the spinning is unstable, and spinnability is bad, and fracture of wire frequently takes place in the spinning, can not stablize and batch silk.Adopt not at all easy undrawn yarn that obtains, stretch similarly to Example 1, thermal treatment.Whereby, obtain the polymer-alloy fibre of 77dtex, 24 threads.This fiber cross sections with the result of tem observation is, mixed stain is big, the polymer particle of the thick cohesion that sporadically appears, and the area ratio of the above island of diameter 200nm in whole islands accounts for 14%.
Then, use alkaline purification, the PET more than 99% is removed in dissolving.At this moment, Fibre diameter does not almost change as different from Example 10.It is carried out the color development evaluation, and the area of the thick pore that diameter 200nm is above, whitens so scattered light is many than greatly to 4.6%, and color emissivity is poor.
Comparative example 6
N6/ copolymerization PET ratio of mixture as 25 weight %/75 weight %, is carried out melt-spinning equally with comparative example 4.Yet the polymkeric substance ejection in the spinning is unstable, and spinnability is bad, and fracture of wire frequently takes place in the spinning, can not stablize and batch silk.Adopt not at all easy undrawn yarn that obtains, stretch for 2.7 times with stretching ratio with 120 ℃ of thermometal plates.Whereby, obtain the polymer-alloy fibre of 85dtex, 24 threads.This fiber cross sections with the result of tem observation is, and is different with comparative example 4, and the difficult deliquescent N6 of alkali is the island, and the easy solvability copolymerization of alkali PET forms the sea.Mixed stain is big, the polymer particle of the thick cohesion that sporadically appears, and the above area ratio of island in whole islands of diameter 200nm accounts for 10%.
With it similarly to Example 10, use alkaline purification, remove the result of extra large copolymerization PET, can obtain the fiber of N6 superfine fibre good bond.Yet the strength detection difficulty of this fiber is as practical fiber, operational difficulty.
Secondly, handle polymer-alloy fibre with formic acid, N6 is removed in dissolving, and simultaneously, copolymerization PET also significantly embrittlement, saccharoid is scattered, breaks easily, as practical fiber operational difficulty.Such polymer-alloy fibre can not get multiporous fiber in fact, and purpose of the present invention does not reach yet.
Comparative example 7
In PET, make copolymerization PET (limiting viscosity 0.6) and polyetherimide (the ゼ ネ ラ Le エ レ Network ト リ Star Network society system of the complete relatively sour composition copolymer-1 0mol% of naphthalic acid second diester, ウ Le テ system-1000) the copolymerization PET of copolymerization reaches 70 weight %, twin shaft with 30mm φ is extruded mixing roll, carries out mixing in 320 ℃.After the polymer alloy thin slice thorough drying that obtains like this, carry out melt-spinning with 6 hole nozzles, single hole spray volume 0.6g/ branch, 315 ℃ of spinning temperatures, spinning speed 500m/ branch.Compare with fusing point as the copolymerization PET of extra large polymkeric substance, because spinning temperature is too high, the spinning instability, fracture of wire is 10 times in the spinning in 12 hours, and spinnability is bad.Adopt the undrawn yarn that obtains on a small quantity,, stretch for 3.0 times, but the silk fracture is frequent with stretching ratio with 90 ℃ of preheat rolls, 120 ℃ of thermometal plates.The drawn yarn intensity that obtains like this is low to 1.3cN/dtex.This is because melting temperature, spinning temperature are too high to the copolymerization PET as main component, and that polymkeric substance is taken place is aging because of pyrolysis.In addition, its U% is 16%, extreme difference.
This copolymerization PET alloy fiber, make flat fabric with warp and parallel, take place but the fracture of silk and fluffing are frequent, operation trafficability characteristic extreme difference only obtains ropy fabric.This fabric was handled 2 hours with 90 ℃ 6 weight % aqueous sodium hydroxide solutions, obtained sponge shape fiber.Yet the intensity of this fiber is extremely low, is 0.3cN/dtex.This is because except that original copolymerization PET thermal ageing, the high concentration alkali long time treatment produces due to the various destructions copolymerization PET.
Therefore, when not setting mixing, the spinning condition that is suitable for polymkeric substance, then can not get high strength and the little silk of silk spot, throwing also worsens.In addition, when the poor solubility of easy solvability polymkeric substance and difficult solvability polymkeric substance hour, also be to cause low intensive reason.
As mentioned above, make mixing, spinning, dissolution conditions to every kind of polymkeric substance optimizing, can obtain beginning can be anti-in the fiber of practicality.
Table 5
Average pore diameter (nm) Thick pore area is than 1 (%) Thick pore area is than 2 (%) Intensity (cN/dtex) ΔMR (％) Color emissivity
Embodiment
14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 Below 20 below 20 45 30 30 0 0 0.5 0 0 0 0 - 0 0 2.5 2.0 2.0 2.0 3.3 5.8 4.8 5.1 5.3 5.0 ◎ ◎ ○ ◎ ◎
Comparative example 3 comparative examples 4 comparative examples 5 comparative examples 6 - - - - 5.0 2.4 4.6 - - - - - 1.4 1.3 1.3 - 2.4 2.3 2.3 - × × × -
Average pore diameter: by the average pore diameter of tem observation estimation
Thick pore area is than 1: the area ratio of the whole relatively fibers of pore that diameter 200nm is above
Thick pore area is than 2: the area ratio of the whole relatively fibers of pore that diameter 500nm is above
Table 6
The sea polymkeric substance The island polymkeric substance Sea/island viscosity ratio The method of mixing Area is than (%) Island mean diameter (n m) Spinnability Intensity (cN/d tex) U％ ( ％) Percent thermal shrinkage (%)
Kind wt ％
Embodiment
14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 N6 N6 N6 N6 N6 80 50 50 80 80 PET 1 PET 2 PET 3 PA0 PLA 1.1 0.2 0.3 0.3 0.7 EXT EXT EXT EXT EXT 0.1 it is following below 0.1 below 5 1.3 0.1 18 25 14 3 80 80 ○ ○ △ ○ ○ 4.1 3.1 3.3 3.5 4.0 1.2 1.8 2.5 1.5 1.3 12 12 10 12 12
Comparative example 3 comparative examples 4 comparative examples 5 comparative examples 6 N6 N6 N6 PET4 50 70 77 75 PET 4 PET 5 PET 6 N6 0.9 0.9 0.9 1.1 Thin slice thin slice thin slice thin slice 10 8 14 10 15 0 12 5 80 - × × × × - - 2.7 - 10 9.1 9.3 11 - - - -
Area ratio: the area ratio on the whole relatively islands of thick cohesion polymer particle that diameter 200nm is above;
PET1:5-sodium sulphur m-phthalic acid 5mol% copolymerization PET;
The copolymerization PET of PET2:5-sodium sulphur m-phthalic acid 12mol%+ m-phthalic acid 26mol%;
PET3: the copolymerization PET of m-phthalic acid 7mol%+ bisphenol-A epoxy ethane affixture 4mol%;
The copolymerization PET of PET4:5-sodium sulphur m-phthalic acid 2.5mol%+ bisphenol-A epoxy ethane affixture 3.5mol%;
The copolymerization PET of PET5:4.5mol%5-sodium sulphur m-phthalic acid+8.5wt%PEG4000;
PET6: homogeneous PET;
PA0: polyalkylene oxide modifier (hot water resolvability polymkeric substance);
EXT: twin shaft is extruded muller;
Thin slice: thin slice mixes.
Embodiment 19
N6 as N66, is carried out melt-spinning, stretching, thermal treatment similarly to Example 8.At this moment, the ratio of mixture of 280 ℃ of spinning temperatures, N66/ copolymerization PET is 80 weight %/20 weight %.Spinnability is good, and the fracture of wire during 24 hours continuous spinnings is zero.The transverse section of resulting polymer-alloy fibre shows with the result of tem observation, does not contain the polymer particle of thick cohesion, and the area ratio on whole relatively islands, the above island of diameter 200nm is below 0.1%, and the area ratio more than the diameter 100nm is also below 1%.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 10 circle knitting after, it is used alkaline purification, whereby, remove the copolymerization PET more than 99%, obtain the round pin fabric products of making by N66 nanoporous fiber.
The fiber cross sections of resulting N66 nanoporous fiber shows that with the result of tem observation pore is a separate wells, and the mean diameter of pore is the scope of 10～20nm, and the above big pore of diameter 50nm does not all have.
The tubular knitted goods that this N66 nanoporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.The good rerum natura of N66 nanoporous fiber is shown in table 7.
Embodiment 20
255 ℃ of fusing points, limiting viscosity 0.63, melt viscosity 830 were moored (280 ℃, 2432 seconds -1) homogeneous PET be the used hot water solubility's polymkeric substance 20 weight % of 80 weight %, embodiment 17, in 275 ℃, extrude mixing roll with twin shaft similarly to Example 1 and carry out melting mixing, obtain b *The polymer alloy particle of value=3.2.With its 280 ℃ of 280 ℃ of temperature, spinning temperatures at fusing department 2, change single hole spray volume and nozzle hole count, carry out melt-spinning similarly to Example 10, the result is that spinnability is good, the fracture of wire during 24 hours continuous spinnings is zero.In addition, the temperature of the 1st hot-rolling 24 is decided to be 90 ℃, stretches similarly to Example 10, thermal treatment, obtains the polymer-alloy fibre of 90dtex, 36 threads, intensity 3.3cN/dtex, degree of stretching 40%, U%1.5%, percent thermal shrinkage 7% thus.The fiber cross sections of resulting polymer-alloy fibre shows with the result (Figure 25) of tem observation, the polymer particle that does not contain thick cohesion, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, and the area ratio more than the diameter 100nm is also below 0.1%.In addition, dense part is PET, and light part is hot water solubility's polymkeric substance.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 8 circle knitting after, it with 100 ℃ of hot-water cure 1 hour, is removed the hot water solubility's polymkeric substance more than 99%, obtain the round pin fabric products of making by PET nanoporous fiber.
The fiber cross sections of resulting PET nanoporous fiber shows that with the result (Figure 26) of tem observation the mean diameter of pore is 20nm, and the above big pore of diameter 50nm does not all have.Here, dense part is PET, and light part is a pore, and pore is a separate wells.The rerum natura of nanoporous fiber is shown in table 7.
The tubular knitted goods that this PET nanoporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.
Embodiment 21
The polymkeric substance that 8 weight %PEG1000, the copolymerization of 7mo1% m-phthalic acid are formed (235 ℃ of fusing points, limiting viscosity 0.65, melt viscosity 920 pools (280 ℃, 2432 seconds -1) be homogeneous PET, in 255 ℃, carry out melting mixing similarly to Example 20, the polymer alloy particulate b that obtains *Value is 3.8.With its 255 ℃ of 255 ℃ of temperature, spinning temperatures, nozzle hole shape at fusing department 2 is the Y section, carries out melt-spinning similarly to Example 19, and spinnability is good as a result, and the fracture of wire during 24 hours continuous spinnings is zero.In addition, stretch similarly to Example 20, thermal treatment, obtain the polymer-alloy fibre of three leaf sections thus.The fiber cross sections of resulting polymer-alloy fibre shows with the result of tem observation, the polymer particle that does not contain thick cohesion, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, and the area ratio more than the diameter 100nm is also below 1%.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 20 circle knitting after, it with 100 ℃ of hot-water cure 1 hour, is removed the hot water solubility's polymkeric substance more than 99%, obtain the round pin fabric products of making by PET nanoporous fiber.
The fiber cross sections of resulting PET nanoporous fiber shows that with the result of tem observation the mean diameter of pore is 20nm, and the above big pore of diameter 50nm does not all have.The result of tem observation shows that pore is a separate wells.The rerum natura of nanoporous fiber is shown in table 7.
The tubular knitted goods that this PET nanoporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.
Embodiment 22,23
Copolymerization PET was moored (280 ℃, 2432 seconds as 220 ℃ of fusing points, melt viscosity 1290 -1) polytrimethylene terephthalate (PTT) or 220 ℃ of fusing points, melt viscosity 550 pools (280 ℃, 2432 seconds -1) poly-terephthaldehyde's fourth diester (PBT), carry out melting mixing, melt-spinning, stretching, thermal treatment similarly to Example 20.The fiber cross sections of resulting polymer-alloy fibre shows with the result of tem observation, the polymer particle that does not contain thick cohesion, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, and the area ratio more than the diameter 100nm is also below 1%.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 20 circle knitting after, it with 100 ℃ of hot-water cure 1 hour, is removed the hot water solubility's polymkeric substance more than 99%, obtain the round pin fabric products of making by the polyester nano multiporous fiber.
The fiber cross sections of resulting polyester nanoporous fiber shows that with the result of tem observation the mean diameter of pore is 20nm, and the above big pore of diameter 50nm does not all have.The result of tem observation shows that pore is a separate wells.The rerum natura of nanoporous fiber is shown in table 7.
The tubular knitted goods that this polyester nano multiporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.
Embodiment 24
As the poly(lactic acid) of using among the embodiment 18 (PLA), melt temperature is 220 ℃, carries out melting mixing similarly to Example 20 PET.220 ℃ of temperature, 220 ℃ of spinning temperatures with fusing department 2 carry out melt-spinning similarly to Example 20, and spinnability is good, and fracture of wire is zero during 24 hours continuous spinnings.In addition, be 90 ℃ with the 1st heat roller temperature 16, stretch similarly to Example 10, thermal treatment.The fiber cross sections of resulting polymer-alloy fibre shows with the result of tem observation, the polymer particle that does not contain thick cohesion, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, and the area ratio more than the diameter 100nm is also below 1%.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 20 circle knitting after, it with 100 ℃ of hot-water cure 1 hour, is removed the hot water solubility's polymkeric substance more than 99%, obtain the round pin fabric products of making by PLA nanoporous fiber.
The fiber cross sections of resulting PLA nanoporous fiber shows that with the result of tem observation pore is a separate wells, and its mean diameter is 20nm, and the above big pore of diameter 50nm does not all have.The rerum natura of nanoporous fiber is shown in table 7.
The tubular knitted goods that this PLA nanoporous fiber constitutes is implemented dyeing, carry out the color emissivity evaluation, color emissivity is good.Particularly the dyestuff of PLA has the low problem of exhaustion rate, can be by nanoporous raising dye exhausting rate, than the color emissivity height of common PLA fiber.In addition,, find the tendency that has biological decomposition speed to increase than common PLA fiber by increasing surface-area, optimum for the medical usage that requires to have biological decomposition speed rapidly.
Embodiment 25,26
Replace PLA with polypropylene (PP) or polymethylmethacrylate (following represent), carry out melting mixing, melt-spinning, stretching, thermal treatment similarly to Example 20 with PMMA.The fiber cross sections of resulting polymer-alloy fibre shows with the result of tem observation, does not contain the polymer particle of thick cohesion, and the area ratio on whole relatively islands, island that diameter 200nm is above is respectively 1.2% and 0.8%.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 20 circle knitting after, it with 100 ℃ of hot-water cure 1 hour, is removed the hot water solubility's polymkeric substance more than 99%, obtain the round pin fabric products of making by PP or PMMA nanoporous fiber.These pores are separate wells, and the rerum natura of nanoporous fiber is shown in table 7.
Embodiment 27
With polymethylpentene (following represent) with PMP as PET 255 ℃ of melt temperatures, carry out melting mixing similarly to Example 20.255 ℃ of the temperature of fusing department 2,255 ℃ of spinning temperatures carry out melt-spinning similarly to Example 20, and spinnability is good, and fracture of wire is zero during 24 hours continuous spinnings.In addition, the 1st heat roller temperature 24 is 90 ℃, stretches similarly to Example 10, thermal treatment.The fiber cross sections of resulting polymer-alloy fibre shows with the result of tem observation, does not contain the polymer particle of thick cohesion, and the area ratio on whole relatively islands, island that diameter 200nm is above is 1.0%.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 20 circle knitting after, it with 100 ℃ of hot-water cure 1 hour, is removed the hot water solubility's polymkeric substance more than 99%, obtain the round pin fabric products of making by PMP nanoporous fiber.
The fiber longitudinal section tem observation result of this PMP nanoporous fiber shows that these pores are separate wells, and its mean diameter is 35nm, and the above big pore of diameter 50nm is 0.6% to the area ratio of whole pores.The rerum natura of nanoporous fiber is shown in table 7.
Embodiment 28
With polyphenylene sulfide (following represent) with PPS as PET, with the N6 that uses among the embodiment 1 as hot water solubility's polymkeric substance, the ratio of mixture of PPS is 90 weight %, carries out melting mixing for 305 ℃ in melt temperature similarly to Example 20.The temperature of fusing department 2 is decided to be 305 ℃, and spinning temperature is decided to be 305 ℃, changes single hole spray volume and nozzle hole count, carries out melt-spinning similarly to Example 20, and fracture of wire is 2 times during 24 hours continuous spinnings.In addition, the 1st heat roller temperature 24 is 90 ℃, stretches similarly to Example 10, thermal treatment.Obtain the polymer-alloy fibre of 150dtex, 48 threads.The fiber cross sections of resulting polymer-alloy fibre shows with the result of tem observation, does not contain the polymer particle of thick cohesion, and the area ratio on whole relatively islands, island that diameter 200nm is above is 1.5%.In addition, show that from fiber longitudinal section tem observation the island is list structure.In addition, Si good rerum natura is shown in table 8.
This polymer-alloy fibre carry out similarly to Example 20 circle knitting after, it was handled 2 hours with formic acid, remove the N6 more than 99%, obtain the round pin fabric products of making by PPS nanoporous fiber.At this moment, pore is a separate wells.The rerum natura of nanoporous fiber is shown in table 7.
Table 7
Average pore diameter (nm) Thick pore area is than 1 (%) Thick pore area is than 2 (%) Intensity (cN/dtex) Color emissivity
Embodiment 19 embodiment 20 embodiment 21 embodiment 22 embodiment 23 embodiment 24 embodiment 25 embodiment 26 embodiment 27 embodiment 28 Below 20 20 20 20 20 20 38 32 35 50 0 0 0 0 0 0 0 0 0 1.4 0 0 0 0 0 0 0.8 0.6 0.6 - 2.2 2.0 2.0 2.0 2.0 2.0 1.8 1.5 1.7 3.6 ◎ ◎ ◎ ◎ ◎ ◎ - - - -
Average pore diameter: by the average pore diameter of tem observation estimation
Thick pore area is than 1: the area ratio of the whole relatively fibers of pore that diameter 200nm is above
Thick pore area is than 2: the area ratio of the whole relatively fibers of pore that diameter 500nm is above
Table 8
The sea polymkeric substance The island polymkeric substance Sea/island viscosity ratio The method of mixing Area is than (%) Island mean diameter (n m) Spinnability Intensity (cN/d tex) U％ ( ％) Percent thermal shrinkage (%)
Kind wt ％
Embodiment 19 embodiment 20 embodiment 21 embodiment 22 embodiment 23 embodiment 24 embodiment 25 embodiment 26 embodiment 27 embodiment 28 N66 PET7 PET8 PTT PBT PLA PP PMMA PMP PPS 80 80 80 80 80 80 80 80 80 90 PET1 PA0 PA0 PA0 PA0 PA0 PA0 PA0 PA0 N6 0.9 0.9 1.0 1.4 0.6 0.6 1.0 1.0 1.0 1.0 Static EXT EXT EXT EXT EXT EXT EXT EXT EXT 0.1 following below 0.1 below 0.1 below 0.1 below 0.1 below 0.1 1.2 0.8 1.0 1.5 33 40 38 34 45 35 40 35 38 52 ○ ○ ○ ○ ○ ○ ○ ○ ○ △ 4.1 3.3 3.4 3.1 3.1 2.9 2.7 2.5 2.6 5.3 1.2 1.5 1.5 1.7 1.8 1.8 2.2 2.4 2.3 2.1 13 7 9 10 9 9 6 - 9 -
Area ratio: the area ratio on the whole relatively islands of thick cohesion polymer particle that diameter 200nm is above;
PET7: homogeneous PE (η=0.63);
The copolymerization PET of the PEG1000+ m-phthalic acid 7mol% of PET8:8wt%;
PA0: polyalkylene oxide modifier (hot water resolvability polymkeric substance);
EXT: twin shaft is extruded muller;
Static: static muller (1,040,000 divide).
Embodiment 29
Change nozzle hole count and spray volume, carry out melt-spinning similarly to Example 1, carry out draw false twisting processing, obtain the N6/ copolymerization PET alloy false twist yarn of 95dtex, 68 threads.Obtain the good rerum natura of intensity 2.7cN/dtex, degree of stretching 22%, percent thermal shrinkage 8%, U%10%, CR38% thus, do not have backtwisting not, curling quality is also good.The crimped filament transverse section of resulting polymer-alloy fibre shows with the result of tem observation, N6 is the island structure of island (light part) for sea (dense part), copolymerization PET, the mean diameter on island is 25nm, obtains the polymer-alloy fibre of copolymerization PET superfineization.Relatively all the area on islands is than below 0.1% on diameter 200nm above island, and the above area of diameter 100nm is than below 0.9%.In addition, the island is the strip dispersion.As the shell silk, the polyurethane fiber silk made from オ プ ロ Application テ Star Network ス (strain) " ラ イ Network ラ " (registered trademark) covers with it.In addition, adopt this covering silk to make the knitted fabrics that tights uses after, carry out alkaline purification similarly to Example 1, make the knitted fabrics that the tights that is made of N6 nanoporous fiber is used.The order of the knitted fabrics that this tights is used is paid and is 100g/m 2The weight ratio of N6 nanofiber and polyurethane fiber silk is respectively 95% and 5%.It is carried out polysiloxane processing, breaking processing.Then, make the knitted fabrics that this tights is used, make tights.Extract N6 nanoporous fiber out from this tights, show that with the tem observation result pore thick more than the diameter 50nm does not all have, the mean diameter of pore is 25nm.In addition, pore is a separate wells.Silk intensity is 2.5cN/dtex.The color emissivity of this tights is good, and Δ MR is up to 5.6%, and the very thin tights demonstration and the moistening tender and lovely feel of human body skin are worn as snug as a bug in a rug.By using with, not only give big elasticity, and the morphological stability during the tights washing is improved also with the polyurethane fiber silk.
Embodiment 30
The polymer-alloy fibre that adopts embodiment 6 to make covers with embodiment 28 same " ラ イ Network ラ ".Make trunks with this silk.Extract N6 nanoporous fiber out from these trunks, show that with the tem observation result pore thick more than the diameter 50nm does not all have, the mean diameter of pore is 25nm.In addition, pore is a separate wells.Silk intensity is 2.5cN/dtex.The color emissivity of these trunks is also good, and △ MR is up to 5.6%, and the very thin tights demonstration and the moistening tender and lovely feel of human body skin are worn as snug as a bug in a rug.The ammonia of these trunks smelly rate that disappears is 55%.By using with, not only give big elasticity, and the morphological stability during the tights washing is improved also with the polyurethane fiber silk.
Embodiment 31
Change single hole spray volume and hole count, carry out melt-spinning similarly to Example 1, obtain the N6/ copolymerization PET alloy fiber of 400dtex, 96 threads.The intensity of this polymer-alloy fibre is 2.5cN/dtex, degree of stretching 100%, U%1.2%.The fiber cross sections of the high directed undrawn yarn of resulting polymer-alloy fibre shows with the result of tem observation, the polymer particle of no thick cohesion, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, area ratio more than the diameter 100nm is below 1%, and the mean diameter on island is 33nm.In addition, adopt the device of Figure 29, similarly to Example 6 it is implemented draw false twisting processing, obtain the false twist yarn of 333dtex, 96 threads.The intensity of resulting false twist yarn is 3.0cN/dtex, degree of stretching 30%, U%1.5%, CR33%.The fiber cross sections of resulting polymer alloy crimped filament shows with the result of tem observation, the polymer particle that does not contain thick cohesion, the area on whole relatively islands, island that diameter 200nm is above compares below 0.1%, and diameter 100nm compares below 0.1% with area.In addition, the mean diameter on island is 27nm, and the island is list structure.
This false twist yarn is implemented weak twist with 300 commentaries on classics/m, twist with the fingers mariages as warp and parallel, make 2/2 twilled fabric with S sth. made by twisting/Z.Then, the twilled fabric that obtain are carried out alkaline purification similarly to Example 6, obtain paying and be 150g/m by the order that N6 nanoporous fiber constitutes 2The curtain fabric.Extract N6 nanoporous fiber from this curtain out with fabric, show that with the tem observation result pore thick more than the diameter 50nm does not all have, the mean diameter of pore is 25nm.In addition, pore is a separate wells.Silk intensity is 2.5cN/dtex.
The color emissivity of this curtain is good, and rate of moisture absorption (Δ MR) shows sufficient water absorbability up to 5.5%.Then, make curtain with this material, the result who is hung between 6 straw mats is the dewfall that can suppress by high-hygroscopicity, because it destroys foul odors, can obtain salubrious indoor environment.Therefore, nanoporous fiber of the present invention is suitable for making the indoor loading and unloading goods of regulating original environment and forming the environmental response type.This curtain can be put into Washing net and wash, dewaters and do not deform with the home washings machine, and is different with the curtain of artificial silk system, shows that existing high moisture absorption, high-hydroscopicity have good morphological stability again.
Embodiment 32
Change single hole spray volume and hole count, squit hole is the Y type, carries out melt-spinning similarly to Example 10.Spin silk and divide with 900m/ and draw, secondly, be 1.3, carry out 2 sections stretchings under the condition of 3.5 times of total multiplying powers at the 1st section stretching ratio, again with nozzle give curl after, the bulk processing thread of batching 500dtex, 90 threads, 9/25mm of number of crimp.The intensity of this is bulk processing silk is 5.0cN/dtex, degree of stretching 25%.The fiber cross sections of resulting polymer alloy crimped filament shows with the result of tem observation, do not contain thick cohesion polymer particle, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, and the area ratio more than the diameter 100nm is below 1%.In addition, the mean diameter on island is 30nm, shows list structure.
Resulting bulk processing silk is taken out 2 Gen Laqi carry out plying, following sth. made by twisting (200T/m) is gone up sth. made by twisting (200T/m) with its 2, twisted joint, in xeothermic 170 ℃ twist with the fingers solid processing after, make the fancy wool yarn as the clipping woollen blanket with known method.
At this moment, adopt the cutting of common level, regulate stitch and make the fancy wool yarn, make reach 1/10 pin, order is paid 1500g/m 2Then, reinforce.When making the fancy wool yarn, the base cloth that uses the blended ratio of acrylic fibers peacekeeping trevira to knit as base cloth.In addition, only alkaline purification is partly carried out in clipping, clipping partly presents the structure that is made of N6 nanoporous fiber.The result of its observation is shown that the above thick pore of diameter 50nm does not all have with TEM, the mean diameter of pore is 30nm, and pore is a separate wells.In addition, extract clipping out, mensuration intensity is 2.0cN/dtex.The color emissivity of this clipping part is good, and △ MR shows sufficient water absorbability up to 5.3%.Same with the curtain of embodiment 31, can obtain lucid and lively indoor environment.
Embodiment 33
Change single hole spray volume and hole count, carry out spinning similarly to Example 10.Behind the 1st take off roll 8 traction fibers, carry out plying, be placed on the feed bin.Secondly, the strand of placing on the feed bin is carried out plying once more, make the tow of 140,000 dtex.It is stretched 3.2 times in 90 ℃ of tanks.By oil supply behind the crimper, cutting.Resulting cutting fibre, filament number are 4dtex, 10/25mm of number of crimp, staple length 51mm.The intensity of this cutting fibre is that 3.3cN/dtex, degree of stretching are 40%.These fiber cross sections show with the result of tem observation, do not conform to the polymer particle of thick cohesion, and relatively all the area on islands is than below 0.1% on diameter 200nm above island, and the area on the island that diameter 100nm is above is than below 1%.In addition, the mean diameter on island is 33nm, shows list structure.
After dividing comb this cutting fibre with cotton card, make web with intersection web machine (Network ロ ス ラ Star プ ウ エ one バ one).Carry out acupuncture (1500 times/cm then 2), make 150g/m 2Fiber complexing non-woven fabrics.Resulting non-woven fabrics carries out alkaline purification similarly to Example 10, obtains N6 nanoporous fabric nonwoven cloth.Take out the nanoporous fiber samples from this non-woven fabrics, with TEM the result of its observation is shown, the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is 30nm, and pore is a separate wells.In addition, the cutting fibre alkaline purification, the sample strength after the mensuration nanofiberization is 2.0cN/dtex.The color emissivity of this non-woven fabrics is good, and Δ MR=5.5% shows sufficient water absorbability.
Embodiment 34
The cutting fibre that the polymer alloy of making among the embodiment 33 is constituted spins, and obtains the polymer alloy spun yarn.Used as organizine and tram, obtain order and pay 150g/m 2Flat fabric.Then, carry out alkaline purification similarly to Example 10, obtain N6 nanoporous fiber fabric.Take out the nanoporous fiber samples from this cloth and silk, with TEM the result of its observation is shown, the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is 30nm.In addition, pore is a separate wells.In addition, extracting nanoporous fiber spun yarn mensuration intensity out from this cloth and silk is 2.0cN/dtex.The color emissivity of this cloth and silk is good, and Δ MR=5.8% shows sufficient water absorbability, and color emissivity is also good.
Embodiment 35
Carry out spinning similarly to Example 25, draw strand, make it open fibre, after capturing with reticulation, start polishing machine, obtain paying 35g/m by the order that polymer-alloy fibre constitutes with getter device 2Non-woven fabrics.Fibre single thread fiber number with the air suction pipe traction is 2dtex, and the spinning speed of obtaining from fiber number is equivalent to the 4500m/ branch.Take out polymer-alloy fibre from this non-woven fabrics, the result who fiber cross sections is observed with TEM shows, do not contain thick cohesion polymer particle, the area ratio on whole relatively islands, island that diameter 200nm is above is below 0.1%, and the area on the island that diameter 100nm is above ratio is also below 1%.In addition, the mean diameter on island is 31nm, shows list structure.
This non-woven fabrics is carried out hot-water cure similarly to Example 24, obtain PP nanoporous fabric nonwoven cloth.Its water-absorbent is good.Extract the nanoporous fiber samples out from this non-woven fabrics, with TEM the result of its observation is shown, the above thick pore of diameter 50nm does not all have, and pore is a separate wells, and its mean diameter is 30nm.Therefore, nanoporous fiber of the present invention, it is suitable being used to make the high-performance non-woven fabrics that does not have before this.
Embodiment 36
Change spray volume and nozzle hole count, carry out melt-spinning similarly to Example 1, obtain 90dtex, 68 threads, intensity and be the high directed undrawn yarn that the polymer alloy of 2.7cN/dtex, degree of stretching 100%, U%1.3% constitutes, batch with 10kg.This polymer-alloy fibre transverse section shows with the result of tem observation, the mean diameter of copolymerization PET is 20nm, with the nano-scale homodisperse, compare below 0.1% the area on whole islands on the thick island more than the diameter 200nm, and the area on the island that diameter 100nm is above ratio is at (Figure 27) below 1%.Carry out result's demonstration that longitudinal section is observed, copolymerization PET is a list structure.
This packing timber is that end face expands, and the good packing timber shape of ear-piercing (ear founds Chi) or skips does not take place.Because different suction swellings with common nylon fiber are suppressed, thus do not take place packing timber through the time destruction, the morphological stability of packing timber is good.Because the high directed undrawn yarn of common nylon, suction swelling during batching and silk is extended is so can not be stable batch can not obtain the packing timber that the high directed undrawn yarn by degree of stretching 70～200% constitutes.Therefore, can not carry out composit false twisting processing etc. with PET, but adopt nylon polymer alloy fiber of the present invention, can stablize the high orientation of batching degree of stretching 70～200% comes drawn yarn, so, have the advantage that can carry out various silk processing.
Comparative example 8
Adopt the N6 that adopts among the embodiment 1 separately, carry out melt-spinning equally with embodiment 36.Yet, because suction swelling in batching makes the silk elongation, to batch so can not stablize, the spalling of silk frequently takes place.
Embodiment 37
The high directed undrawn yarn that obtains among the embodiment 36 and the 70dtex of approach preparation in addition, the common N6 drawn yarn (intensity is that 6cN/dtex, degree of stretching are 45%) of 34 threads are carried out composit false twisting.At this moment, 1.02 times of stretching ratios, 165 ℃ of heater temperatures.Adopt the composit false twisting silk of resulting CR25%, similarly to Example 1, make tubular knitted goods, carry out alkaline purification.
Extract N6 nanoporous fiber from resulting tubular knitted goods out, with result's judgement of tem observation, the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is the scope of 10-20nm, and silk intensity is 2.5cN/dtex.In addition, pore is a separate wells.The color emissivity of this cloth and silk is also good, and Δ MR also is 4.5%, shows sufficient water absorbability.In addition, its is soft and have a good feel that touches up very very thin.Therefore, by polymerization au-alloy fiber of the present invention and other fiber blended, as can to obtain having good hand best cloth and silks that are suitable for doing dress material.
When particularly adopting nylon, owing to can not get the high directed undrawn yarn of high ductility originally, so feel is restricted, but that works obtains the cloth and silk of good hand easily as embodiment among the present invention.
Embodiment 38
The common N6 fiber of the polymer-alloy fibre of making among the embodiment 13 and 70dtex, 96 threads, carry out with the nozzle that interweaves that gas is mixed to be knitted.Adopt it as organizine and tram, make order and pay 150g/m 2Flat fabric and is implemented 10 to carry out alkaline purification equally, obtains the cloth and silk that is made of N6 nanoporous fiber and common N6 thus.
Result with this N6 nanoporous fiber of tem observation shows that the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is the scope of 10-20nm, and silk intensity is 3.3cN/dtex.In addition, pore is a separate wells.The color emissivity of this cloth and silk is also good, and Δ MR also is 4%, shows sufficient water absorbability.In addition, its is soft and have a good feel that touches up very very thin.
Embodiment 39
The polymer alloy crimped filament that obtains among the embodiment 1 as organizine, as the viscose rayon tram, is made 2/2 Dou pattern fabric to 72dtex, 27 threads, order is paid reached 150g/m 2With its with implement 1 to carry out alkaline purification equally.
From the cloth and silk that obtains, to extract N6 nanoporous fiber out and show that with the tem observation result the above thick pore of diameter 50nm does not all have, the mean diameter of pore is below the 20nm, silk intensity is 2.5cN/dtex.In addition, pore is a separate wells.The color emissivity of this cloth and silk is also good, and Δ MR also is 7%, shows sufficient water absorbability.In addition, its is soft and have a good feel that touches up very very thin.Therefore, fiber blended by nanoporous fiber of the present invention and other, make feel and water absorbability higher, be suitable for the cloth and silk that senior dress material is used most.
Embodiment 40
Polymer alloy cutting fibre that obtains among the embodiment 33 and cotton are carried out blending with weight ratio 50%/50%, obtain containing the blended ratio of polymer-alloy fibre.With it and embodiment 34 same plain weaves, and implement 1 and carry out alkaline purification equally.The color emissivity of this cloth and silk is also good, and Δ MR=4.8% show sufficient water absorbability, and color emissivity is also good.
From the cloth and silk that obtains, extract the spun yarn that contains N6 nanoporous fiber out, the result who measures intensity is 2.0cN/dtex.Show with the tem observation result that from the sampling of N6 nanoporous fiber the above thick pore of diameter 50nm does not all have, the mean diameter of pore is 30nm.Pore is a separate wells.
Embodiment 41
In the cloth and silk that the PET nanoporous fiber of making in embodiment 20 constitutes, with bath raio 1: 40,130 ℃ of treatment temps, 1 hour treatment time triphenyl phosphoric acid exhaustion as the 20%owf (by fabric weight) of fire retardant.Then, after its washing, soap with aqueous sodium carbonate (80 ℃).Home washings is 10 times again.The adhesion amount of this moment is 7%, and the result who estimates of burning shows good fire extinguishing certainly.Therefore, nanoporous fiber of the present invention is because intake function material easily, and can be encapsulated, so can improve washing resistance, is suitable for most processing as function and uses precursor.
Comparative example 9
To common PET cloth and silk, with the fire-retardant processing of embodiment 41 same enforcements.With its adhesion amount that washs after 10 times is 1 weight %, and the result who estimates of burning does not show from fire extinguishing property.
Embodiment 42
In the cloth and silk that the PET nanoporous fiber of making in embodiment 20 constitutes, ' SR1000 ' (10% water-dispersion product) of making as the high terebinth (strain) of moisture adsorbent are exhausted.The processing conditions of this moment: moisture adsorbent solids component 20% (by fabric weight), bath raio 1: 20,130 ℃ of treatment temps, 1 hour treatment time.Obtain the exhaustion rate more than 12%, more than the Δ MR=4%, have cotton equal or above good hygroscopic PET cloth and silk.Therefore, nanoporous fiber of the present invention is because intake function material easily, and can form encapsulated structure, so can improve the exhaustion rate of functional mass, is suitable for most processing as function and uses precursor.
Comparative example 10
To common PET cloth and silk, with embodiment 42 same enforcement moisture absorption processing, the exhaustion rate of moisture adsorbent almost is zero, does not also find water absorbability.
Embodiment 43
In the cloth and silk that the PET nanoporous fiber that makes constitutes, contain the natural oil composition of from the liver of shark, extracting out in embodiment 20, make to exhaust the squalane that has the skin care effect because of preserving moisture.The treatment condition of this moment: squalene 60% and emulsifying dispersant 40% be the blended material in addition, rises with concentration 7.5g/ and disperse bath raio 1: 40,130 ℃ of temperature, 60 minutes treatment times in water.After the processing, in 80 ℃ of washings 2 hours, the squalene adhesion amount of this moment was 21 weight % to cloth and silk.Then, the squalene adhesion amount after the home washings 20 times is 12 weight % to cloth and silk, shows sufficient washing resistance.
The tubular knitted goods that adopts the nanoporous fiber of the PET that this squalene is processed into to constitute is made socks, and the result who is being worn the test of 1 week by dry serious trier 10 people of heel is that dry skin obtains mitigator 8 people.This is because the squalene testee's who captures in the pore sweat is slowly extracted the back out with due to the skin contact.
Comparative example 11
To common PET cloth and silk and the embodiment 43 same exhaustions processing of implementing squalenes, the result is that the relative cloth and silk of adhesion amount after the washing reaches 21 weight %, but the adhesion amount after the home washings 10 times is 0 weight %, does not have washing resistance fully.
Embodiment 44
The N6 nanoporous fiber fabric that makes among the embodiment 10 is immersed in the ion exchanged water, then, adds 1, two (trimethoxysilyl) ethane of 2-stirred 3 hours.Restir is 13 hours after room temperature is placed 14 hours, leaves standstill 14 hours restir 7 hours, polymerization silica again in room temperature.Then, tubular knitted goods is done with ion-exchange water washing after wind.By this operation, cast out N6 nanoporous fiber pore, obtain the N6/ silica composite material of cloth and silk shape.This is the quality matetrial that sufficient rigidity and flexibility have concurrently.In addition, also be mixing material with excellent flame retardancy.In addition, the ratio of silica is 30 weight % in this complex body.
Therefore, nanoporous fiber of the present invention makes their polymerizations after exhausting certain monomer that polymerizability is arranged or oligopolymer, is easy to as matrix material.Therefore, optimum usefulness acts on obtain the having inorganic functional organic materials of (flame retardant resistance, catalysis) or the precursor with tip materials such as inorganic materials of flexibility.
Embodiment 45
The tights of making among the embodiment 29 that is made of N6 nanoporous fiber is immersed in " the new Port リ カ イ Application liquid " of roc medicine society manufacturing, carries out drying.Obtain to come by sweat the tights of stripping pompholyx medicine thus.This tights by pompholyx patient dress, is more renewed tights every day.Continuously it was being worn 1 month, owing to slowly discharge pompholyx medicine, doing well,improving.Therefore, nanoporous fiber of the present invention is owing to have the slow-release capability of effective component, pretend for medical articles be suitable.
Embodiment 46
The cloth and silk that the N6 nanoporous fiber that makes among the embodiment 1 is constituted in 50 ℃ of dippings 1 minute, makes the N6 nanoporous fiber-loaded in diethylenetriamine in the aqueous solution of diethylenetriamine 3%.It is that benchmark is estimated with ammonia that its acetyl formaldehyde is removed ability, and the result is that concentration reduces 1ppm from 30ppm in 10 minutes, shows the good ability of removing.Therefore, because nanoporous fiber of the present invention has the sorbent-loaded ability, so, be suitable as industry material products such as chemical filter or gas filters.
Embodiment 47
The polymer alloy of making among the embodiment 1 as the core composition, as shell component, after 270 ℃ of fusions, is spun into core shell composite filament to the N6 that adopts among the embodiment 1 with 275 ℃ of spinning temperatures, divides traction, obtain high directed undrawn yarn with 3800m/.It is implemented draw false twisting similarly to Example 1.Here, the compound ratio of polymer alloy is decided to be 80 weight %.The performance of the crimped filament that is made of the core shell conjugated fibre that obtains is: 150dtex, 76 threads, intensity 4.1cN/dtex, degree of stretching 27%, U%1.0, percent thermal shrinkage 10%, CR45%.In addition, mean diameter as the island copolymerization PET in the polymer alloy of shell component is 26nm, with the nano-scale homodisperse, compare below 0.1% the area on whole islands on the thick island more than the diameter 200nm, and compare below 1% the area on whole islands on the thick island more than the diameter 100nm.The island polymkeric substance disperses with strip.The crimped filament that adopts resulting core shell conjugated fibre to constitute here similarly to Example 1, is made tubular knitted goods, carries out alkaline purification, obtains the tubular knitted goods that is made of N6 nanoporous fiber.
From wherein extracting N6 nanoporous fiber out, with the result of tem observation be, the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is 20nm.The area of nanoporous part is 77% of a fiber cross sections.In addition, the silk intensity of nanoporous fiber is 3.3cN/dtex, is in a ratio of high strength with embodiment 1, and the antifriction consumption might as well.And pore is a separate wells.This cloth and silk is compared with embodiment 1 has distinct color emissivity, and Δ MR also is 4.5%, shows sufficient water absorbability.
Embodiment 48
Core composition and shell component are exchanged, the polymer alloy ratio is 50 weight %, operate equally with embodiment 47, make core shell composite filament, implement draw false twisting, obtain the crimped filament that the core shell conjugated fibre by 150dtex, 76 threads, intensity 4.1cN/dtex, degree of stretching 27%, U%1.0%, percent thermal shrinkage 10%, CR45% constitutes.In addition, mean diameter as the island copolymerization PET in the polymer alloy of shell component is 26nm, with the nano-scale homodisperse, compare below 0.1% the area on whole islands on the thick island more than the diameter 200nm, and compare below 1% the area on whole islands on the thick island more than the diameter 100nm.In addition, the island polymkeric substance disperses with strip.Here, the crimped filament that adopts resulting core shell conjugated fibre to constitute, same with embodiment 47, make tubular knitted goods, carry out alkaline purification, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber.From wherein extracting N6 nanoporous fiber out, with the result of tem observation be, the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is 20nm.The area of nanoporous part is 45% of a fiber cross sections.In addition, the nanoporous fibre strength is 3.5cN/dtex, is in a ratio of high strength with embodiment 1.In addition, pore is a separate wells.The color emissivity of this cloth and silk, Δ MR is 4%, shows sufficient water absorbability.
Embodiment 49
The independent side of N6 is made parallel type with the material that embodiment 1 makes with the compound ratio of 50 weight %/50 weight % with the high viscosity N6 that adopts among the embodiment 14, polymer alloy side, operates equally with embodiment 48, carries out conjugate spinning.At this moment, the viscosity of high viscosity N6 is more than 2 times of polymer alloy viscosity.Resulting undrawn yarn with 1.2 times of operations similarly to Example 10 of stretching ratio, is implemented stretching thermal treatment.Obtain the crimped filament arranged side by side of 110dtex, 34 threads, intensity 4.1cN/dtex, degree of stretching 27%, U%1.2%, percent thermal shrinkage 10%, 20/25mm of number of crimp.In addition, mean diameter as the island copolymerization PET in the polymer alloy of the outer lateral element that curls is 26nm, with the nano-scale homodisperse, on the other hand, compare below 0.1% the area on whole islands on thick island more than the diameter 200nm, and compare below 1% the area on whole islands on the thick island more than the diameter 100nm.In addition, the island polymkeric substance disperses with strip.Adopt resulting crimped filament arranged side by side here, same with embodiment 48, make tubular knitted goods, carry out alkaline purification, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber.From wherein extracting N6 nanoporous fiber out, with the result of tem observation be, the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is 20nm.The area of nanoporous part is 44% of a fiber cross sections.In addition, silk intensity is 3.5cN/dtex, is high strength.In addition, pore is a separate wells.The color emissivity of this cloth and silk, Δ MR is 4%, shows sufficient water absorbability.When this cloth and silk Xi Shui Time bulkiness higher.
Embodiment 50
The independent side of N6 is operated with embodiment 49 with the material that embodiment 14 makes equally with the low viscosity N6 that adopts among the embodiment 1, polymer alloy side, carries out conjugate spinning, stretching thermal treatment.Obtain the crimped filament arranged side by side of 110dtex, 34 threads, intensity 4.0cN/dtex, degree of stretching 25%, U%1.2%, percent thermal shrinkage 10%, 18/25mm of number of crimp.
Disperse with mean diameter 18nm as the island copolymerization PET in the polymer alloy of lateral element in curling, the above thick island of diameter 100nm to the area on whole islands than below 0.1%.Adopt resulting crimped filament arranged side by side here, same with embodiment 49, make tubular knitted goods, carry out alkaline purification, obtain the tubular knitted goods that constitutes by N6 nanoporous fiber.
From wherein extracting the nanoporous fiber out, with the result of tem observation be, the above thick pore of diameter 50nm does not all have, and the mean diameter of pore is 20nm.In addition, the area of nanoporous part is 45% of a fiber cross sections.In addition, the nanoporous fiber has sufficient bulkiness, and silk intensity 3.4cN/dtex is high strength.In addition, pore is a separate wells.The color emissivity of this cloth and silk, Δ MR is 4%, shows sufficient water absorbability.As this cloth and silk suction water Time, crimp extension, braiding mesh enlarge, and air permeability is higher.
Embodiment 51
The tubular knitted goods of the polymer-alloy fibre manufacturing that obtains among the embodiment 10, handled 20 minutes with 2% aqueous sodium hydroxide solution (95 ℃, bath raio 1: 40), make 50% of copolymerization PET in the polymer-alloy fibre decompose stripping (weight-loss ratio as fiber is 10%).Stripping is to carry out annularly from the fiber top layer, and nanoporous portion reaches 50% to fiber cross sections.This part result of tem observation, pore is a separate wells, and its mean diameter is 20nm, and the above thick pore of diameter 50nm does not all have.
This tubular knitted goods shows the good moisture absorption adsorptivity that Δ MR is 4%, ammonia disappears smelly rate=50%.In addition, water retention is abundant, reaches 60%.This nanoporous fiber also shows the reversible water-swellable, and the swelling rate is 4%, compares the dimensional stability height of Peng Run Time with embodiment 10.In addition, silk intensity 3cN/dtex compares higher with embodiment 10.
Embodiment 52
Adopt the polymer alloy crimped filament of making among the embodiment 1 as organizine and tram, make 170g/m 2The high-density flat fabric.Similarly to Example 1 it is carried out alkaline purification, make the flat fabric of making by N6 nanoporous fiber.From wherein extracting the nanoporous fiber out, measure the form transitivity, obtain value similarly to Example 1.It is implemented polished finish, make nanoporous fiber top layer fibrillation, generate the protofibril about many Fibre diameter 0.01～1 μ m, cover fiber surface.Thus, not only can obtain softness and the feel of silk sense arranged, even and be not coated with hydrophobic in naturely yet, be suitable as the Sportswear cloth and silk.
Comparative example 12
Adopt common N6 false twist yarn (77dtex, 34 threads), make the high-density flat fabric equally with embodiment 51, it is implemented polished finish, fibrillation is insufficient, and protofibril does not cover fiber surface, can not get softness and has the feel of silk sense.In order to carry out fibrillation, when carrying out Pao Guang Chu Li Time, cloth and silk breaks.
Embodiment 53
Adopt the polymer alloy crimped filament of making among the embodiment 1 as tram, adopt common N6 fiber (44dtex, 12 threads), to make 180g/m as organizine 25 the inside satin fabrics.Similarly to Example 1 it is carried out alkaline purification, make the inside satin fabric of making by N6 nanoporous fiber.From wherein extracting the nanoporous fiber out, measure the form transitivity, obtain value similarly to Example 1.It is implemented polished finish, make nanoporous fiber top layer fibrillation, generate the protofibril about many Fibre diameter 0.01～1 μ m, the covering fabric surface.Then, it is implemented water bore processing, make protofibril further open fibre.It is suitable as the cloth for wiping or dusting cloth and silk.
Embodiment 54
The non-woven fabrics of being made by N6 nanoporous fiber that obtains among the embodiment 33 is implemented polished finish, still generate the protofibril about many Fibre diameter 0.01～1 μ m, cover nonwoven surface.It is unexistent to skin softish sense of touch that it has original nylon nonwoven fabrics.
Embodiment 55
The non-woven fabrics of being made by PP nanoporous fiber that obtains among the embodiment 35 is implemented polished finish, generate the protofibril about many Fibre diameter 0.01～1 μ m, cover nonwoven surface.It is the excellent material that is more suitable for strainer than original PP spun bond nonwoven fabric.
The possibility of utilizing on the industry
The porous fibre that the present invention makes, its fiber bodies or adopt the fiber structures such as silk, cotton, felt, packing timber or fibre of this fiber, these have than original liquid-absorbent and adsorptivity very fast growth effect have been arranged. Utilizing this nano-porous structure, can obtain these various functions in addition, is can be at the use De in each field Hua Time material in generation.
That is, because various functional mass enter the nanometer pore, process than function easy to implement with original Fiber Phase.
For example, can adopt the conducts such as moisture absorption section, fire retardant, hydrophober, NMF, cold-retaining agent, heat preserving agent or smooth agent to give object, perhaps, its proterties is not limited to acinous, can also add the medicament of the promotion health beauty treatments such as poly-phenol and amino acid, protein, capsicim, vitamins, or the skin disease medicament such as pompholyx (water worm) etc., in addition, can also add the pharmaceuticals such as disinfectant, antiinflammatory, analgestic.
Perhaps, the medicament that add to be used for again the adsorption-decomposition function of the harmful substances such as polyamine or photochemical catalyst nano particle in addition can be as required, after the monomer exhaustion that has the organic or inorganic polymer and form ability is adhered to, make their polymerizations, can lightheartedly make composite material etc. thus.
By applying flexibly its broad specific area, its pore wall is carried out chemical process make its activate and have the absorption of selection and catalysis, also be possible certainly.
As required, can lightheartedly have above-mentioned various function, therefore, not only can be implemented in the product that is suitable in the dress material purposes such as panty hose, tight, underwear, shirt, jacket, pants, overcoat, but also be applicable to the dress material material applications such as oversleeve or liner, or the life material product such as the interior decoration purposes such as curtain or carpet, cushion, furniture even cloth for wiping or dusting even the industry material applications such as abrasive cloth or filter cloth, vehicle interior decorative use etc., launch to use.
In addition, by adsorption function molecule or medicament etc., also can at the base cloth of health cosmetic dependent merchandise, pharmaceuticals, as the fiber construct of medical instruments, also can be used as the relevant most advanced materials'use of the environment such as electrode, medical science or IT (information communication) of fuel cell.
In this manual, " more than " expression " more than or equal to ", " following " expression " smaller or equal to ".

Claims (19)

1. a particle is the polymer alloy particle that is made of polymeric amide and polyester, it is characterized in that, the average dispersion diameter of dispersed polymeres is 1～50nm.
2. according to the described particle of claim 1, it is characterized in that in the particulate transverse section, being converted into circular diameter is the area ratio of the above thick dispersed polymeres of 100nm, is below 3% with respect to the whole dispersed polymeres in the particle transverse section.
3. a particle is the polymer alloy particle that is made of polymeric amide and polyester, it is characterized in that, it is 30～90 weight % that copolymerization has the ratio of mixture of the polyester of 1.5～15mol% sulfonate, and a particulate weight in average is 2～15mg.
4. according to claim 1 or 3 described particles, it is characterized in that the terminal base unit weight of amine is 6 * 10 -5Below mol equivalent/g.
5. particle, it is by being selected from polymeric amide, polyester, polyolefin polymers and having the polymer alloy particle that hot water solubility's polyether ester constitutes, it is characterized in that the ratio of mixture of polyether ester is 10～30 weight %, the b of chromogenic indicator as particulate *Value is below 10.
6. polymer-alloy fibre, it is characterized in that, the two or more polymkeric substance different by solvability constitute, the polymkeric substance that solvability is different in fiber cross sections has laminate structure, easily the mean thickness of solvability polymer layer is 1～100nm, as easy solvability polymer layer in the fiber longitudinal section is the laminate structure of list structure, has more than 50% in the unit surface of fiber cross sections.
7. according to the described polymer-alloy fibre of claim 6, it is characterized in that the blend level of island polymkeric substance is 10～30 weight % with respect to whole fibers.
8. according to the described polymer-alloy fibre of claim 6, it is characterized in that it is a conjugated fibre, this conjugated fibre is bonded with polymer alloy and the polymkeric substance beyond it.
9. a fibre product is characterized in that, this fibre product has the described polymer-alloy fibre of a part of claim 6 at least.
10. according to the described fibre product of claim 9, it is characterized in that fibre product is fabric, knitted fabrics or non-woven fabrics.
11. a multiporous fiber has the following pore of diameter 100nm, it is characterized in that, diameter is that the area ratio that the above pore of 200nm accounts for whole fiber cross sections is below 1.5%, and pore exists as communicating aperture, and intensity is more than the 1.0cN/dtex.
12., it is characterized in that the area ratio that the above pore of diameter 50nm accounts for whole fiber cross sections is below 0.1% according to the described multiporous fiber of claim 11.
13., it is characterized in that the mean diameter of pore is 5～30nm according to the described multiporous fiber of claim 11.
14., it is characterized in that the part of multiporous fiber is by fibrillation according to the described multiporous fiber of claim 11, this fibriilar diameter is 0.001～5 μ m.
15. according to the described multiporous fiber of claim 11, it is characterized in that, contain 80 weight % above polyester or polymeric amide.
16., it is characterized in that nanoporous portion off-centre is present in the fiber cross sections according to the described multiporous fiber of claim 11, the area of nanoporous portion is more than 30% with respect to whole fiber cross sections.
17. a fibre product is characterized in that, has the described multiporous fiber of a part of claim 11 at least.
18. according to the described fibre product of claim 17, wherein, fibre product is fabric or knitted fabrics or non-woven fabrics.
19. according to the described fibre product of claim 17, it is characterized in that, contain functional substance.
CN 200710084713 2002-08-05 2003-07-28 Porous fiber Pending CN101003681A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102422470A (en) * 2009-07-08 2012-04-18 三菱丽阳株式会社 Porous electrode base material, and process for production thereof
CN103668535A (en) * 2012-09-19 2014-03-26 东丽纤维研究所（中国）有限公司 Polyamide fiber, fabric containing polyamide fiber and production method
CN105247119A (en) * 2013-06-12 2016-01-13 金伯利-克拉克环球有限公司 Porous polyolefin fibers
CN105264128A (en) * 2013-06-12 2016-01-20 金伯利-克拉克环球有限公司 Multi-functional fabric
CN106574404A (en) * 2014-05-26 2017-04-19 株式会社可乐丽 Polyamide fibers, fiber structure using same, and clothing
CN106811815A (en) * 2015-12-02 2017-06-09 中国科学院化学研究所 A kind of porous polyolefin fiber containing micro-nano hole and its preparation method and application

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102422470A (en) * 2009-07-08 2012-04-18 三菱丽阳株式会社 Porous electrode base material, and process for production thereof
CN103668535A (en) * 2012-09-19 2014-03-26 东丽纤维研究所（中国）有限公司 Polyamide fiber, fabric containing polyamide fiber and production method
CN105247119A (en) * 2013-06-12 2016-01-13 金伯利-克拉克环球有限公司 Porous polyolefin fibers
CN105264128A (en) * 2013-06-12 2016-01-20 金伯利-克拉克环球有限公司 Multi-functional fabric
CN106574404A (en) * 2014-05-26 2017-04-19 株式会社可乐丽 Polyamide fibers, fiber structure using same, and clothing
CN106811815A (en) * 2015-12-02 2017-06-09 中国科学院化学研究所 A kind of porous polyolefin fiber containing micro-nano hole and its preparation method and application
CN106811815B (en) * 2015-12-02 2020-01-31 中国科学院化学研究所 porous polyolefin fibers containing micro-nano holes and preparation method and application thereof

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